KR20160069617A - Hard coating layer, method for forming thereof and display deviece comprising the same - Google Patents

Abstract

The present invention relates to a hard coating layer which includes: a unit represented by chemical formula 1; a unit represented by chemical formula 2; and zinc oxide, wherein the content of zinc oxide in the hard coating layer is 0.03-0.6 wt%. The hard coating layer of the present invention can exhibit anti-reflective, fingerprint resistant, and antibacterial properties with only a single layer.

Description

Technical Field [0001] The present invention relates to a hard coating layer, a method of manufacturing the same, and a display device including the hard coating layer.

The present invention relates to a hard coating layer, a method of manufacturing the same, and a display device including the hard coating layer. More particularly, the present invention relates to a hard coating layer capable of realizing antibacterial, antireflection and anti- To a display device.

BACKGROUND ART [0002] Recently, a liquid crystal display device (LCD), an organic light emitting display (OLED), an electrophoretic display (EPD), a plasma display panel (PDP), a field emission display device (FED), an electroluminescence display device (ELD), and an electro-wetting display (EWD) Has been used in the field.

On the other hand, a film or a coating layer having an anti-reflection function is applied to the flat panel display device to prevent glare due to external light incidence. Conventionally, in order to perform an antireflection function, a method of applying multilayer reflective films, which are manufactured by depositing inorganic derivative materials having different refractive indexes in 20 or more layers under vacuum conditions, or forming nano-sized regular protrusions on the substrate surface Respectively. However, in the case of the above-mentioned multilayer reflective film, since the manufacturing process is complicated and a high temperature is required for vapor deposition, it is not suitable for use in materials such as plastics, and the interlayer adhesive force is not excellent and problems such as peeling of the coating film occur. In addition, in the case of the method of forming the nano-sized protrusions, since the manufacturing cost is very high and the etching process is used to form the protrusions, there is a problem that the material of the usable substrate is limited. In addition, there is a problem that the image quality of the display device may be deteriorated because the diffusions are generated by the protrusions and the haze increases.

Meanwhile, as the number of display devices to which the touch function has been applied recently, researches are being conducted on films or coating films that can realize the fingerprint performance together with the anti-reflection function. Korean Patent No. 10-1244883 (Patent Document 1) discloses an antireflection film for performing antireflection and fingerprint function by forming a plurality of protruding structures on a substrate surface by dry etching a substrate, depositing inorganic particles thereon, Lt; / RTI > However, in the case of the method of Patent Document 1, since the etching process for forming the protruding structure and the deposition process for the inorganic particles must be performed, the manufacturing process is complicated, the manufacturing cost is high, and the haze The image quality of the display device may be deteriorated. In addition, since the inorganic particle layer is formed in a multi-layered structure in which the inorganic particle layer is present on the protruding structure, the thickness of the inorganic particle layer is increased.

On the other hand, as the use of electronic products such as smart phones and tablet PCs has increased recently, bacterial growth has occurred in these devices due to hand or saliva, and bacterial infections are increasingly occurring from such proliferated bacteria. Accordingly, interest in an electronic product having an antibacterial function is increasing.

The present invention has been made to solve the above problems, and it is an object of the present invention to provide a hard coating layer which can be produced by a simple manufacturing process, and which can realize antibacterial, antireflection and anti- .

It is another object of the present invention to provide a display device having excellent anti-reflection, anti-microbial, and anti-fingerprint characteristics, including the hard coating layer.

According to one embodiment, the hard coating layer of the present invention comprises a unit represented by the following general formula (1); A unit represented by the following formula (2); And zinc oxide, wherein the zinc oxide is contained in an amount of 0.03 wt% to 0.6 wt% in the hard coat layer.

[Chemical Formula 1]

In the [Formula _1], R 1 is hydrogen or C _{1 ~ 10} alkyl group, R ₂ is hydrogen or C _{1 ~ 10} alkyl group, R ₃ is one or more hydrogen is a C _{1 ~ 10} alkyl group substituted with F .

(2)

In the above formula (2), R ₄ and R ₅ are each independently a C _1-10 alkyl group, and R ₆ is a C _1-20 alkyl group substituted by at least one hydrogen atom.

According to another embodiment, the method for producing a hard coat layer of the present invention is a method for producing a hard coat layer comprising a fluorine-based polymer containing a repeating unit represented by the following formula (3), a fluorine-based silane represented by the following formula Applying a composition for hard coating; And curing the hard coating composition. At this time, the hard coating composition contains zinc oxide in an amount of 0.03 parts by weight to 0.5 parts by weight based on 100 parts by weight of the composition for hard coating.

(3)

The [formula 3], R ₁ is hydrogen or C _{1 ~ 10} alkyl group, R ₂ is hydrogen or C _{1 ~ 10} alkyl group, R ₃ is an at least one hydrogen is substituted by F C _{1 ~ 10} alkyl group, .

[Chemical Formula 4]

R _4, R ₅ and R ₇ are each independently a C _1-10 alkyl group, and R ₆ is a C _1-20 alkyl group substituted by at least one hydrogen atom.

According to yet another embodiment, a display device of the present invention includes a display panel; And the hard coating layer of the present invention, which is disposed on the display panel and is formed as a single layer.

The hard coating layer according to the present invention can realize both antireflection, fingerprint proofing and antibacterial performance with only a single layer. Therefore, when the hard coating layer is applied, a thin display device can be economically realized.

In addition, the hard coating layer according to the present invention can simplify the manufacturing process and reduce the processing time and process cost.

1 is a view showing a display device according to an embodiment of the present invention.
2 and 3 are views for explaining a display panel of a display device according to the present invention.
4 is a view illustrating a display device according to another embodiment of the present invention.
5 is a view illustrating a display device according to another embodiment of the present invention.
6 and 7 are views for explaining a touch panel of a display device according to the present invention.
8 is a photograph showing the results of measurement of the antibacterial activity of the hard coat layer prepared in Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention.
9 is a graph showing the extent of increase of the reflectance depending on the content of the zinc oxide particles.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described below, but may be embodied in various forms. The following embodiments are merely intended to provide a complete disclosure of the present invention and are provided to enable those of ordinary skill in the art to fully understand the scope of the invention and that the present invention is defined by the scope of the claims do.

The shapes, sizes, ratios, angles, numbers, and the like described in the drawings for describing the embodiments of the present invention are merely exemplary and the present invention is not limited thereto. Like reference numerals refer to like elements throughout the specification. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

In the case where the word 'includes', 'having', 'done', etc. are used in this specification, other parts can be added unless '~ only' is used. Unless the context clearly dictates otherwise, including the plural unless the context clearly dictates otherwise.

In interpreting the constituent elements, it is construed to include the error range even if there is no separate description.

In the case of a description of the positional relationship, for example, if the positional relationship between two parts is described as 'on', 'on top', 'under', and 'next to' Or " direct " is not used, one or more other portions may be located between the two portions.

In the case of a description of a temporal relationship, for example, if a temporal posterior relationship is described by 'after', 'after', 'after', 'before', etc., 'Is not used and is not contiguous.

The first, second, etc. are used to describe various components, but these components are not limited by these terms. These terms are used only to distinguish one component from another. Therefore, the first component mentioned below may be the second component within the technical spirit of the present invention.

Each of the features of the various embodiments of the present invention may be partially or wholly combined or combinable with each other, and technically various interlocking and driving are possible, and each embodiment may be practiced independently of one another or in association with one another. You may.

Hereinafter, the present invention will be described in more detail.

The inventors of the present invention have conducted intensive studies to develop a hard coating layer for a display device which is simple in manufacturing process and can perform various functions as one layer. As a result, it has been found that a fluororesin composition containing a fluoropolymer, a fluorosilane compound and a specific content of zinc oxide It has been found that the above object can be achieved when a hard coating layer is formed using a composition for hard coating, and the present invention has been completed.

First, a method for producing the hard coat layer of the present invention will be described.

The hard coating layer according to the present invention is prepared by applying a hard coating composition comprising a fluorine-based polymer, fluorine-based silane and zinc oxide on a substrate, and curing the composition.

At this time, the fluorine-based polymer is intended to realize a high hardness, antireflection effect and fingerprint effect, and it may preferably be a fluorine-containing urethane-modified polymer formed using urethane acrylate. Such a fluorine-based polymer not only has an antireflection effect because of its low refractive index, but also has an effect of improving the surface hardness of the coating layer after curing by the urethane functional group introduced from urethane acrylate. Further, the fluorine-based polymer contains fluorine excellent in water repellency and oil repellency, so that a fingerprint effect can be obtained. On the other hand, the fluorinated polymer used in the present invention preferably has a weight average molecular weight of about 1,000 to 100,000.

More preferably, the fluorine-based polymer may include a repeating unit represented by the following formula (3).

(3)

In the formula (3), R ₁ is hydrogen or an alkylene group having _{1 to 10} carbon atoms, more preferably an alkylene group having _{1 to 4} carbon atoms.

In addition, the R ₂ is hydrogen R ₂ is hydrogen or C _{1 ~ 10} alkyl group, more preferably an alkyl group of C _{1 ~ 4.}

R ₃ is a C _1-10 alkyl group in which at least one hydrogen is substituted by F, more preferably - (CF ₂ ) ₁ -CF ₃ . Here, l is an integer of 0 to 10. As described above, when F is included at the end of R ₃ , fluorine is likely to be disposed on the surface side of the coating layer, and as a result, it is more effective in implementing the fingerprint effect.

The fluoropolymer is preferably contained in an amount of 10 parts by weight to 50 parts by weight based on 100 parts by weight of the composition for hard coating. When the content of the fluorine-based polymer satisfies the above range, a coating layer having excellent antireflection and fingerprint resistance and having high hardness can be obtained.

Next, the fluorine-based silane is used for imparting the fingerprint performance to the coating layer, and may preferably be a compound represented by the following formula (4).

[Chemical Formula 4]

In the formula (4), R _4, R ₅ and R ₇ are each independently a C _1-10 alkyl group, preferably a C _1-4 alkyl group.

R ₆ is a C _1-20 alkyl group in which at least one hydrogen is substituted by F, and more preferably - (CF ₂ ) _m -CF ₃ . Herein, m is an integer of 1 to 10. As described above, when F is included at the end of R ₆ , fluorine is likely to be disposed on the surface side of the coating layer, and as a result, it is more effective in implementing the fingerprint effect.

It is preferable that the fluorine-based silane is contained in an amount of 10 to 40 parts by weight based on 100 parts by weight of the composition for hard coating. When the content of the fluorine-based silane satisfies the above range, an excellent fingerprint effect can be obtained.

Next, the zinc oxide (ZnO) is used to impart antimicrobiality to the coating layer, and is contained in an amount of 0.03 parts by weight to 0.5 parts by weight based on 100 parts by weight of the hard coating composition. When the content of zinc oxide is less than 0.03 parts by weight, the antimicrobial effect is insignificant. When the content is more than 0.5 parts by weight, the antireflection performance sharply decreases.

On the other hand, the zinc oxide preferably has an average particle diameter of about 15 nm to 25 nm. When the average particle diameter of the zinc oxide satisfies the above range, it is possible to form a hard coat layer having excellent antireflection and antimicrobial properties.

Meanwhile, the hard coating composition may further contain a solvent for viscosity control and the like. The solvent may be, for example, an alcohol-based organic solvent and may be, for example, dipropylene glycol (DPG), monoethyleneglycol (MEG), diethylene glycol (DEG), triethylene glycol ), Tripropylene glycol, 1,4-butanediol (BDO), 1,5-pentanediol, 1,6-hexanediol, 1,3-propanediol, 1,2-propanediol and 2,2- , 3-propanediol (neopentyl glycol), and the like.

The solvent may be contained in an amount of 20 parts by weight or less, preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the composition for hard coating.

On the other hand, the hard coating composition may further contain an acrylic monomer as necessary. The acrylic monomer may be a (meth) acrylate monomer having at least one functional group for controlling the viscosity of the hard coating composition and improving the hardness and curling property of the coating layer. More specifically, the acrylic monomer may be at least one selected from the group consisting of dipentaerythritol penta (meth) acrylate, dipentaerythol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate, tri (Meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, 1,3-butanediol di (meth) acrylate, propylene glycol (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, diethyleneglycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (Meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, and isobornole (meth) acrylate.

The acrylic monomer is contained in an amount of 20 parts by weight or less, preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the composition for hard coating.

The hard coating composition may further comprise a photopolymerization initiator. As the photopolymerization initiator, a photopolymerization initiator generally known in the art can be used without limitation. For example, at least one selected from the group consisting of hydroxy ketones, aminoketones and hydrogen recyclable photopolymerization initiators is used . More specifically, the photopolymerization initiator may be selected from the group consisting of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, diphenyl ketone benzyl dimethyl ketal, 2- 1-phenyl-1-on, 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylacetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, Acetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, and combinations thereof.

The photopolymerization initiator may be contained in an amount of 5 parts by weight or less, preferably 1 to 5 parts by weight, and more preferably 1 to 3 parts by weight, based on 100 parts by weight of the composition for hard coating.

The hard coating composition is coated on one side or both sides of the substrate, and then irradiated with active energy rays such as ultraviolet rays to cure the hard coating layer. At this time, the substrate may be a light-transmitting substrate, and the material thereof is not particularly limited. For example, the substrate may be a glass substrate or a plastic substrate.

On the other hand, the substrate may be a substrate existing separately from a display panel or a touch panel of a display device, which will be described later, or may be a substrate constituting a part of a display panel or a touch panel. When a hard coating layer is formed using a substrate constituting a display panel or a part of a touch panel, the hard coating layer is formed integrally with the display panel or the touch panel.

According to the method of the present invention, it is possible to form a hard coat layer having anti-reflection, anti-fingerprint and antimicrobial effects through a simple method of applying a hard coating composition and photo-curing the composition, have.

On the other hand, the hard coating layer according to the present invention manufactured through the above process includes a unit derived from a fluorine-based polymer, a unit derived from a fluorine-based silane, and zinc oxide.

In this case, the unit derived from the fluorine-based polymer may be represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1), R ₁ is hydrogen or an alkylene group having _{1 to 10} carbon atoms, preferably an alkylene group having _{1 to 4} carbon atoms. On the other hand, R ₂ is hydrogen or an alkyl group having _{1 to 10} carbon atoms, preferably an alkyl group having _{1 to 4} carbon atoms. R ₃ is a C _1-10 alkyl group in which at least one hydrogen is substituted by F, preferably - (CF ₂ ) ₁ -CF ₃ . Here, l is an integer of 0 to 10.

The unit represented by the formula (1) is formed by reacting a fluorinated polymer containing a repeating unit represented by the formula (3) and a fluorinated silane compound represented by the formula (4). The hard coating layer has a high hardness, Effect and a fingerprint effect.

Next, the unit derived from the fluorine-based silane may be represented by the following formula (2).

(2)

In the above formula (2), R ₄ and R ₅ are each independently an alkyl group having _{1 to 10} carbon atoms, preferably an alkyl group having _{1 to 4} carbon atoms. R ₆ is a C _1-20 alkyl group in which at least one hydrogen is substituted by F, and more preferably - (CF ₂ ) _m -CF ₃ . Herein, m is an integer of 1 to 10.

On the other hand, the unit represented by the formula (2) is formed by reacting the fluorine-based silane compound represented by the formula (4) with a fluorine-based polymer or a hydroxyl group or a ketone group existing on the surface of the substrate, .

On the other hand, the hard coat layer according to the present invention contains, in a molar ratio of 1: 1 to 2: 1, a unit represented by the formula (1): [Formula 2] To 1.5: 1. ≪ / RTI >

Next, the zinc oxide imparts antimicrobial properties to the hard coat layer, and is contained in an amount of about 0.03% to 0.6% by weight in the hard coat layer. When the content of zinc oxide in the hard coat layer is less than 0.03% by weight, the antibacterial effect is insignificant. When the content of zinc oxide is more than 0.6% by weight, the antireflection performance sharply decreases.

The zinc oxide preferably has an average particle diameter of about 15 nm to 25 nm. When the average particle diameter of the zinc oxide satisfies the above range, it is possible to form a hard coat layer having excellent antireflection and antimicrobial properties.

Meanwhile, the hard coating layer of the present invention may further include a unit derived from an acrylic monomer to improve hardness and curling characteristics of the coating layer. Here, the acrylic monomer may be a (meth) acrylate monomer having at least one functional group, and examples thereof include dipentaerythritol penta (meth) acrylate, dipentaerythol hexa (meth) acrylate, pentaerythritol (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, styrene tri (meth) acrylate, Acrylate, propylene glycol (meth) acrylate, 1,3-butanediol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate, (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, , Neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2- (Meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (Meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate and isobonole (meth) acrylate.

The hard coating layer of the present invention as described above is a single layer and can provide excellent anti-reflection, anti-fingerprint and antibacterial effects. More specifically, the hard coat layer of the present invention has a reflectance of 2% or less, preferably 1.7% or less, an antibacterial activity measured by JIS Z 2801 of 3 or more, preferably 4 or more, and a water contact angle of 100 ° or more , Preferably about 100 DEG to 130 DEG. On the other hand, when the antibacterial activity measured by the above JIS Z 2801 is 3 or more, it means that the antibacterial activity is 99.9% or more, and when it is 4 or more, the antibacterial activity is 99.99% or more.

Next, a display device according to the present invention will be described. 1 to 5 show implementations of display devices according to the present invention. Hereinafter, a display device according to the present invention will be described in detail with reference to the drawings.

1 shows a display device according to a first embodiment of the present invention. 1, the display device according to the present invention includes a display panel 300 and a hard coating layer 100. [ At this time, the hard coat layer 100 is the same as that described above. Therefore, the description of the hard coating layer 100 will be omitted, and the remaining components of the display device will be described below.

First, the display panel 300 may be a liquid crystal display panel or an organic light emitting display panel.

FIG. 2 shows a case where the display panel 300 is a liquid crystal display panel. As shown in FIG. 2, the liquid crystal display panel 300 includes a first substrate 301 and a second substrate 302 bonded together with a liquid crystal layer 380 interposed therebetween. The hard coating layer 100 may be coated on the exposed surface of the first substrate 301 or the second substrate 302 of the display panel 300.

Although not shown in the drawing, a backlight unit may be disposed under the liquid crystal display panel 300. Also, although not shown in the figure, the display panel 300 may include a polarization unit to which a polarization function is added.

On one side of the first substrate 301, a gate line and a data line are arranged so as to cross each other with a gate insulating layer 352 interposed therebetween to define a pixel region. The pixel region is provided with a thin film transistor (TFT), which is connected to the pixel electrode 357 provided in each pixel region and the contact hole formed in the insulating layer 356. That is, the first substrate 301 may be referred to as a thin film transistor substrate.

The thin film transistor TFT includes a gate electrode 351, a gate insulating film 352, a semiconductor layer 353, a source electrode 354, and a drain electrode 355. Although the bottom gate structure in which the gate electrode 351 of the thin film transistor is disposed below the semiconductor layer 353 is shown in the drawing, the structure is not limited thereto, and the gate electrode 351 And a top gate structure disposed on the semiconductor layer 353. In addition, the configuration and the like of the thin film transistor can be variously modified and modified within a range not departing from the technical idea of the present invention.

In addition, on one surface of the second substrate 302 of the liquid crystal display panel 300, a grid-like black (not shown) covering a pixel region and covering a non-display region in which a thin film transistor A matrix 371 is formed. Inside these lattices, R (red), G (green), and B (blue) color filter layers 372 which are sequentially and repeatedly arranged corresponding to the respective pixel regions are included and transparent common electrodes 373 covering all of them . That is, the second substrate 302 may be a color filter substrate.

A first alignment layer 358 and a second alignment layer 374 are interposed between the liquid crystal layer 380 and the pixel electrode 357 and between the liquid crystal layer 380 and the common electrode 373. The first alignment layer 358 and the second alignment layer 374 can align the initial alignment state of the liquid crystal molecules and the alignment direction uniformly.

However, the drawings illustrate the liquid crystal display panel according to the present invention in a simplified manner, but the present invention is not limited thereto. For example, although the thin film transistor is represented by a single thin film transistor in the drawing, the thin film transistor may be composed of one or more thin film transistor combinations depending on the characteristics of operation.

In addition, a method of controlling the arrangement of liquid crystal molecules can be variously applied to an IPS (In Plane Switching) mode or an FFS (Fringe Field Switching) mode in addition to a TN (Twisted Nematic) mode and a VA (Vertical Alignment) mode. Although the pixel electrode 357 is formed on the first substrate 301 and the common electrode 373 is formed on the second substrate 302 in the drawing, the pixel electrode 357 and the common electrode 373 ) Can also be changed and modified. The pixel electrode 357 and the common electrode 373 may be formed on the first substrate 301 in an IPS (In Plane Switching) mode or an FFS (Fringe Field Switching) mode.

The liquid crystal display panel 300 may include a thin film transistor, a color filter layer and a black matrix formed on a first substrate 301 and a second substrate 302 with a liquid crystal layer interposed therebetween. Or a liquid crystal display panel having a color filter on transistor (COT) structure. That is, a thin film transistor may be formed on the first substrate 301, a protective film may be formed on the thin film transistor, and a color filter layer may be formed on the protective film. In addition, a pixel electrode is formed on the first substrate 301 to be in contact with the thin film transistor. At this time, in order to improve the aperture ratio and simplify the mask process, the black matrix may be omitted, and the common electrode may be formed to serve also as the black matrix.

That is, the liquid crystal display panel 300 is not limited to the representation of the drawings, and various changes and modifications can be made without departing from the technical idea of the present invention.

3, the display panel 300 is an organic light emitting display panel. Referring to FIG. 3, the display panel 300 is an organic light emitting display panel.

3, the organic light emitting display panel 300 includes a first substrate 301 on which a thin film transistor (TFT) and an organic light emitting diode OL electrically connected to the thin film transistor TFT are formed, And a second substrate 302 for protecting the organic light emitting diode OL. At this time, the hard coating layer 100 of the present invention may be coated on the exposed surface of the first substrate 301 or the second substrate 302 of the display panel 300.

An encapsulation layer 324 may be formed between the first substrate 301 and the second substrate 302. Although the encapsulation layer 324 is shown as a single layer in the drawing, the encapsulation layer 324 may be composed of a plurality of layers such as a protective layer and an adhesive layer. Also, although not shown in the figure, the display panel 300 may include a polarization unit to which a polarization function is added.

A thin film transistor (TFT) is formed on one surface of the first substrate 301 of the organic light emitting display panel 300. The thin film transistor (TFT) includes a semiconductor layer 311, a gate electrode 313, a source electrode 315, and a drain electrode 316.

The semiconductor layer 311 includes a source region 311a, a channel region 311b and a drain region 311c and a gate insulating layer 312 is formed on the semiconductor layer 311. The gate insulating layer 312 A gate wiring 313 and a gate electrode 313 branched from the gate wiring are formed. An interlayer insulating film 314 is formed on the gate wiring and the gate electrode 313.

A source electrode 315 branched from the data line, and a drain electrode 316 spaced apart from the source electrode 315 by a predetermined distance, the data line crossing the gate line with the interlayer insulating film 314 therebetween, Is formed. The source electrode 315 and the drain electrode 316 are electrically connected to each other through an interlayer insulating layer 314 formed on the gate electrode 313 and a contact hole formed through the gate insulating layer 312, And is in contact with the source region 311a and the drain region 311c.

A protective film 317 is formed on the source electrode 315 and the drain electrode 316 and a contact hole exposing the drain electrode 316 is formed on the protective film 317. The exposed drain electrode 316 is electrically connected to the connection electrode 318 formed on the passivation layer 317. A planarization film 319 is formed on the entire surface of the first substrate 301 including the thin film transistor TFT and a contact hole exposing the connection electrode 318 is formed on the planarization film 319.

The organic light emitting diode OL is electrically connected to the TFT through a contact hole formed in the planarization layer 319. [ The organic light emitting device OL includes a lower electrode 320, an organic light emitting layer 322, and an upper electrode 323.

More specifically, the lower electrode 320 of the organic light emitting diode OL is formed on the exposed connection electrode 318. Although the lower electrode 320 of the organic light emitting diode OL and the drain electrode 316 of the thin film transistor TFT are shown as being connected through the connection electrode 318 in the drawing, the connection electrode 318 is omitted, The lower electrode 320 of the light emitting device OL and the drain electrode 116 of the thin film transistor TFT may be directly in contact with each other through the planarization film 319 having the contact holes.

A bank pattern 321 is formed on the lower electrode 320 to expose the lower electrode 320 in units of pixel regions. An organic light emitting layer 322 is formed on the exposed lower electrode 320. The organic light emitting layer 322 may be formed of a single layer made of a light emitting material or may include a hole injection layer, a hole transporting layer, an emitting material layer, and an electron transporting layer an electron transporting layer, and an electron injection layer.

An upper electrode 323 is formed on the organic light emitting layer 322. When the lower electrode 320 is an anode, the upper electrode 323 is a cathode, and when the lower electrode 320 is a cathode, the upper electrode is an anode .

A sealing portion is formed on the first substrate 301 on which the thin film transistor TFT and the organic light emitting diode OL are formed. For example, on the upper electrode 323, a sealing layer 324 for protecting the display elements is formed. The sealing layer 324 may be formed of a plurality of layers and may be bonded to the second substrate 302. The second substrate 302 may be an encapsulation substrate for encapsulation. However, the sealing part disposed on the first substrate 301 is not limited to the sealing layer 324 and the second substrate 302, and may be formed by various sealing methods known in the art to prevent the inflow of oxygen or moisture. Additional applications can be applied.

The configuration of the display device according to the present invention is not limited to the drawings, and various changes and modifications can be made without departing from the technical idea of the present invention.

4 shows a display device according to a second embodiment of the present invention. Hereinafter, a display device according to a second embodiment of the present invention will be described with reference to FIG.

Referring to FIG. 4, the display device according to the second embodiment of the present invention includes a display panel 300 and a base substrate 200 disposed between the hard coating layer 100. That is, a base substrate 200 is formed on the display panel 300, and a hard coating layer 100 is formed on the base substrate 200. The hard coating layer 100 may be coated on the upper surface of the base substrate 200. Since the hard coating layer 100 and the display panel 300 are the same as those described above, a detailed description thereof will be omitted.

Meanwhile, the base substrate 200 may be a polarizing plate. In detail, the base substrate 200 may be a linear polarizer or a circular polarizer. When the display panel 300 is a liquid crystal display panel, the base substrate 200 may be a linear polarizer. In addition, when the display panel 300 is an organic light emitting display panel, the base substrate 200 may be a circular polarizer for preventing reflection of external light.

Although the base substrate 200 is disposed on only the upper portion of the display panel 300 in the drawing, when the base substrate 200 is a polarizer, the base substrate 200 is divided into upper and lower portions of the display panel 300, As shown in FIG. For example, the display panel 300 is a liquid crystal display panel, and the base substrate 200 is a linear polarizer, and may be disposed on the upper and lower surfaces of the display panel 300 of the base substrate 200. At this time, the hard coating layer 100 may be formed on the upper surface of the base substrate 200 disposed on the upper surface of the display panel 300.

In addition, the base substrate 200 may be a transparent substrate. That is, the light transmitted through the base substrate 200 may be unpolarized light. At this time, the base substrate 200 may be glass or plastic. For example, the base substrate 200 can be made of a material selected from the group consisting of glass, cellulose esters (e.g., cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and nitrocellulose), polyimide, polycarbonate, For example, polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene 1,2-diphenoxyethane-4,4'-dicarboxylate, and polybutylene terephthalate) , Polystyrenes such as syndiotactic polystyrenes, polyolefins such as polypropylene, polyethylene and polymethylpentene, polysulfone, polyethersulfone, polyarylate, polyether-imide, polymethylmethacrylate Polyether ketones, polyvinyl alcohols and polyvinyl chlorides, and combinations thereof. Is selected may include any of them. However, the present invention is not limited thereto, and a substrate or a film that does not hinder transparency is sufficient for the base substrate 200.

When the base substrate 200 is formed of a transparent substrate through which unpolarized light is transmitted, the hard coating layer 100 may be formed on both sides of the base substrate 200, though not shown in the drawing.

Hereinafter, a display device according to a third embodiment of the present invention will be described with reference to FIGS. 5 to 7. FIG. 5 is a view showing a display device according to a third embodiment of the present invention. 6 and 7 are views for explaining a touch panel of a display device according to the present invention.

Referring to FIG. 5, a display device according to a third embodiment of the present invention includes a display panel 300, a touch panel 400 disposed on the display panel 300, and a hard coating layer 100. In addition, the display device includes a base substrate 200 disposed on the touch panel 400. That is, the touch panel 400 may be disposed between the base substrate 200 and the display panel 300. Since the display panel 300, the base substrate 200, and the hard coating layer 100 are the same as those described above, a detailed description thereof will be omitted.

Although the touch panel 400 is shown separately from the base substrate 200 and the display panel 300 in the drawing, the touch panel 400 may be integrally formed with the base substrate 200 As shown in FIG. The touch panel 400 may be formed integrally with the display panel 300.

In detail, the touch panel 400 may be an add-on type touch panel 400. In addition, the touch panel 400 may be an integrated type touch panel 400.

When the touch panel 400 is an external touch panel 400, the touch panel 400 may have a separate structure from the display panel 300. A transparent adhesive layer may be formed between the touch panel 400 and the display panel 300.

The touch panel 400 may be formed separately from the base substrate 200 or may be formed integrally with the base substrate 200. When the touch panel 400 is formed separately from the base substrate 200, a transparent adhesive layer may be formed between the touch panel 400 and the base substrate 200. When the touch panel 400 is formed integrally with the base substrate 200, a sensing electrode may be formed on the back surface of the base substrate 200. That is, a separate adhesive layer is not required between the touch panel 400 and the base substrate 200.

When the touch panel 400 is an embedded touch panel 400, the touch panel 400 may be formed integrally with the display panel 300. That is, a separate adhesive layer is not required between the touch panel 400 and the display panel 300. The touch panel 400 may be an on-cell type or an in-cell type.

When the touch panel 400 is an on-cell type, a sensing electrode may be formed on the upper surface of the display panel 300. In detail, a sensing electrode or the like may be formed directly on the substrate disposed on the display panel 300. Like the external touch panel 400, the touch panel 400 may be formed separately from the base substrate 200, or may be integrally formed with the base substrate 200. Referring to FIG.

When the touch panel 400 is an in-cell type, a sensing electrode may be formed between the first substrate and the second substrate of the display panel 300. That is, a sensing electrode or the like may be formed together when the display panel 300 is formed. At this time, the base substrate 200 is formed as a separate structure that is different from the touch panel 400. Further, a transparent adhesive layer may be formed between the base substrate 200 and the display panel 300.

The touch panel 400 will be described in more detail with reference to FIGS. 5 and 6. FIG. 5 and 6 show an example in which the external touch panel is formed separately from the base substrate 200. The configuration of the touch panel 400 is not limited to the drawings. The touch panel 400 may be applied to both the external and internal touch panels as described above.

5 and 6, the touch panel 400 may be divided into a display area AA through which light is transmitted and a non-display area IA through which light is not transmitted. The non-display area IA is a concept opposite to the display area AA and is activated even when the user touches the display area AA. And the touch command input is not performed.

5, the touch panel 400 may include a sensing electrode 421 and a wiring 422 on a first surface of a first touch substrate 401. Referring to FIG. The first touch substrate 401 may include, but is not limited to, tempered glass, semi-tempered glass, soda lime glass, reinforced plastic or soft plastic.

The sensing electrode 421 may be disposed on the display area AA and the wiring 422 may be disposed on the non-display area IA. Although not shown in the drawing, a print layer may be further formed in the non-display area IA of the first touch substrate 401. [ In addition, a wiring 422 may be formed on the print layer.

The sensing electrode 421 may include a conductive material. For example, the sensing electrode 421 may be selected from the group consisting of a transparent conductive material, a metal, a nanowire, a photosensitive nanowire film, a carbon nanotube (CNT), a graphene, a conductive polymer, And may include any one of them.

The sensing electrode 421 may include a first sensing electrode 411 and a second sensing electrode 412. The first sensing electrode 411 and the second sensing electrode 412 may include the same material or may include different materials. The first sensing electrode 411 and the second sensing electrode 412 may be disposed on the same surface of the first touch substrate 401.

When the first sensing electrode 411 and the second sensing electrode 412 are disposed on the same surface of the first touch substrate 401, the first sensing electrode 411 and the second sensing electrode 412 Should not be in contact with each other. To this end, an insulating layer and a bridge electrode may be further disposed.

In detail, one of the first sensing electrode 411 and the second sensing electrode 412 is disposed below the insulating layer, and the other is disposed at both ends of the bridge electrode formed on the insulating layer Can be connected and electrically connected. Accordingly, the first sensing electrode 411 and the second sensing electrode 412 can be electrically connected to each other without being short-circuited by the bridge electrode and the insulating layer.

The first sensing electrode 411 and the second sensing electrode 412 may be disposed on the display area AA to sense a touch. in details. The first sensing electrode 411 may extend in one direction on the display area AA and the second sensing electrode 412 may extend in a direction different from the first direction.

The wiring 420 may include a first wiring 421 and a second wiring 422. In detail, the wiring 420 may include the first wiring 421 connected to the first sensing electrode 411 and the second wiring 422 connected to the second sensing electrode 412. have.

The first wiring 421 and the second wiring 422 may be connected to a printed circuit board (not shown). More specifically, the first wiring 421 and the second wiring 422 are mounted on a driving chip (not shown) through a touch signal detected from the first sensing electrode 411 and the second sensing electrode 412, To the printed circuit board (not shown) to perform a touch operation. The printed circuit board (not shown) may be, for example, a flexible printed circuit board (FPCB).

The first wiring 421 and the second wiring 422 may include a conductive material. For example, the first wiring 421 and the second wiring 422 may include a metal material such as silver (Ag) or copper (Cu).

Although not shown in the drawing, a protective layer (not shown) may be further formed on the wiring 420. The protection layer (not shown) may protect the wiring 420. Specifically, the protective layer (not shown) can prevent the reliability of the wiring 420 from being deteriorated due to oxidation of the wiring 420 due to exposure to oxygen, or moisture penetration.

Referring to FIG. 6, the touch panel 400 may include a first touch substrate 402 and a second touch substrate 403. The first touch substrate 402 and the second touch substrate 403 may include, but are not limited to, tempered glass, semi-tempered glass, soda lime glass, reinforced plastic or soft plastic. The first touch substrate 402 and the second touch substrate 403 may be bonded using a transparent adhesive such as an optical transparent adhesive (OCA).

A first sensing electrode 411 may be disposed on the display area AA of the first touch substrate 402. In addition, a first wiring 421 connected to the first sensing electrode 411 may be disposed in the non-display area IA of the first touch substrate 402.

A second sensing electrode 412 may be disposed on the display area AA of the second touch substrate 403. [ In addition, a second wiring 422 connected to the second sensing electrode 412 may be disposed in the non-display area IA of the second touch substrate 403. The first wiring 421 and the second wiring 422 may be electrically connected to a printed circuit board (not shown), respectively.

However, the touch panel 400 is not limited to the drawings and the above description, and may be an input device capable of inputting in a manner that the touch panel 400 is in contact with the front face of the display device using a finger, a stylus pen, or the like Do. That is, the touch panel 400 can be applied without limitation as long as it is generally used.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

≪ Example 1 >

45 parts by weight of a fluorine-based polymer, 30 parts by weight of a fluorine-based silane, 0.03 parts by weight of zinc oxide having an average particle diameter of 20 nm, 5 parts by weight of an acrylic monomer, 2.5 parts by weight of a photopolymerization initiator and a residual solvent were mixed to prepare 100 parts by weight of a composition for hard- Respectively.

At this time, as the fluorinated polymer, a fluorinated urethane-modified polymer containing a repeating unit represented by the following formula (5) was used.

[Chemical Formula 5]

As the fluorine-based silane compound, a compound represented by the following formula (6) was used.

[Chemical Formula 6]

The hard coating composition was coated on one side of a polymethylmethacrylate (PMMA) film and cured by UV irradiation to form a hard coating layer.

≪ Example 2 >

A hard coat layer was formed in the same manner as in Example 1, except that zinc oxide was mixed in an amount of 0.1 part by weight.

≪ Example 3 >

A hard coat layer was formed in the same manner as in Example 1, except that 0.3 part by weight of zinc oxide was mixed.

<Example 4>

A hard coat layer was formed in the same manner as in Example 1, except that 0.5 part by weight of zinc oxide was mixed.

&Lt; Example 5 >

A hard coat layer was formed in the same manner as in Example 1, except that zinc oxide having an average particle diameter of 15 nm was used.

&Lt; Example 6 >

A hard coat layer was formed in the same manner as in Example 1, except that zinc oxide having an average particle diameter of 25 nm was used.

&Lt; Example 7 >

A hard coat layer was formed in the same manner as in Example 1, except that zinc oxide having an average particle diameter of 35 nm was used.

&Lt; Comparative Example 1 &

A hard coat layer was formed in the same manner as in Example 1, except that zinc oxide was mixed in an amount of 0.0.1 part by weight.

&Lt; Comparative Example 2 &

A hard coat layer was formed in the same manner as in Example 1, except that 1 part by weight of zinc oxide was mixed.

<Experimental Example>

The reflectance, transmittance and haze value of the hard coat layer prepared in Examples 1 to 7 and Comparative Examples 1 and 2 were measured. As a measuring instrument, Konica Minolta (CM-2600D) was used. D65 light source and 2 degree observer were used. The reflectance was measured by attaching a black adhesive tape (Toyohozai Co., Ltd. Black Adhesive Film) to the remaining surfaces except the coated surface.

The antibacterial activity of the hard coat layer prepared in Examples 1 to 7 and Comparative Examples 1 and 2 was measured by the JIS Z 2801 method. The measurement results are shown in Table 1 below. 8 is a photograph showing the state after the antibacterial activity of the hard coating layers of Examples 1 to 4 and Comparative Examples 1 and 2 was measured.

division reflectivity(%) Transmittance (%) Hayes Antibacterial activity Example 1 1.4 to 1.6 94.71 0.16 4 to 5 Example 2 1.4 to 1.6 94.73 0.15 4 to 5 Example 3 1.4 to 1.6 94.69 0.17 4 to 5 Example 4 1.4 to 1.6 94.65 0.38 4 to 5 Example 5 1.4 to 1.6 94.79 0.2 4 to 5 Example 6 1.4 to 1.6 94.64 0.3 4 to 5 Example 7 1.9 to 2.0 94.88 1.5 3 Comparative Example 1 1.3 to 1.5 94.78 0.15 2 Comparative Example 2 2.25 93.58 0.95 4 to 5

<Experimental Example 2>

Compositions for hard coating were prepared while varying the zinc oxide content in the composition for hard coating from 0 to 1 part by weight. At this time, the remaining components and content in the hard coating composition were the same as in Example 1, and a hard coating layer was prepared in the same manner as in Example 1. [

Then, the reflectance of the hard coat layers was measured, and a change graph of reflectance was calculated on the zinc oxide content. The graph is shown in FIG. 9, when the content of zinc oxide in the hard coating composition exceeds 0.5 parts by weight, the reflectance increases sharply. On the other hand, in the case of the hard coating layer formed of the composition for hard coating having a zinc oxide content of 0.5 weight part, the content of zinc oxide in the hard coating layer was about 0.6 wt%.

100: hard coat layer
200: base substrate
300: Display panel
400: touch panel

Claims (18)

A unit represented by the following formula (1);
A unit represented by the following formula (2); And
Zinc oxide,
Wherein the zinc oxide is contained in the hard coat layer in an amount of 0.03 wt% to 0.6 wt%.
[Chemical Formula 1]

The Formula 1 in, R ₁ is hydrogen or C _{1 ~ 10} alkyl group, R ₂ is hydrogen or C _{1 ~ 10} alkyl group, R ₃ is an at least one hydrogen is substituted by F C _{1 ~ 10} alkyl group, .

(2)

Wherein R ₄ and R ₅ are each independently an alkyl group having _{1 to 10} carbon atoms and R ₆ is a C _1-20 alkyl group substituted with at least one hydrogen atom.
The method according to claim 1,
Wherein the unit represented by the formula (1) and the unit represented by the formula (2) are contained in a molar ratio of 1: 1 to 2: 1.
The method according to claim 1,
Further comprising a unit derived from an acrylic monomer.
The method of claim 3,
The acrylic monomer may be at least one selected from the group consisting of dipentaerythritol penta (meth) acrylate, dipentaerythol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythron tetra (meth) acrylate, ditrimethylol propane (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate, tri (meth) (Meth) acrylate, propylene glycol (meth) acrylate, 1,3-butanediol di (meth) acrylate, (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) (Meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxy (meth) acrylate, isobutyl (meth) acrylate, Ethyl (meth) acrylate, and isobonole (meth) acrylate.
The method according to claim 1,
Wherein R ₃ is - (CF ₂ ) ₁ -CF ₃ (wherein, 1 is an integer of 0 to 10).
The method according to claim 1,
Wherein R ₆ is - (CF ₂ ) _m -CF ₃ (wherein m is an integer of 1 to 10).
The method according to claim 1,
Wherein the zinc oxide has an average particle diameter of 15 nm to 25 nm.
The method according to claim 1,
The hard coating layer has a reflectance of 2% or less.
The method according to claim 1,
Wherein the hard coat layer has a antibacterial activity of 3 or more as measured by JIS Z 2801. [
Applying a hard coating composition comprising a fluorine-based polymer containing a repeating unit represented by the following formula (3), a fluorine-based silane represented by the following formula (4), and zinc oxide on a substrate; And
And curing the hard coating composition,
Wherein the hard coating composition comprises zinc oxide in an amount of 0.03 parts by weight to 0.5 parts by weight based on 100 parts by weight of the composition for hard coating.
(3)

The [formula 3], R ₁ is hydrogen or C _{1 ~ 10} alkyl group, R ₂ is hydrogen or C _{1 ~ 10} alkyl group, R ₃ is an at least one hydrogen is substituted by F C _{1 ~ 10} alkyl group, .

[Chemical Formula 4]

R _4, R ₅ and R ₇ are each independently a C _1-10 alkyl group, and R ₆ is a C _1-20 alkyl group substituted by at least one hydrogen atom.
11. The method of claim 10,
The hard coating composition may contain,
With respect to 100 parts by weight of the composition for hard coating,
10 to 50 parts by weight of a fluorine-based polymer containing a repeating unit represented by the following formula (3)
10 to 40 parts by weight of a fluorine-based silane represented by the following formula (4)
0.03 parts by weight to 0.5 parts by weight of zinc oxide, and
Lt; RTI ID = 0.0 &gt;%&lt; / RTI &gt; solvent.
11. The method of claim 10,
Wherein the hard coating composition further comprises an acrylic monomer.
Display panel; And
A hard coating layer disposed on the display panel and formed as a single layer,
Wherein the hard coat layer comprises a unit represented by the following formula (1); A unit represented by the following formula (2); And zinc oxide, and the zinc oxide is contained in an amount of 0.03% by weight to 0.6% by weight of the hard coat layer.
[Chemical Formula 1]

The Formula 1 in, R ₁ is hydrogen or C _{1 ~ 10} alkyl group, R ₂ is hydrogen or C _{1 ~ 10} alkyl group, R ₃ is an at least one hydrogen is substituted by F C _{1 ~ 10} alkyl group, .

(2)

Wherein R ₄ and R ₅ are each independently an alkyl group having _{1 to 10} carbon atoms and R ₆ is a C _1-20 alkyl group substituted with at least one hydrogen atom.
14. The method of claim 13,
Wherein the display panel is a liquid crystal display panel or an organic electroluminescence display panel.
14. The method of claim 13,
Wherein a base substrate is further disposed between the display panel and the hard coating layer, and the hard coating layer is formed on an upper surface of the base substrate.
16. The method of claim 15,
And a hard coating layer is further formed on a bottom surface of the base substrate.
16. The method of claim 15,
Wherein the base substrate is a polarizing plate.
16. The method of claim 15,
And a touch panel is further disposed between the base substrate and the display panel.

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