KR20160117868A

KR20160117868A - Transparent conductor, method for preparing the same and optical display apparatus comprising the same

Info

Publication number: KR20160117868A
Application number: KR1020150045769A
Authority: KR
Inventors: 신동명; 김도영; 김영훈; 강경구
Original assignee: 삼성에스디아이 주식회사
Priority date: 2015-03-31
Filing date: 2015-03-31
Publication date: 2016-10-11
Also published as: KR101900538B1; WO2016159664A1

Abstract

The present invention is a transparent body comprising a base layer and a conductive layer formed on the base layer, wherein the conductive layer comprises metal nanowires and a matrix, the matrix comprising (A) a pentafunctional or hexafunctional urethane (meth) (B) a trifunctional (meth) acryl-based monomer, (C) a fluorine-based monomer, and (D) a nanosilica.

Description

TECHNICAL FIELD [0001] The present invention relates to a transparency, a method of manufacturing the same, and an optical display device including the transparent display. [0002]

The present invention relates to a transparent body, a method of manufacturing the same, and an optical display device including the same.

Transparency as a whole is used in various fields such as a touch screen panel and a flexible display included in a display device. Transparency The mainstream of transparency is the demand for transparent ITO films that have been deposited on PET films, as well as for the development of thin, lightweight and flexible displays. On the other hand, in order to make a large area touch panel, the patterned transparency of low resistance is required by the touch sensing accuracy and the reaction speed problem. However, it is difficult to satisfy both optical characteristics and low sheet resistance. It is necessary that the entire transparency to be applied to a large-area or high-performance touch panel in the future improves such a problem and has a light characteristic equal to or higher than the light characteristic at a high resistance even under a low resistance condition. In this connection, Japanese Laid-Open Patent Application No. 2012-011637 describes a transparent conductive film laminate including silver nanowires and a touch panel device including the same.

A problem to be solved by the present invention is to provide an entire transparency which is excellent in optical characteristics of haze, transmittance, and transmission b * with good low surface resistance and excellent in processability, reliability, durability and etching appearance with appropriate etching time.

Another problem to be solved by the present invention is to provide a method for manufacturing the entire transparency.

Another object of the present invention is to provide an optical display device including the entire transparency.

The transparent whole of the present invention is a transparent body including a base layer and a conductive layer formed on the base layer. The conductive layer includes metal nanowires and a matrix, and the matrix is composed of (A) a pentafunctional or hexafunctional urethane (Meth) acrylic oligomer, (B) a trifunctional (meth) acrylic monomer, (C) a fluorine-based monomer, and (D) nano-silica.

A method for producing a transparent body according to the present invention comprises the steps of: forming a metal nanowire network layer on a substrate layer; forming on the metal nanowire network layer (A) a pentafunctional or hexafunctional urethane (meth) acrylic oligomer, (Meth) acrylic monomer, (C) a fluorine-based monomer, and (D) a nanosilica.

The optical display device of the present invention may include all of the above transparency.

The present invention provides a transparent body having a low sheet resistance, good optical characteristics of transmittance, haze and transmission b *, excellent reliability, durability and excellent etching appearance, a method of manufacturing the transparent body, and an optical display device including the transparent body as a whole.

1 is a cross-sectional view of a transparent body according to an embodiment of the present invention.
2 is a cross-sectional view of a transparent body according to another embodiment of the present invention.
3 is a cross-sectional view of a transparent body according to another embodiment of the present invention.
4 is a cross-sectional view of the entire transparency of another embodiment of the present invention.
5 is a cross-sectional view of an optical display device according to an embodiment of the present invention.
6 is a cross-sectional view of a display portion of an embodiment of the present invention.
7 is a cross-sectional view of an optical display device according to another embodiment of the present invention.
8 is a cross-sectional view of an optical display device according to still another embodiment of the present invention.

The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification. In this specification, 'upper' and 'lower' are defined with reference to the drawings, and 'upper' may be changed to 'lower' and 'lower' may be changed to 'upper' depending on viewing time. Also, 'on' may be 'upper' or 'lower' depending on the case. As used herein, '(meth) acrylic' may mean acrylic and / or methacrylic.

As used herein, the term " oligomer " means that the number of repeating units is 2 or more, and the weight average molecular weight is 10,000 or less.

In the present specification, the 'rate of change in resistance' is a value obtained by sequentially laminating a transparent adhesive film (3M company, Optically Clear Adhesives 8215) and a PET film having a thickness of 100 탆 (Toyobo, A4300) After the sample was prepared, the prepared sample was measured for the initial sheet resistance (a) by a noncontact method using a non-contact type sheet resistance measuring device EC-80P (NAPSON), and left for 240 hours at a temperature of 85 캜 and a relative humidity of 85% And then measuring the sheet resistance (b) in the same manner, the resistance change rate calculated by the following equation (1).

[Formula 1]

Resistance change rate = b-a / a x 100

Hereinafter, the transparency of an embodiment of the present invention will be described with reference to FIG.

Referring to FIG. 1, a transparent body 100 of the present embodiment includes a base layer 110, and a conductive layer 120 formed on a base layer 110.

The substrate layer 110 may be a film having transparency and having a total light transmittance of 85% to 100%, for example, 90% to 99%. Also, the substrate layer 110 may be a film having a refractive index of from about 1.5 to about 1.65. The optical characteristics of the entire transparency can be improved in the above range.

Specifically, the base layer 110 may be a flexible insulating film. For example, polyesters such as polycarbonate, cyclic olefin polymer, polyethylene terephthalate (PET), polyethylene naphthalate and the like, polyolefine, poly But are not limited to, polysulfone, polyimide, silicone, polystyrene, polyacryl, and polyvinylchloride, and the like. These may be used alone or in combination of two or more.

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 from 10 占 퐉 to 200 占 퐉, specifically from about 30 占 퐉 to about 150 占 퐉, from 40 占 퐉 to 125 占 퐉, and more specifically, from 50 占 퐉 to 100 占 퐉. Within this range, it may be advantageous for use in a display, for example, a flexible display.

The conductive layer 120 is formed on the base layer 110 and includes metal nanowires 121 and a matrix 122. The conductive layer 120 has a structure in which the network formed of the metal nanowires 121 is impregnated into the matrix 122 and can have conductivity and good flexibility and flexibility. The conductive layer 120 can be patterned by a patterning method such as etching to form an electrode, and flexibility can be ensured and used for a flexible device. In an embodiment, the electrode may have a plurality of line shapes in a first direction and a second direction perpendicular to the first direction.

The metal nanowires 121 have better dispersibility than metal nanoparticles due to their nanowire shape. Also, the sheet resistance of the entire transparency can be remarkably lowered.

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 200 to 1,500. 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, specifically 500 to 700.

The diameter d of the cross section of the metal nanowires 121 may be 100 nm or less. For example, the diameter d of the cross section may be 30 nm to 100 nm, specifically 60 nm to 100 nm. The metal nanowires 121 may have a length L of 20 mu m or more. For example, the length L may be 20 占 퐉 to 50 占 퐉. With a diameter and a length in the above range, high transparency can be realized with high L / d and high conductivity and low sheet resistance.

The metal nanowires 121 may comprise nanowires made of any metal. For example, a metal such as Ag, Cu, Pt, Sn, Fe, Ni, Co, Al, Zn, (Cu), indium (In), and titanium (Ti). Specifically, silver nanowires or mixtures containing them can be 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 through reduction reaction of a metal salt (for example, silver nitrate (AgNO ₃ )) in the presence of a polyol and poly (vinyl pyrrolidone). Alternatively, commercially available products (e.g., ClearOhm Ink G4-05, Cambrios) 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 form a network layer on the substrate layer 110. In a specific example, a metal nanowire composition in which metal nanowires 121 are dispersed in a liquid may be applied on the substrate layer 110 to form a network layer. Herein, the liquid composition in which the metal nanowires 121 are dispersed is referred to as a " 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 Alkoxylates, ethylene oxides, propylene oxides, and the like can be used. These may be used singly or in the form of a mixture or copolymer of two or more.

The method of coating the metal nanowire composition on the base layer is not particularly limited and may be bar coating, spin coating, dip coating, roll coating, flow coating, die coating and the like. The coating thickness of the metal nanowire composition may be from 10 nm to 1 탆, specifically from 20 nm to 200 nm, more specifically from 30 nm to 130 nm, or from 50 nm to 100 nm. The metal nanowires may be coated on the substrate layer and then dried to form metal nanowire network layers on the substrate layer. The drying can be carried out, for example, at about 80 캜 to 140 캜 for 1 minute to 30 minutes.

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 can be exposed at the top of the conductive layer 120 and provides an adhesive force between the conductive layer 120 and the base layer 110. In addition, the optical transparency 100 may have improved optical properties, chemical resistance, solvent resistance, and the like.

The matrix 122 is a composition for a matrix comprising (A) a pentafunctional or hexafunctional urethane (meth) acrylic oligomer, (B) a trifunctional (meth) acrylic monomer, (C) a fluorine monomer, and . The matrix 122 is formed of a composition comprising (A) a pentafunctional or hexafunctional urethane (meth) acrylic oligomer, (B) a trifunctional (meth) acrylic monomer, (C) a fluorine monomer, and , Low transparency with low sheet resistance, good optical properties, and excellent reliability and durability.

The (A) bifunctional or hexafunctional urethane (meth) acrylic oligomer can be prepared, for example, by the reaction of a polyhydric alcohol, a polyisocyanate and a hydroxy (meth) acrylate. Specifically, the reaction can be conducted by reacting a polyol with a diisocyanate to prepare an intermediate having an isocyanate terminal and reacting the hydroxy (meth) acrylate with an isocyanate, but the present invention is not limited thereto.

Examples of the polyhydric alcohol include neopentylglycol, 3-methyl-1,5-pentanediol, ethyleneglycol, propyleneglycol, 1,4- Butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecanedimethylol, bis- [hedehyde] (Hydroxymethyl) -cyclohexane), and the like. A polyester polyol obtained by the reaction of the polyhydric alcohol with a polybasic acid, a polycaprolactone polyol obtained by the reaction of the polyhydric alcohol and? -Caprolactone, a polycarbonate polyol polycarbonate polyol, and polyether polyol. The polycarbonate polyol may be a polycarbonate diol obtained by reacting 1,6-hexanediol with diphenyl carbonate, or the like. have. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethyleneoxide modified bisphenol A, and the like. , But are not necessarily limited thereto.

The polyisocyanate may include an isocyanate having 2 to 6 isocyanate groups. Specifically, it is possible to use isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-diisocyanate, dicyclopentanyl diisocyanate, and the like, but not always limited thereto.

Examples of the hydroxy (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Acrylates such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (Meth) acrylate, 1,3,5-pentanetriol di (meth) acrylate, trimethylolpropane di (meth) acrylate trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Penta (meth) acrylate can be a (pentaerythritol penta (meth) acrylate), pentaerythritol hexa (meth) acrylate (pentaerythritol hexa (meth) acrylate), but are not necessarily limited thereto.

(A) the pentafunctional or hexafunctional urethane (meth) acrylate oligomer is used in an amount of 1 to 40% by weight, specifically 1 to 30% by weight, based on the total weight of (A) + (B) + , More specifically from 5% to 30% by weight. Within the above range, the matrix is excellent in adhesion, chemical resistance and etching property.

The (A) pentafunctional or hexafunctional urethane (meth) acrylic oligomer has a weight average molecular weight (Mw) of 1,000 to 5,000, specifically 1,000 to 4,000, more specifically 1,000 to 3,000. In the above range, the matrix has an advantage of excellent adhesion and etching property.

The (B) trifunctional (meth) acryl-based monomer may be a non-urethane-based trifunctional monomer having no urethane group. By including the (B) trifunctional (meth) acrylic monomer in the matrix composition, the matrix can be densely laminated within the network structure of the metal nanowires 121 and the adhesion to the substrate layer 110 can be improved . The trifunctional (meth) acrylic monomer (B) may include at least one of a trifunctional monomer of a polyhydric alcohol having 3 to 20 carbon atoms, and a trifunctional monomer of a polyhydric alcohol having 3 to 20 carbon atoms modified with an alkoxy group. The trifunctional monomer of the polyhydric alcohol having 3 to 20 carbon atoms is more specifically trimethylolpropane tri (meth) acrylate, glyceryl tri (meth) acrylate, But are not limited to, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and the like. These may be used alone or in combination of two or more.

The (B) trifunctional (meth) acrylic monomer may include a trifunctional (meth) acrylic monomer modified with an alkoxy group. The trifunctional (meth) acrylic monomer modified with an alkoxy group may be, for example, a trifunctional (meth) acrylic monomer of a polyhydric alcohol having 3 to 20 carbon atoms modified with an alkoxy group. The trifunctional (meth) acryl-based monomer of the polyvalent alcohol having 3 to 20 carbon atoms modified with an alkoxy group can further improve transparency and reliability of the transparency as compared with the trifunctional (meth) acryl-based monomer having no alkoxy group, It is possible to prevent the conductive layer from being distorted in yellow. Specifically, the trifunctional (meth) acrylic monomers having an alkoxy group (e.g., an alkoxy group having 1 to 5 carbon atoms) include ethoxylated trimethylolpropane tri (meth) acrylate, Propoxylated glyceryl tri (meth) acrylate, and the like, but are not limited thereto. These may be used alone or in combination of two or more.

The (B) trifunctional (meth) acrylic monomer may be used in an amount of 0.1 to 20% by weight, specifically 0.1 to 15% by weight, based on the total weight of (A) + (B) + By weight to 10% by weight. Within the above range, the matrix is excellent in adhesiveness and etching property.

The (meth) acrylate monomer having 5 functional groups or 6 functional urethane (meth) acrylate oligomers and (B) trifunctional (meth) acrylic monomers is preferably used in a composition of 6: 1 to 1: 1, specifically 5: 1 to 2: And in the above range, the transparency of the transparent body 100 can be enhanced and the reliability thereof can be enhanced. When the (A) bifunctional or hexafunctional urethane (meth) acrylic oligomer is more than (B) the trifunctional (meth) acrylic monomer, the adhesion of the conductive layer 120 to the base layer 110 increases, Chemical and etching properties.

(C) The fluorine-based monomer can be cured with the (A) bifunctional or hexafunctional urethane (meth) acrylic oligomer or the (B) trifunctional (meth) acrylic monomer of the conductive layer 120, The refractive index can be further lowered. Specifically, the fluorine-based monomer (C) may be a low refractive index monomer having a refractive index of 1.4 or less, for example, 1.33 to 1.38. By lowering the refractive index of the conductive layer 120 in the refractive index range, the transmission b * of the entire transparency can be lowered and the transparency of the entire transparency can be increased. Specifically, by controlling the fluorine content in the matrix to 6 wt% or less, 5 wt% or less, specifically 2 to 5 wt%, the refractive index control effect can be realized.

Specifically, the fluorine-containing monomer (C) is a fluorine-based monomer having a pentaerythritol skeleton, a fluorine-based monomer having a dipentaerythritol skeleton, a fluorine-based monomer having a trimethylolpropane skeleton, but are not limited to, fluorine-containing monomers having a ditrimethylolpropane skeleton, fluorine-containing monomers having a cyclohexyl skeleton, fluorine-containing monomers having a straight chain skeleton, or mixtures thereof. For example, (C) the fluorine-based monomer may be represented by any one of the following formulas (1) to (3).

[Chemical Formula 1]

(In the above formula (1), R ₁ is hydrogen (H),

or

, R ₂ and R ₃ are each

or

And R < ₄ > is

,

Or -CH ₃ , n is an integer between 1 and 5, and * is a binding site, provided that R ₁ is hydrogen (H), R ₂ and R ₃ are

, R ₄ is

)

(2)

(Wherein R ₅ to R ₁₆ each represent a fluorine (F), fluorine

or

With the proviso that both R ₅ to R ₁₆ are both fluorine (F) and both

)

(3)

(A) n - (B) m

(Wherein A is a hydrocarbon group having 1 to 20 fluorine-containing carbon atoms, B is an acrylate group, a methacrylate group, a fluorine-containing acrylate group or a fluorine-containing methacrylate group, n is an integer of 1-6, and m is an integer of 1-16.

The fluorine-containing monomer represented by the general formula (1) may be specifically 1 or 2. The fluorine-containing monomer represented by the general formula (1) is, for example,

,

,

,

,

,

,

,

,

,

But is not necessarily limited thereto.

In the fluorine-based monomer represented by the general formula (2), fluorine among R ₅ to R ₁₆ may be 10 or less. E.g,

,

,

,

,

,

,

,

But is not necessarily limited thereto.

(C) the fluorine-containing monomer is used in an amount of 1 to 40% by weight, specifically 5 to 35% by weight, more specifically 5 to 30% by weight, based on the total weight of (A) + (B) + % By weight. In the above range, the transmittance b * of the entire transparency can be lowered and the transparency of the entire transparency can be increased. In the matrix 122, the (A) 5-functional or 6-functional urethane (meth) acrylic oligomer or (B) It is possible to form the matrix 122 in which the content of the monomer is not too low.

(D) The nanosilica can use untreated untreated nanosilica or surface treated nanosilica. The surface-treated nanosilica may be nanosilica surface-treated with a curable functional group. For example, nanosilica surface-treated with (meth) acrylate groups may be used. The surface-treated nanosilica can be cured with the (A) bifunctional or hexafunctional urethane (meth) acrylic oligomer or (B) trifunctional (meth) acrylic monomer of the conductive layer 120, And may be more tightly coupled to the conductive layer 120. Specifically, 10% to 90%, specifically 20% to 70%, and more specifically 40% to 60% of the entire outer surface area of the (D) nano silica can be surface-treated with (meth) acrylate compounds, It has excellent durability and bondability in the range. (D) nanosilica surface-treated with a (meth) acrylate compound is commercially available commercially and can be prepared by a conventional method. For example, it can be prepared by first coating (D) the surface of the nanosilica with a silane group-containing compound and carrying out an addition reaction with a (meth) acrylate compound. The (D) nanosilica may have an average particle diameter of 10 nm to 200 nm, specifically 10 nm to 160 nm, more specifically 10 nm to 140 nm. Within the above range, transparency has the advantage of increased transparency and excellent reliability. The (D) nanosilica is present in the total weight of (A) + (B) + (C) + (D) in an amount of 30 wt% to 90 wt%, specifically 40 wt% to 90 wt%, more specifically 40 wt% 85% by weight. In the above range, the entire transparency has an advantage that the haze is low and the transparency is increased.

In one embodiment, the composition for a matrix comprises 1 to 40% by weight of a pentafunctional or hexafunctional urethane (meth) acrylate oligomer (A) + (B) + ) 0.1 to 20% by weight of a trifunctional (meth) acrylic monomer, (C) 1 to 40% by weight of a fluorine-containing monomer, and (D) 30 to 90% by weight of a nano-silica.

In another embodiment, the composition for a matrix comprises 5 to 30% by weight of a pentafunctional or hexafunctional urethane (meth) acrylic oligomer (A) + (B) + (C) + 1) to 10% by weight of a trifunctional (meth) acrylic monomer, (C) 5 to 30% by weight of a fluorine monomer, and (D) 40 to 85% by weight of a nano silica. The transmittance, reliability, and durability of the transparent body 100 can be enhanced within the above range.

The composition for a matrix may further comprise a surfactant. The surfactant (D) has a hydrophobic portion which is compatible with the nanosilica and a hydrophilic portion which is compatible with the solvent. Thus, the surfactant allows (D) the nanosilica to be stably dispersed in the matrix 122. The surfactant is not particularly limited and includes, for example, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ether, Polyoxyethylene alkyl allyl ethers such as polyoxyethylene alkyl ether, ethers and polyoxyethylenenonyl phenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan monostearate and sorbitan monooleate; siloxane surfactants such as Dynol 980 (manufactured by Air Products); and surfactants such as F Top EF301, EF303, EF352 (manufactured by TOKEM PRODUCTS CO., LTD. ), Megapack F171 and F173 (manufactured by Dainippon Ink and Chemicals, Inc.). Fluorinated surfactants such as Prorad FC430 and FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Chaplon S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., A siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and other silicone surfactants.

The surfactant is used in an amount of 0.001 to 0.5 parts by weight, specifically 0.001 to 0.3 parts by weight, more specifically 0.001 to 0.1 parts by weight, based on 100 parts by weight of (A) + (B) + (C) + 0.01 part by weight to 0.05 part by weight. Within the above range, (D) balance of dispersion of nanosilica and thin film coating property can be achieved.

The composition for a matrix may further comprise an adhesion promoting agent. The adhesion promoter can improve the adhesion of the metal nanowires 121 to the base layer 110 and improve the reliability of the transparent body 100. Examples of the adhesion promoting agent include at least one of a silane coupling agent, a monofunctional monomer, a bifunctional monomer, and a trifunctional monomer.

As the silane coupling agent, a conventional silane coupling agent can be used. For example, a silane coupling agent having an amino group or an epoxy group can be used. In this case, 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, ethyleneglycol di (meth) acrylate, neopentylglycol di (meth) acrylate, (meth) acrylate, hexanediol di (meth) acrylate, and cyclodecane dimethanol di (meth) acrylate. However, Limited Do not.

The adhesion promoting agent is added in an amount of 0.1 to 10 parts by weight, specifically 0.1 to 5 parts by weight, more specifically 0.1 to 2 parts by weight, based on 100 parts by weight of (A) + (B) + (C) &Lt; / RTI > Adhesiveness can be improved while maintaining the reliability and conductivity of the entire transparency within the above range.

The composition for a matrix may further comprise an antioxidant. The antioxidant may prevent oxidation of the metal nanowire network of the conductive layer 120. Specifically, at least one of a phosphorus-based antioxidant such as a triazole-based antioxidant, a triazine-based antioxidant, a phosphite-based phosphorus-based antioxidant, a Hinder amine light stabilizer (HALS) . &Lt; / RTI > For example, by mixing two or more kinds of them, oxidation of the metal nanowires 121 can be prevented and reliability can be enhanced. When two or more kinds of antioxidants are used, oxidation prevention and reliability can be more excellent. In one embodiment, the antioxidant may be a mixture of phosphorus and phenol, a mixture of phosphorus and HALS, or a mixture of phenol and HALS, especially phosphorus and HALS, or a triazole, Phosphorous, or a mixture of triazine, phenol, and phosphorous. The transparency 100 includes the phosphorus antioxidant so that the conductivity b * of the conductive layer 120 can be lowered without affecting the conductivity.

For example, tris (2,4-di-tert-butylphenyl) phosphite is used as the phosphorus antioxidant, pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and the like The HALS antioxidant is bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl- (2,2,6,6-tetramethyl-4-piperidinyl sebacate), bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, Bis (2,2,6,6-tetramethyl-5-piperidinyl) sebacate), 4-hydroxy-2,2,6,6-tetramethyl- (N-butyl-N-methyl-2-pyrrolidone), dimethylsuccinate (4-hydroxy-2,2,6,6-tetramethyl- 1-cyclohexyloxy-2,2,6,6-tetra 4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine (N-butyl N- (1-cyclohexyloxy- 2,2,6,6-tetramethylpiperidine-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine).

The antioxidant is used in an amount of 0.01 to 5 parts by weight, specifically 0.01 to 5 parts by weight, more specifically 0.01 to 1 part by weight (based on 100 parts by weight of (A) + (B) + &Lt; / RTI > Within this range, oxidation of the metal nanowire network can be prevented and the transmission b * value can be lowered.

The composition for a matrix may further include an initiator. As the initiator, a conventional photopolymerization initiator may be used. Specifically, the initiator may be alpha-hydroxy ketone series, alpha-amino ketone series or phosphine oxide series. For example, the initiator may be selected from the group consisting of alpha-hydroxy ketone series 1-hydroxycyclohexyl phenyl ketone, alpha-amino ketone series alpha-amino acetophenone series, phosphine oxide series 2,4,6-trimethylbenzoyl- A pin oxide or a mixture containing it may be used. The initiator is added in an amount of 0.01 to 10 parts by weight, specifically 0.01 to 5 parts by weight, more specifically 0.011 to 1 part by weight per 100 parts by weight of (A) + (B) + (C) + .

The composition for a matrix may comprise a solvent. Specific examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and propanol; Ketones such as methyl isobutyl ketone and methyl ethyl ketone; Esters such as methyl acetate, ethyl acetate and propylene glycol methyl ether acetate; Aromatic compounds such as toluene, xylene, and benzene; And ethers such as dimethyl ether and the like. These may be used alone or in combination of two or more.

The composition for a matrix may further include an additive for improving performance, and the additive may include a thickener, a dispersant, or a UV stabilizer.

The method for coating the composition for a matrix on the metal nanowire network layer is not particularly limited, but may be bar coating, spin coating, dip coating, roll coating, flow coating, die coating and the like. The metal nanowire network layer is formed by coating the metal nanowire composition on the substrate layer followed by drying, and the composition for the matrix coated on the metal nanowire network layer is permeated into the metal nanowire network layer. Thus, the metal nanowires are impregnated into the matrix composition to form a conductive layer containing the metal nanowires and the matrix. The metal nanowire may be present either as a whole impregnated in the matrix or partially exposed on the conductive layer surface.

Coating the composition for a matrix, and then drying the composition. For example, at 80 ° C to 120 ° C for 1 minute to 30 minutes.

After drying, one or more of photocuring and thermosetting may be performed. Photocuring can be carried out by irradiating light with a wavelength of 400 nm or less at a dose of 150 mJ / cm 2 to 1000 mJ / cm 2, and thermal curing may include thermal curing at 50 ° C to 200 ° C for 1 hour to 120 hours.

The thickness of the conductive layer 120 may be 10 nm to 1 탆, specifically 20 nm to 200 nm, more specifically 30 nm to 130 nm, or 50 nm to 120 nm. Within the above range, the transparency 100 may be used as a film for a touch panel. Within this range, the contact resistance may be lowered, durability and chemical resistance may be improved, and an effect of having excellent optical characteristics may be obtained.

Although not shown in FIG. 1, a functional layer may be further laminated on one side or both sides of the base layer 110. The functional layer may be a hard coating layer, a corrosion preventing layer, an antireflection layer, an adhesion promoting layer, an oligomer elution preventing layer, and the like, but is not limited thereto.

The transparency 100 may have transparency in a visible light region, for example, a wavelength of 400 nm to 700 nm. In an embodiment, the transparency 100 may have a haze of 0.5% to 1.0%, specifically 0.7% to 1.0%, more specifically 0.7% to 0.9%, as measured by a haze meter at a wavelength of 400 nm to 700 nm. The total light transmittance may be 88% to 99%, specifically 90% to 99%, more specifically 91% to 99%. In the above range, the transparency 100 is high in transparency, and transparency is good, and transparency can be used for the entire application. The rate of resistance change is low, and the transparent electrode 100 can be used as a transparent electrode film by patterning the transparency 100.

The transmission b * value of the transparency 100 may be 0.5 to 1.2, specifically 0.7 to 1.2, or 0.8 to 1.2. Within this range, the transparency of the entire transparent body 100 is high, the resistance change rate is low, and the transparent electrode film can be used as a transparent electrode film by patterning the transparent body 100. Of course, due to the matrix 122, durability, chemical resistance, solvent resistance, etc. of the entire transparency can be obtained.

The transparency 100 may have a sheet resistance of 50 (Ω / □) or less, specifically 30 to 50 (Ω / □), or 40 to 50 (Ω / □) as measured by a non-contact sheet resistance meter (NAPPON company, EC80P) . In the above range, since the sheet resistance is low, it can be used as an electrode film for a touch panel, and can be applied to a large-area touch panel.

The transparency 100 may have a resistance change rate of 10% or less, for example, 0% or more and 10% or less, specifically 0% or more and 8% or less. The entire transparency in the above range is advantageous in terms of reliability.

The thickness of the transparent transparency 100 is not limited, but may be 10 탆 to 250 탆, for example, 50 탆 to 200 탆. In 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 entire transparency is in the form of a film, which is patterned by etching or the like, and can be used as a transparent electrode film of a touch panel, E-paper, or solar cell.

1 illustrates an embodiment in which a conductive layer including a metal nanowire 121 and a matrix 122 is formed on an upper surface of a base material layer 110. However, A case where a conductive layer is further formed may also be included in the scope of the present invention.

Hereinafter, the transparency of another embodiment of the present invention will be described with reference to FIG.

Referring to FIG. 2, a transparent conductive layer 120 'is formed on the base layer 110 and the upper surface of the base layer 110, according to another embodiment of the present invention. The patterned conductive layer 120 'may include a metal nanowire-containing conductive layer 120a and a metal nanowire-free conductive layer 120b. The metal nanowire-containing conductive layer 120a includes a metal nanowire 121 and a matrix 122. The metal nanowire-free conductive layer 120b is composed of only the matrix 122 and does not include metal nanowires. Is substantially the same as the transparency 100 of the embodiment of the present invention except that the conductive layer 120 'is patterned.

The conductive layer 120 'may be patterned by a predetermined method, for example, etching using an acidic solution. The conductive layer 120' may be patterned to form x and y channels and used as a conductor.

Although not shown in FIG. 2, a pattern layer is formed on the conductive layer 120 'to distinguish a portion to be etched from a portion to be etched in the etching step.

When etching is performed, the etching solution may be an acidic etching solution, the pH may be 2 to 5, and the temperature may be 30 to 45 占 폚. It is possible to perform etching with the line width required for the transparent conductor in the above range. The etching solution may be an aqueous solution containing at least one of phosphoric acid, nitric acid, and acetic acid. Specifically, 75 to 85% by weight of phosphoric acid at 85% concentration (by volume), 3 to 5% by weight of nitric acid at 70% concentration (by volume), 1 to 10% by weight of acetic acid at a concentration of 99.7% It can be an aqueous solution containing water, and etching can be performed with a line width required in the above range.

For example, as shown in FIG. 2, the metal nanowire-containing conductive layer 120a is not etched by the pattern layer and contains metal nanowires, and the metal nanowire-free layer 120b is formed by etching the metal nanowires So that only the matrix containing no metal nanowires is formed. The on-set time at which the silver nano wire disappears in the etching process may be 90 seconds to 240 seconds, specifically 90 seconds to 200 seconds. There is an advantage that the transparency as a whole is excellent in the fairness within the above range.

The entire transparency may include an overcoat layer formed on the conductive layer.

Hereinafter, referring to FIG. 3, the transparency of another embodiment of the present invention will be described.

3, the transparent body 200 includes a base layer 110, a conductive layer 120 formed on the upper surface of the base layer 110 and including metal nanowires 121 and a matrix 122, And an overcoat layer 130 formed on the upper surface of the conductive layer 120. [ Although not shown in FIG. 3, the conductive layer 120 and the overcoat layer 130 may be integrally formed. The 'integral type' may mean that the conductive layer 120 and the overcoat layer 130 are not bonded to each other by an adhesive layer or the like and are not independently separated. The transparent body 200 of this embodiment has substantially the same structure as the transparent body 100 according to an embodiment of the present invention except that the overcoat layer 130 is further formed. ) Will be mainly described.

The overcoat layer 130 is formed on the conductive layer 120 and may be formed of a single layer or a multiple layer. The overcoat layer 130 can have various compositions according to the required physical properties, and can protect the entire transparency (200, 250), prevent reflection or prevent electrification, and the invention is not limited thereto.

For example, the overcoat layer 130 can be formed by coating a substrate with a composition for forming an overcoat layer in which a thermosetting or radiation-curable resin or a curing initiator is dissolved in a solvent, followed by curing with heat and radiation.

The thermosetting or radiation-curable resin may be a compound having two or more functional groups. Specifically, there can be mentioned an unsaturated double bond such as (meth) acrylate and a reactive substituent such as an epoxy group or a silanol group. Specific examples of the compound having such a functional group include ethylene glycol diacrylate, neopentylglycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate ( 1,6-hexanediol (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyol poly Di (meth) acrylate of polyolpoly (meth) acrylate, bisphenol A-diglycidyl ether; di (meth) acrylate of bisphenol A-diglycidyl ether; (Meth) acrylate, polysiloxanacrylate, urethane (meth) acrylate, urethane (meth) acrylate, urethane acrylate and urethane acrylate obtained by esterifying a polyhydric alcohol, a polyvalent carboxylic acid or an anhydride thereof with acrylic acid, (meth) acrylate, pentaerythritol tetramethacrylate, glyceryl trimethacrylate, and the like. Containing fluorine-containing epoxy acrylate, fluorine-containing alkoxy silane, and the like can be used. Perfluorodecyl ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropylacrylate, 3-perfluoroethyl acrylate, 3-perfluoroethyl acrylate, - (perfluoro-9-mehtyldecyl) -1,2-epoxypropane, (meth) acrylate-2,2,2-trifluoro 2-trifluoromethyl-3, (meth) acrylate-2,2,2-trifluoroethyl, (meth) acrylate- 3,3-trifluoropropyl). These compounds may be used singly or in combination of two or more.

The curing initiator serves to help cure the coating liquid. Specific examples thereof include benzoin, benzoin methyl ether, acrylphosphine oxide compounds, peroxide compounds such as benzoin peroxide and butyl peroxide, and isopropyl thioxanthone benzoin-based compounds such as isopropyl thioxanthone and benzoin isopropyl ether, carbonyl compounds such as benzyl, benzophenone and acetophenone, azo compounds such as azobisisobutylnitrile An azo compound such as azodibenzoyl, a mixture of diketone and a tertiary amine, a cationic photoinitiator, anhydride, peroxide, an? -Hydroxyalkylphenone compound,?, a-dialkoxyacetophenone, an? -hydroxyalkylphenone compound, an? -aminoalkylphenone derivative compound, an? -hydroxyalkylphenone polymer compound, a thioxanthone derivative Compound, a water-soluble aromatic ketone compound, a Ti compound, such as nano-metallocene of the initiator may be used. The curing initiator may comprise 0.1 to 20 parts by weight based on 100 parts by weight of the thermosetting or radiation curable resin. Within the above range, it is advantageous in that the reactivity is good, the hardness is excellent, and the haze due to the unreacted initiator is prevented from increasing.

Specific examples of the solvent for forming the composition for forming an overcoat layer include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and propanol; Ketones such as methyl isobutyl ketone and methyl ethyl ketone; Esters such as methyl acetate and ethyl acetate; Aromatic compounds such as toluene, xylene, and benzene; And ethers such as dimethyl ether, but the present invention is not limited thereto.

The formation of the overcoat layer 130 may include inorganic fine particles for adjustment of refractive index, surface tension, and hardness in addition to the above-described organic compounds. Examples of the inorganic fine particles include SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , ZnO, In ₂ O ₃ , SnO, Sb ₂ O ITO and ATO. In the case of using ITO (Indium Tin Oxide) or ATO (antimony doped tin oxides), an antistatic function can be additionally provided.

The composition for the overcoat layer can be coated in the same manner as the metal nanowire composition, and the thickness of the overcoat layer 130 is 20 nm to 200 nm, specifically 30 nm to 130 nm, or 50 nm to 100 nm. The visibility of the entire transparency is increased in the above range, and the conductive layer is protected. Specifically, the overcoat layer 130 is formed by applying a composition for an overcoat layer using roll coating, dip coating, knife coating, bar coating, spin coating, and the like, and then UV curing using a halogen lamp, a high pressure mercury lamp, Or by performing thermal curing.

Although not shown, it may further include at least one of a high refractive index layer and a low refractive index layer on the overcoat layer 130.

The high refractive index layer is formed using a high refractive index composition comprising metal oxide fine particles, a binder, a solvent and a curing initiator.

The metal oxide fine particles are used to make the refractive index of the high refractive index layer satisfy the range of 1.6 to 1.9. For example, zinc oxide, titanium oxide, cerium oxide, aluminum oxide, ITO, ATO, zirconium oxide, have. The size of the fine particles may have a particle diameter of 1 nm to 1,000 nm, specifically, 10 nm to 100 nm. In the case of wet coating, it may have a particle diameter of 10 nm to 50 nm in terms of stability of particle dispersion.

The binder contained in the high refractive index composition may be suitably used as long as it is a hydroxyl group-containing polymer. Specifically, a polyvinyl acetal resin, a polyvinyl alcohol resin, a polyacrylic resin polyphenol resin, a phenoxy resin and the like are used singly or in combination of two or more. The amount of the binder added to the high refractive index composition is preferably 1 to 100 parts by weight based on 100 parts by weight of the inorganic oxide particles in consideration of the adhesion of the high refractive index layer to the overcoat layer. It is easy to control the refractive index in the above range.

The high-refractive-index composition may further comprise a compound having a thermo-photopolymerizable functional group capable of reacting with the binder. Examples of the compound having a thermo-photopolymerizable functional group include t-butylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylamino N-diethylaminoethyl acrylate, N-methacryloxy-N, N-methacryloxy-N, N-dicarboxymethyl-p-phenylene diamine, N-methacryloxy-N-carboxymethylpiperidin, and 4-methacryloxyethyl anhydride trimellitic acid. The term " methacryloxypropylmethylpiperidine " These may be used alone or in combination of two or more. The content of the compound having a thermo-photopolymerizable functional group may be in the range of 10 to 300 parts by weight based on 100 parts by weight of the inorganic oxide particles. In this range, the curing is sufficiently performed, and the refractive index is increased. As the curing initiator, a radical generator or an acid generator may be used, and it is more preferable to use both of them. It is also preferable to use a compound having a functional group such as a compound having a thermo-photopolymerizable functional group to enhance thermal reactivity.

The solvent contained in the high refractive index composition may be the same as or similar to the solvent used in the overcoat layer and the low refractive index layer. For example, alcohols, ketones, esters, ethers, and the like can be used. In the specific examples, the handling property of the high refractive index composition is improved by using a mixed solvent of two or more kinds of solvents, and excellent antireflection property and transparency of high refractive index can be obtained. The solvent may be used in an amount of 50 to 20,000 parts by weight based on 100 parts by weight of the inorganic oxide particles. The viscosity of the coating liquid is easily controlled within the above range.

The curing initiator included in the high refractive index composition may be the same as or similar to the curing initiator used in the overcoat layer and the low refractive index layer, but is not limited thereto.

The high refractive index layer may be formed by dry or wet coating using a high refractive index composition. In the specific example, it may be formed by a wet coating method for large-size and cost reduction of the optical display device. The wet coating method includes roll coating, spin coating, dip coating and bar coating.

The thickness of the high refractive index layer may be about lambda / 4 after drying, and the thickness thereof is from 50 nm to 200 nm. The refractive index of the high refractive index layer may range from 1.6 to 1.9.

The low refractive index layer is formed by coating a low refractive index composition including a polymer of a fluorine-containing or fluorine-free compound, inorganic particles, a curing initiator, and a solvent on the high refractive index layer and curing it.

The low refractive index layer may have a refractive index of 1.33 to 1.55. In order to satisfy the refractive index as described above, a polymer of an inorganic particle and / or a fluorine-containing organic compound such as silicon oxide, magnesium fluoride, and cerium fluoride may be used, or a polymer of a fluorine-free organic compound may be used.

As the fluorine-containing compound, a fluorine-containing compound containing an alkyl group or a polyfluoro ether group; A fluorine-containing compound containing a hydroxyl group, a carboxyl group, and an alkoxysilyl group having polarity; A copolymer of an unsaturated fluorine-containing compound having a polyfluoro ether group and an unsaturated fluorine-containing compound having a polarity, or the like can be used. As the polymer of the fluorine-free organic compound, for example, olefins, acrylates, styrene derivatives, vinyl ethers, vinyl esters, acrylamides, methacrylamides and the like may be used.

As the solvent, a fluorine-based solvent or a general organic solvent capable of dissolving a fluorine-containing or fluorine-free compound may be used. Examples of the perfluorocarbons include perfluorocarbons such as perfluoro pentane, perfluoro hexane, and perfluoro octane; Perfluoropolyethers; And hydrochloro-carbonated fluorides. Examples of common organic solvents include hexane, toluene, methyl ethyl ketone, octane, chloroform, carbon tetrachloride, xylene, cyclohexane, cyclopentane, methanol, ethanol, ethyl acetate and isopropyl alcohol. These solvents may be used alone or in combination of two or more. For the uniformity and leveling effect of the coating, two or more kinds having a difference in boiling point can be mixed and used.

The curing initiator included in the low refractive index composition may be the same as or similar to the curing initiator used in the overcoat layer and the high refractive index layer, but is not limited thereto.

The thickness of the low refractive index layer may be about lambda / 4, the thickness of the low refractive index layer may be 50 nm to 200 nm, and the refractive index of the low refractive index layer may be 1.33 to 1.55.

4, the transparency entire body 250 includes a base layer 110, a conductive layer 120 formed on the upper surface of the base layer 110 and including metal nanowires 121 and a matrix 122, An overcoat layer 130 formed on the upper surface of the conductive layer 120 and a conductive layer 120 and an overcoat layer 130 may be further formed on the lower surface of the base layer 110. Except that a conductive layer 120 and an overcoat layer 130 are further formed on the lower surface of the base layer 110. The transparent conductive layer 120 is formed on the entire surface of the base layer 110,

Hereinafter, a method for manufacturing a transparent body according to an embodiment of the present invention will be described.

A method of manufacturing a transparent body according to an embodiment of the present invention includes the steps of forming a metal nanowire network layer with a metal nanowire composition on a substrate layer, and forming a metal nanowire network layer on the metal nanowire network layer with (A) five or six functional urethane (meth) (B) a trifunctional (meth) acrylic monomer, (C) a fluorine-based monomer, and (D) a nanosilica. Another manufacturing method according to this embodiment is a method in which metal nanowires and a composition for a matrix are coated at the same time to form a conductive layer without coating the metal nanowires and then coated with a composition for a matrix, A good overall transparency can be obtained.

The metal nanowire composition is a liquid composition in which metal nanowires are dispersed, and can be prepared by including a binder for dispersing metal nanowires. The metal nanowire composition is specifically as described with respect to the transparency 100 of one embodiment of the present invention.

The method of coating the metal nanowire composition on the substrate layer is not particularly limited, but it can be performed by bar coating, spin coating, dip coating, roll coating, flow coating, die coating and the like. nm to 1 占 퐉, specifically 20 nm to 200 nm, more specifically 30 nm to 130 nm, or 50 nm to 100 nm. The metal nanowires may be coated on the substrate layer and then dried to form metal nanowire network layers on the substrate layer. The drying can be carried out, for example, at about 80 캜 to 140 캜 for 1 minute to 30 minutes.

The composition for a matrix may include (A) a pentafunctional or hexafunctional urethane (meth) acrylic oligomer, (B) a trifunctional (meth) acrylic monomer, (C) a fluorine-based monomer, and (D) a nanosilica. Specifically, as described with respect to the transparent body 100 of the embodiment of the present invention.

The method for coating the matrix composition on the metal nanowire network layer is not particularly limited, but may be bar coating, spin coating, dip coating, roll coating, flow coating, die coating and the like. The metal nanowire network layer is formed by coating the metal nanowire composition on the substrate layer followed by drying, and the composition for the matrix coated on the metal nanowire network layer is permeated into the metal nanowire network layer. Thus, the metal nanowires are impregnated into the matrix composition to form a conductive layer containing the metal nanowires and the matrix. The metal nanowire may be present either as a whole impregnated in the matrix or partially exposed on the conductive layer surface.

The method of manufacturing a transparent body according to an embodiment of the present invention may further include forming an overcoat layer. Specifically, the composition for the overcoat layer is as described for the transparent body 200, 250 of another embodiment of the present invention. The composition for the overcoat layer may be coated in the same manner as the transparent body 200, 250 of another embodiment of the present invention, and the coating thickness of the composition for the overcoat layer may be 20 nm to 200 nm, specifically 30 nm to 130 nm, Or 50 nm to 100 nm.

The method of manufacturing a transparent body according to another embodiment of the present invention may further include forming at least one of a high refractive index layer and a low refractive index layer on the overcoat layer. Specifically, the composition for the high refractive index layer and the low refractive index layer is as described for the entire transparency of another embodiment of the present invention.

The optical display device according to an embodiment of the present invention may include the entire transparency of the embodiment of the present invention. Specifically, an optical display device including a touch panel, a touch screen panel, a flexible display, etc., E-paper, or a solar cell, but is not limited thereto.

Hereinafter, an optical display device according to an embodiment of the present invention will be described with reference to FIGS. 5 to 6. FIG. FIG. 5 is a cross-sectional view of an optical display device according to an embodiment of the present invention, and FIG. 6 is a cross-sectional view according to an embodiment of the display unit of FIG.

5, an optical display device 300 according to an embodiment of the present invention includes a display portion 350a, a polarizing plate 370 formed on a display portion 350a, a transparent electrode member 380 formed on a polarizing plate 370, And a window layer 390 formed on the transparent electrode member 380. The transparent electrode member 380 may include the entire transparency of the embodiments of the present invention.

The display portion 350a is for driving the optical display device 300 and may include an optical element including an OLED, an LED, or an LCD element formed on the substrate and the substrate. 6 is a cross-sectional view according to an embodiment of the display unit of FIG. 6, the display portion 350a includes a lower substrate 310, a thin film transistor 316, an organic light emitting diode 315, a planarization layer 314, a protective layer 318, an insulating layer 317, an adhesive layer 330 ), And an upper substrate 320.

The lower substrate 310 supports the display portion 350a and can be adhered to the upper substrate 320 by the adhesive layer 330. [ A thin film transistor 316 and an organic light emitting diode 315 are formed on the lower substrate 310. A flexible printed circuit board (FPCB) for driving the transparent electrode assembly 380 may be formed on the lower substrate 310. The flexible printed circuit board may further include a timing controller for driving the organic light emitting diode array, a power supply unit, and the like.

The lower substrate 310 may include a substrate formed of a flexible resin. The lower substrate 310 may include a flexible substrate such as a silicone substrate, a polyimide substrate, a polycarbonate substrate, or a polyacrylate substrate, but is not limited thereto .

A plurality of pixel regions are defined by a plurality of driving wirings (not shown) and sensor wirings (not shown) crossing the display region of the lower substrate 310, and thin film transistors 316 and thin film transistors 316 And an organic light emitting diode (OLED) 315 connected to the organic light emitting diode array. The non-display region of the lower substrate may be formed in the form of a panel in which a gate driver for applying an electrical signal to the driving wiring is a gate. The gate-in panel circuit portion may be formed on one side or both sides of the display region.

The thin film transistor 316 may be formed on the lower substrate 310 by controlling a current flowing through the semiconductor by applying an electric field perpendicular thereto. The thin film transistor 316 may include a gate electrode 310a, a gate insulating film 311, a semiconductor layer 312, a source electrode 313a, and a drain electrode 313b. The thin film transistor 316 includes an oxide thin film transistor using an oxide such as indium gallium zinc oxide (IGZO), ZnO, or TiO.sub.2 as the semiconductor layer 312, an organic thin film transistor using an organic material as a semiconductor layer, an amorphous silicon An amorphous silicon thin film transistor to be used, or a polycrystalline silicon thin film transistor using polycrystalline silicon as a semiconductor layer.

The planarization layer 314 may cover the thin film transistor 316 and the circuit portion 310b so that the top surface of the thin film transistor 316 and the circuit portion 310b may be planarized to form the organic light emitting diode 315. [ The planarization layer 314 may be formed of a spin-on-glass (SOG) film, a polyimide-based polymer, a polyacrylic polymer, or the like, but is not limited thereto.

The organic light emitting diode 315 may be formed on the planarization layer 314 by self-emission to realize a display. The organic light emitting diode 315 may include a first electrode 315a, an organic light emitting layer 315b, and a second electrode 315c sequentially stacked. The adjacent organic light emitting diodes may be separated through an insulating film 317. [ The organic light emitting diode 315 may include a bottom emission structure in which light generated in the organic emission layer 315b is emitted through the bottom substrate or a front emission structure in which light generated in the organic emission layer 315b is emitted through the top substrate have.

The passivation layer 318 covers the organic light emitting diode 315 to protect the organic light emitting diode 315. The passivation layer 318 is formed of an inorganic insulating material such as SiOx, SiNx, SiC, SiON, SiONC, and aC (amorphous carbon) Acrylate, an epoxy-based polymer, an imide-based polymer, and the like.

The adhesive layer 330 may be formed of an ultraviolet curable resin such as a (meth) acrylic, epoxy, or urethane resin or a thermosetting resin by adhering the lower substrate 310 and the upper substrate 320 including the protective film 318 to each other. . The adhesive layer 330 may further include moisture or an oxygen absorbing agent to protect the organic light emitting diode.

The upper substrate 320 protects the organic light emitting diode 315 and the thin film transistor 316 and may be formed of the same material as or different from the material of the lower substrate 310. Specifically, the upper substrate 320 may include a flexible substrate such as a silicon substrate, a polyimide substrate, a polycarbonate substrate, and a polyacrylate substrate, but is not limited thereto.

Referring again to FIG. 5, the polarizing plate 370 may implement polarized light or prevent reflection of external light to realize a display, or increase the contrast ratio of the display. The polarizer 370 may be composed of a polarizer alone. Or the polarizing plate 370 may include a polarizing film and a protective film formed on one or both sides of the polarizing film. Or the polarizer 370 may include a polarizer and a protective coating layer formed on one or both sides of the polarizer. The polarizer, the protective film, and the protective coating layer may be conventional ones known to those skilled in the art.

The transparent electrode unit 380 senses a change in capacitance caused when a conductor such as a human body or a stylus touches the touch panel, and generates an electrical signal. The display unit 350a can be driven by this signal. The transparent electrode body 380 may include the entire transparency of the embodiments of the present invention and may include, for example, a touch panel screen. The transparent electrode member 380 is formed by patterning a flexible conductive conductive material. The transparent electrode member 380 may include a first sensor electrode and a second sensor electrode formed between the first sensor electrode and the first sensor electrode. have. The conductor for the transparent electrode member 380 may include, but is not limited to, metal nanowires, conductive polymers, carbon nanotubes, and the like.

The window layer 390 may be formed at the outermost portion of the optical display device 300 to protect the display device.

Although not shown in FIG. 5, between the display portion 350a and the polarizing plate 370 and / or between the polarizing plate 370 and the transparent electrode body 380 and / or between the transparent electrode body 380 and the window layer 390 By further forming the adhesive layer, the bonding between the display portion, the polarizing plate, the transparent electrode body, and the window layer can be strengthened. The pressure-sensitive adhesive layer may be formed of a pressure-sensitive adhesive composition comprising a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent.

The (meth) acrylic resin is a (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an aromatic group, a carboxylic acid group, an alicyclic group, a heteroalicyclic group, or the like and may include a conventional (meth) acrylic copolymer. Specifically, a (meth) acrylic monomer having an unsubstituted C1 to C10 alkyl group, a (meth) acrylic monomer having a C1 to C10 alkyl group having at least one hydroxyl group, a (meth) acrylic monomer having an C6 to C20 aromatic group (Meth) acrylic monomer having a carboxylic acid group, a (meth) acrylic monomer having a C3 to C20 alicyclic group, a C3 to C10 heteroalicyclic group having at least one of nitrogen (N), oxygen (O) (Meth) acryl-based monomer having at least one group selected from the group consisting of (meth) acryl-based monomers.

The curing agent may be a bifunctional (meth) acrylate such as hexanediol diacrylate as a polyfunctional (meth) acrylate; Trifunctional (meth) acrylates of trimethylolpropane tri (meth) acrylate; Tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate; Pentafunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; (Meth) acrylate such as dipentaerythritol hexa (meth) acrylate, but are not limited thereto.

The initiator may be a photoinitiator, but is not limited thereto. The photoinitiator may include the photo-radical initiator described above as a typical photoinitiator.

The silane coupling agent may include a silane coupling agent having an epoxy group such as 3-glycidoxypropyltrimethoxysilane and the like.

The composition for the adhesive layer may comprise 100 parts by weight of a (meth) acrylic resin, 0.1 to 30 parts by weight of a curing agent, 0.1 to 10 parts by weight of a photoinitiator, and 0.1 to 20 parts by weight of a silane coupling agent. Within this range, the optical elements can be sufficiently adhered.

The thickness of the adhesive layer may be 10 [micro] m to 100 [micro] m. It is possible to sufficiently adhere the optical elements in the above range.

Although not shown in FIG. 5, a polarizing plate is further provided under the display unit 350a, so that polarized light can be realized.

Hereinafter, an optical display device according to another 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 another embodiment of the present invention.

7, an optical display device 400 according to another embodiment of the present invention includes a display portion 350a, a transparent electrode body 380 formed on a display portion 350a, and a transparent electrode body 380 And a window layer 390 formed on the polarizing plate 370 and the transparent electrode member 380 may include the entire transparency of the embodiments of the present invention. Is substantially the same as the optical display device 300 according to the embodiment of the present invention, except that the transparent electrode body 380 is directly formed on the display portion 350a.

Since the transparent electrode member 380 is formed on the display unit 350a, the thickness of the transparent electrode member 380 is thinner and brighter than that of the optical display device according to an embodiment of the present invention. The transparent electrode member 380 can be formed by vapor deposition or the like, but is not limited thereto.

7, between the display portion 350a and the transparent electrode body 380 and / or between the transparent electrode body 380 and the polarizer 370 and / or between the polarizer 370 and the window layer 390, By further forming the adhesive layer, the mechanical strength of the display device can be increased. The pressure-sensitive adhesive layer may be formed of a pressure-sensitive adhesive composition comprising a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent. The pressure-sensitive adhesive composition is as described above.

Further, although not shown in FIG. 7, a polarizing plate is further formed under the display unit 350a to induce polarization of the internal light to improve the image of the optical display device.

Hereinafter, an optical display device according to another embodiment of the present invention will be described with reference to FIG. 8 is a cross-sectional view of an optical display device according to another embodiment of the present invention.

8, an optical display apparatus 500 according to another embodiment of the present invention includes a display unit 350b, a window layer 390 formed on a display unit 350b, a display unit 350b, May include a transparent electrode body, and the transparent electrode body may include the entire transparency according to the embodiments of the present invention. Is substantially the same as the optical display device according to an embodiment of the present invention, except that the device can be driven only by the display part 350b, the polarizing plate is excluded, and the transparent electrode body is included in the display part 350b.

The display portion 350b may include an LCD, an OLED, or an optical element including an LED element formed on the substrate. Although not shown, the display portion 350b may include a transparent electrode body 380 formed therein . Specifically, the transparent electrode member 380 may include the entire transparency according to the embodiments of the present invention, and may include, for example, a touch panel screen.

Although not shown in FIG. 8, an adhesive layer is further formed between the display portion 350b and the window layer 390, thereby increasing the mechanical strength of the optical display device. The pressure-sensitive adhesive layer may be formed of a pressure-sensitive adhesive composition comprising a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent. The pressure-sensitive adhesive composition is as described above.

Further, although not shown in FIG. 8, a polarizing plate is further formed under the display unit 350b, so that polarization of the internal light can be induced to improve the image of the optical display device.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Example 1

(1) Preparation of metal nanowire composition

37 parts by weight of a solution containing a metal nanowire (product name: Clearohm ink G4-05 (manufactured by Cambrios)) was added to 63 parts by weight of distilled water of ultra pure water and stirred to prepare a metal nanowire composition.

(2) Preparation of Composition for Matrix

3% by weight of SR9020 (propoxylated (3) glyceryl triacrylate) as a trifunctional (meth) acrylate oligomer, 11% by weight of EB9390 (Urethane acrylate oligomer) (100 parts by weight) of a mixture of 11% by weight of AR-110 (Daikin) and 75% by weight of a mixture of SST250U (Ranco, butyl acetate dispersion, solid content 50%) as nano silica was mixed with 100 parts by weight of an antioxidant mixture 2.7 parts by weight of a phenol antioxidant Irganox 1010 and a phosphorus antioxidant Irgafos 168 (BASF)), 5.4 parts by weight of adhesion promoter KBM-303 (SHIN-ETSU), initiator Irgacure 184 (CIBA) 2.7 By weight was prepared. To 3.3 parts by weight of the obtained mixture, 96.7 parts by weight of methyl isobutyl ketone was added to prepare a composition for a matrix.

A metal nanowire composition was coated on a polycarbonate (PC) film (Teijin, thickness: 50 占 퐉) by a spin coater and dried in an oven at 80 占 폚 for 2 minutes and at 140 占 폚 for 2 minutes to form a metal nanowire network layer Respectively. Then, the composition for a matrix was coated on the metal nanowire network layer by a spin coater, dried in an oven at 80 ° C for 2 minutes, dried in an oven at 120 ° C for 2 minutes, and UV-cured at 300 mJ / cm ² to obtain a conductive layer having a thickness of 90 nm Lt; / RTI >

Examples 2 to 6 and Comparative Examples 1 to 6

The transparency was prepared in the same manner as in Example 1 except that the composition for a matrix was changed to the contents shown in the following table. The content of the surfactant (E) is expressed in parts by weight based on 100 parts by weight of (A) + (B) + (C) + (D).

(A) (B) (B ') (C) (D) (E) (b1) (b2) (c1) (c2) Example 1 11 3 0 0 11 0 75 0 Example 2 11 3 0 0 11 0 75 0.02 Example 3 12 4 0 0 0 2 82 0.02 Example 4 19 6 0 0 19 0 56 0.02 Example 5 26 8 0 0 25 0 41 0.02 Example 6 11 0 3 0 11 0 75 0.02 Comparative Example 1 0 14 0 0 11 0 75 0.02 Comparative Example 2 14 0 0 0 11 0 75 0.02 Comparative Example 3 12 5 0 0 0 0 83 0.02 Comparative Example 4 44 13 0 0 43 0 0 0.02 Comparative Example 5 70 30 0 0 0 0 0 0 Comparative Example 6 10 0 0 4 11 0 75 0.02

(A) Five or Six Functional Urethane (Meth) Acrylic Oligomer: Entis, EB9390 (hexafunctional urethane acrylate oligomer, weight average molecular weight 1000) was used.

(B) a trifunctional (meth) acrylic monomer

(b1) Alkoxy-modified trifunctional (meth) acrylic monomer: Sartomer, SR9020 (propoxylated glyceryl triacrylate) was used.

(b2) Trimeric polypropane triacrylate (TMPTA) manufactured by Entis, Inc. was used as the non-alkoxy-modified trifunctional (meth) acrylic monomer.

(B ') monofunctional monomer: Sartomer, SR256 (2- (2-ethoxyethoxy) ethyl acrylate) was used.

(C) a fluorine-containing monomer

(c1) Daikin, AR-110

(c2) Kyoeisha, LINC-3A

(D) Nano-silica: SST250U (butyl acetate dispersion, solid content 50%, surface treatment with methyl / methacrylate, average particle size of 10 nm to 15 nm) was used.

(E) Surfactant: Dynol 980 (siloxane-based nonionic surfactant) from Air Products was used.

The following transparencies of Examples 1 to 6 and Comparative Examples 1 to 6 were evaluated for the following physical properties, and the results are shown in Table 2 below. The etching and the reliability were evaluated only when the rubbing evaluation was OK.

Property evaluation method

(1) Haze and transmittance (%): The haze and the transmittance were measured using a haze meter (NDH-2000) at a wavelength of 400-700 nm with respect to the entire transparency.

(2) Transmission b *: Transmission color coordinates were measured using a CM3600A (Konica Minolta) at a wavelength of 400 nm to 700 nm with respect to the entire transparency.

(3) Surface resistance (Ω / □): The sheet resistance was measured for the entire transparency using a non-contact sheet resistance measuring instrument EC-80P (NAPSON).

(4) Etching time: Wet etching was performed by dipping in a beaker by photolithography, and an on-set time (unit: second) in which the silver nano wire disappeared by an optical microscope was measured .

(5) Rubbing: Isopropanol was dropped as a syringe on the conductive layer and rubbed with a wiper 10 times, and then the appearance change and resistance change were confirmed. &Quot; OK "when the appearance change by the naked eye was not changed, " NG" when the resistance change rate according to the following formula 1 was 10% or less, and when the appearance change or the resistance change rate exceeded 10%.

(6) Reliability: Transparency of Examples and Comparative Examples A transparent adhesive film (3M, Optically Clear Adhesives 8215) having a thickness of 125 占 퐉 and a PET film (Toyobo, A4300) having a thickness of 100 占 were successively laminated on the entire surface, . (A) was measured by a non-contact type method using a non-contact type sheet resistance measuring device EC-80P (NAPSON), and the sheet was allowed to stand at 85 ° C and 85% relative humidity for 240 hours. b) were measured. The resistance change rate was calculated by the following formula 1 to evaluate the reliability. When the resistance change rate is 10% or less, it is judged to be reliable.

[Formula 1]

Resistance change rate = b-a / a x 100

(7) Etching Appearance: After etching, the outer appearance of the patterned film was observed by observation with a microscope and an optical microscope. "Good" when the line width is uniform and fully etched when observed with an optical microscope, and "Bad" otherwise. In the evaluation, Respectively.

Haze (%) Transmittance (%) Transmission b * Sheet resistance (Ω / □) Etching Time (sec) Rubbing Reliability (%) Etching appearance Example 1 0.76 91.36 0.80 48.31 180 OK 4 Good Example 2 0.77 91.33 0.83 46.44 180 OK 5 Good Example 3 0.78 91.15 0.82 47.63 120 OK 5 Good Example 4 0.81 91.30 0.82 44.49 180 OK 6 Good Example 5 0.91 90.67 0.84 44.99 210 OK 6 Good Example 6 0.79 91.14 0.83 47.35 120 OK 7 Good Comparative Example 1 0.82 91.08 0.80 49.46 - NG - - Comparative Example 2 0.80 91.16 0.82 47.34 - NG - - Comparative Example 3 0.82 91.14 0.91 44.04 240 OK 9 Bad Comparative Example 4 1.07 90.05 0.92 47.68 120 OK 10 Good Comparative Example 5 1.09 89.79 0.98 50.23 - NG - - Comparative Example 6 0.90 91.02 0.80 52.84 - NG - -

As shown in Table 2, the transparency of the present invention has good optical properties such as transmittance, haze and transmission b *, as well as low sheet resistance, and is excellent in reliability, durability and etching appearance.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims

A base layer, and a conductive layer formed on the base layer,
Wherein the conductive layer comprises metal nanowires and a matrix,
The matrix preferably has a transparency formed of a composition for a matrix comprising (A) a pentafunctional or hexafunctional urethane (meth) acrylic oligomer, (B) a trifunctional (meth) acrylic monomer, (C) a fluorine- all.

The transparency of claim 1, wherein the (A) pentafunctional or hexafunctional urethane (meth) acrylic oligomer has a weight average molecular weight of 1,000 to 5,000.

The transparency as claimed in claim 1, wherein the trifunctional (meth) acrylic monomer (B) comprises a trifunctional (meth) acrylic monomer modified with an alkoxy group.

The transparency of claim 1, wherein the (D) nanosilica has an average particle diameter of 10 nm to 200 nm.

The transparency composition according to claim 1, wherein the matrix composition comprises 30% by weight to 90% by weight of the total weight of (D) the nano-silica in (A) + (B) + (C) + (D).

The transparency of claim 1, wherein the matrix composition further comprises a surfactant.

The transparent body according to claim 1, wherein the composition for matrix further comprises at least one of an initiator, an adhesion promoter and an antioxidant.

The method of claim 1, wherein the metal nanowire is selected from the group consisting of Ag, Cu, Pt, Sn, Fe, Ni, Co, , Zinc (Zn), copper (Cu), indium (In), and titanium (Ti).

The transparent conductor according to claim 1, further comprising an overcoat layer formed on the conductive layer.

The transparency of 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 the base layer.

The transparency of claim 1, wherein the conductive layer is patterned.

Forming a metal nanowire network layer on the substrate layer,
(B) a trifunctional (meth) acrylic monomer, (C) a fluorine-based monomer, and (D) a nanosilica on the metal nanowire network layer, A method for producing a transparent transparency comprising forming a conductive layer with a composition.

13. The method of claim 12, further comprising forming an overcoat layer.

An optical display device comprising the entire transparency of any one of claims 1 to 11.

The liquid crystal display according to claim 14, wherein the optical display device comprises a display portion, a polarizing plate formed on the display portion, a transparent electrode body formed on the polarizing plate, and a window layer formed on the transparent electrode body, The optical display device according to any one of claims 1 to 11, wherein the transparency is the entirety.

16. The optical display apparatus of claim 15, wherein the display unit further comprises a polarizer at a lower portion thereof.

The optical display device according to claim 15, wherein the optical display further comprises at least one adhesive layer between the display part and the polarizing plate, between the polarizing plate and the transparent electrode, or between the transparent electrode and the window layer.

The liquid crystal display according to claim 14, wherein the optical display device comprises a display portion, a transparent electrode body formed on the display portion, a polarizing plate formed on the transparent electrode body, and a window layer formed on the polarizing plate, The optical display device according to any one of claims 1 to 11, wherein the transparency is the entirety.

19. The optical display device of claim 18, wherein the display unit further comprises a polarizer at a lower portion thereof.

The optical display device according to claim 18, wherein the optical display device further comprises at least one adhesive layer between the display portion and the transparent electrode body, between the transparent electrode body and the polarizing plate, or between the polarizing plate and the window layer.

15. The optical display device according to claim 14, wherein the optical display device comprises a display portion and a window layer formed on the display portion,
Wherein the display portion includes a transparent electrode body, and the transparent electrode body is the entire transparency of any one of Claims 1 to 11.

The optical display device according to claim 21, wherein the optical display device further comprises an adhesive layer between the display portion and the window layer.

22. The optical display apparatus of claim 21, wherein the display section further comprises a polarizing plate on an upper portion or a lower portion.