KR20170097534A - Composition for window film and flexible window film prepared using the same - Google Patents

Abstract

Provided are a window film composition and a flexible window film produced therefrom, wherein the window film composition comprises: a first fluorine-containing silicon resin of chemical formula 1, (R_aSiO_((4-a)/2))_x(X_bSiO_((4-b)/2))_y; a second silicon resin having an epoxy group or an epoxy group-containing functional group; and an initiator. A window film having an excellent external appearance and a low reflection rate can be obtained. Moreover, a flexible window film having excellent hardness and flexibility can be obtained. Furthermore, a window film having a screen quality improving effect can be obtained.

Description

FIELD OF THE INVENTION The present invention relates to a composition for a window film,

The present invention relates to a composition for a window film and a flexible window film formed therefrom.

Flexible display devices have been developed that can be folded and unfolded while replacing a glass substrate or a hardened substrate with a film in a display device. The flexible display device is thin, light, strong against impact, and can be folded and unfolded. The window film is positioned at the outermost portion of the display device, so that flexibility and hardness are good. The window film is prepared by coating a coating solution on a substrate layer. If the coating solution is not uniformly applied, the appearance may be poor, which may cause distortions on the display, and the reflectance is high, .

The background art of the present invention is disclosed in Japanese Laid-Open Patent Application No. 2007-176542.

A problem to be solved by the present invention is to provide a composition for a window film which is excellent in appearance and can realize a window film having low reflectance.

Another object of the present invention is to provide a composition for a window film which can realize a flexible window film excellent in hardness and flexibility.

Another object of the present invention is to provide a composition for a window film which can realize a window film having an effect of improving screen quality.

Another object of the present invention is to provide a flexible window film having excellent appearance, low reflectance and excellent hardness and flexibility.

The composition for a window film of the present invention may include a first fluorine-containing silicone resin represented by the following formula (1), a second silicone resin having an epoxy group or an epoxy group-containing functional group, and an initiator:

≪ Formula 1 >

(R _a SiO _{(4-a) / 2} ) _x (X _b SiO _{(4-b) / 2} ) _y

(Wherein R, X, a, b, x and y are as defined in the detailed description of the present invention).

The flexible window film of the present invention includes a base layer and a coating layer formed on the base layer. The flexible window film may have a RIQ of 85 or more, a pencil hardness of 4H or more, and a radius of curvature of 5.0 mm or less.

The present invention provides a composition for a window film which is excellent in appearance and can realize a window film having low reflectance.

The present invention provides a composition for a window film capable of realizing a flexible window film excellent in hardness and flexibility.

The present invention provides a composition for a window film capable of realizing a window film having an effect of improving screen quality.

The present invention provides a flexible window film having excellent appearance, low reflectance, and excellent hardness and flexibility.

1 is a cross-sectional view of a flexible window film according to an embodiment of the present invention.
2 is a cross-sectional view of a flexible window film according to another embodiment of the present invention.
3 is a cross-sectional view of a flexible display device according to an embodiment of the present invention.
4 is a cross-sectional view according to an embodiment of the display unit of FIG.
5 is a cross-sectional view of a flexible display device according to another embodiment of the present invention.
6 is a cross-sectional view of a flexible display device according to another embodiment of the present invention.

The present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention. 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.

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

In the present specification, "RIQ (Reflected Image Quality)" is used to measure the sharpness of the reflected image of the window coating layer surface. The RIQ is measured by Rhopoint's Rhopoint IQ. The RIQ can be a value ranging from 0 to 100. The larger the RIQ value, that is, the closer to 100, the more smooth and smooth the surface of the window coating layer. However, RIQ can be measured as a conventional device capable of measuring RIQ in addition to Rhopoint's Rhopoint IQ.

As used herein, the term " epoxy group "means a glycidyl group, a glycidoxin group or an epoxidized C4 to C20 cycloalkyl group, and an" epoxy group-containing functional group "means a C5 to C20 cycloalkyl group having a C1 to C20 alkyl group or an epoxy group having an epoxy group to be.

As used herein, "halogen" means fluorine, chlorine, bromine, or iodine, "(meth) acryl" means acryl and / or methacrylic, and "substituted" A hydrogen atom is replaced by a hydroxyl group, an unsubstituted C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C3 to C10 cycloalkyl group, an unsubstituted C6 to C20 aryl group, a C7 to C20 arylalkyl group, A substituted C6 to C20 aryl group, or a C1 to C10 alkyl group substituted with a C1 to C10 alkoxy group.

"Gp" is a 3-glycidoxypropyl group, "Me" is a methyl group, "Fd" is 1, 1H, 2H, 2H, 2H, Perfluorodecyl group, and "Fo" is a 1H, 1H, 2H, 2H-perfluorooctyl group.

Hereinafter, a composition for a window film according to an embodiment of the present invention will be described.

The composition for a window film according to an embodiment of the present invention may include a first fluorine-containing silicone resin, a second silicone resin, and an initiator. The composition for a window film according to the present embodiment includes a first fluorine-containing silicone resin to improve the appearance of a window film, reduce diffuse reflection, increase the transparency of the window film, and improve the coating property of the composition for a window film . The composition for a window film according to this embodiment contains a first fluorine-containing silicone resin and a second silicone resin to improve the hardness and flexibility of a window film, thereby realizing a flexible window film. The first fluorine-containing silicone resin and the second silicone resin are different from each other and may be contained in the composition for a window film alone or in combination of two or more.

The first fluorine-containing silicone resin may be represented by the following Formula 1:

≪ Formula 1 >

(R _a SiO _{(4-a) / 2} ) _x (X _b SiO _{(4-b) / 2} ) _y

(Wherein R represents an epoxy group, an epoxy group-containing functional group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C5 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

X is a substituted or unsubstituted C1 to C30 alkyl group containing at least one fluorine, a substituted or unsubstituted C5 to C20 cycloalkyl group containing at least one fluorine, or a substituted or unsubstituted group containing at least one fluorine A substituted or unsubstituted C6 to C20 aryl group,

a is an integer of 0 to 3, b is an integer of 1 to 3, 0? x <1, 0 <y? 1, x + y = 1).

And for example when a is _{2 (R 2 SiO 2/2} ) in formula (I), this can mean that the two R bound to Si, and wherein R is the same or different. The same is true when a is 1 or 3. A For example, if b is _{2 (X 2 SiO 2/2} ) in the general formula (2), this means that the two X are bonded to Si, and wherein X may be the same or different. The same also applies when b is 1 or 3.

Specifically, R is an epoxy group or an epoxy group-containing functional group, which is a C1 to C20 alkyl group having an epoxidized C4 to C20 cycloalkyl group, a C1 to C20 alkyl group having a glycidoxy group, or a C1 to C10 alkyl group, An epoxycyclohexylethyl group, a glycidoxypropyl group, a methyl group or an ethyl group. Specifically, X is a C1 to C10 fluoroalkyl group, a C1 to C10 perfluoroalkyl group, a C1 to C10 alkyl group having a C1 to C10 fluoroalkyl group, or a C1 to C10 perfluoroalkyl group having a C1 to C10 perfluoroalkyl group. C10 &lt; / RTI &gt; alkyl group. More specifically, X is at least one selected from the group consisting of 1H, 1H, 2H, 2H-perfluorodecyl group, 1H, 1H, 2H, perfluorooctyl group, . Specifically, 0.0001? X? 0.9999, 0.0001? Y? 0.9999, more specifically 0.8000? X? 0.9999, 0.0001? Y? 0.2000, more specifically 0.9000? X? 0.995, . Within this range, the appearance of the window film may be improved, the transparency may be improved, and the reflectance may be lowered.

In one embodiment, the first fluorine-containing silicone resin may be represented by the following Formulas 1-1, 1-2, or 1-3:

&Lt; Formula 1-1 >

(RSiO _3/2 ) _x (XSiO _3/2 ) _y

(1-2)

(RSiO3 / ₂ ) _x1 (RR'SiO2 _{/ 2} ) _x2 (XSiO3 / ₂ ) _y

<Formula 1-3>

(RSiO3 / ₂ ) _x1 (R'SiO3 / ₂ ) _x2 (XSiO3 / ₂ ) _y

(Wherein R and X are as defined in Formula 1, and R 'is an epoxy group, an epoxy group-containing functional group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C5 0 &lt; y < 1, x + y = 1, 0 < x1 < 1 , 0 <x2 <1, 0 <y <1, x1 + x2 + y = 1). Specifically, in the formulas 1-1 to 1-3, 0.0001? X or x1 + x2? 0.9999, 0.0001? Y? 0.9999, 0.8000? X or x1 + x2? 0.9999, 0.0001? Y? 0.2000, X or x1 + x2? 0.995, and 0.005? Y? 0.1000. Within this range, the appearance of the window film may be improved, the transparency may be improved, and the reflectance may be lowered.

More specifically, the first fluorine-containing silicone resin may be represented by the following formulas 1-1-1 to 1-1-10:

&Lt; Formula 1-1-1-1 &

(EcSiO3 / ₂ ) _x (FdSiO3 / ₂ ) _y

(1-1-2)

(EcSiO _3/2 ) _x (FoSiO _3/2 ) _y

&Lt; Formula 1-1-3 &

(GpSiO _3/2 ) _x (FdSiO _3/2 ) _y

&Lt; Formula 1-1-4 &

(GpSiO _3/2 ) _x (FoSiO _3/2 ) _y

<Formula 1-1-5>

_{(EcSiO 3/2) x1 ((Me} ) 2 SiO 2/2) x2 (FdSiO 3/2) y

<Formula 1-1-6>

_{(EcSiO 3/2) x1 ((Me} ) 2 SiO 2/2) x2 (FoSiO 3/2) y

&Lt; Formula 1-1-7 &

_{(GpSiO 3/2) x1 ((Me} ) 2 SiO 2/2) x2 (FdSiO 3/2) y

&Lt; Formula 1-1-8 &

_{(GpSiO 3/2) x1 ((Me} ) 2 SiO 2/2) x2 (FoSiO 3/2) y

&Lt; Formula 1-1-9 &

(EcSiO3 / ₂ ) _x1 (GpSiO3 / ₂ ) _x2 (FdSiO3 / ₂ ) _y

<Formula 1-1-10>

(EcSiO3 / ₂ ) _x1 (GpSiO3 / ₂ ) _x2 (FoSiO3 / ₂ ) _y

1, 0 <x <1, 0 <x <1, 0 <x <1, 0 <x <1, 0 <y <1, x1 + x2 + y = 1).

The first fluorine-containing silicone resin preferably has a fluorine content of 0.1 wt% to 50 wt%, specifically 0.2 wt% to 30 wt%, more specifically 0.5 wt% to 20 wt%, even more specifically 1 wt% to 10 wt% . In the above range, the appearance of the window film may be improved and the transparency may be good. The first fluorine-containing silicone resin may have a weight average molecular weight of 2,000 to 20,000, specifically 4,000 to 10,000, more specifically 4,500 to 6,000. Within the above range, the appearance of the window film can be improved and transparency can be enhanced. The first fluorine-containing silicone resin preferably has a polydispersity (PDI) of 1.0 to 3.0, specifically 1.5 to 2.5, and an epoxy equivalent of 0.1 to 100 mol / 100 g, specifically 0.3 mol / 100 to 0.8 mol / . Within the above range, coating properties of the composition are good and coating properties may be stable. The first fluorine-containing silicone resin is used in an amount of 0.1 to 50% by weight, specifically 0.2 to 30% by weight, more specifically 0.5 to 20% by weight, based on the total amount of the first fluorine-containing silicone resin and the second silicone resin . Within this range, the appearance of the window film may be improved and the transparency may be good.

Hereinafter, the second silicone resin will be described in detail.

The second silicone resin is a binder that forms a window film and can improve the hardness and flexibility of the window film and is a fluorine-free non-fluorinated silicone resin, which can be represented by the following formula (2)

(2)

(R ¹ SiO _3/2 ) _x (R ² R ³ SiO _2/2 ) _y (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _z (SiO _4/2 ) _w

(Wherein R ¹ represents an epoxy group or an epoxy group-containing functional group,

R ² and R ³ are each independently hydrogen, a crosslinkable functional group, an unsubstituted or substituted C 1 to C 20 alkyl group, or an unsubstituted or substituted C 5 to C 20 cycloalkyl group,

R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of hydrogen, a crosslinkable functional group, an unsubstituted or substituted C 1 to C 20 alkyl group, an unsubstituted or substituted C 5 to C 20 cycloalkyl group, An aryl group of C30,

0 &lt; y < 1, 0? Y <1, 0? Z <1, 0? W <1, x + y + z + w = 1).

Specifically, R ¹ is a C1 to C20 alkyl group having an epoxidized C4 to C20 cycloalkyl group, or a C1 to C20 alkyl group having a glycidoxy group, more specifically an epoxycyclohexylethyl group, or a glycidoxypropyl group have. Specifically, R ² and R ³ may be independently a C1 to C20 alkyl group having a C4 to C20 cycloalkyl group which is epoxidized, a C1 to C10 alkyl group, more specifically an epoxycyclohexylethyl group or a methyl group. In the formula (2), the crosslinkable functional group means an epoxy group, an epoxy group-containing functional group, an oxetanyl group or an oxetanyl group-containing functional group. The second silicone resin of the following formulas (2-1) and (2-2) is more preferable for securing appearance, hardness and the like of the window film.

In one embodiment, the second silicone resin may be represented by the following formula (2-1) or (2-2): &lt; EMI ID =

&Lt; Formula (2-1)

(R ^1a SiO _3/2 ) _{x 1} (R ^1b SiO _3/2 ) _{x 2}

(In the above formula 2-1, R ^1a, R ^1b is an epoxy group or the epoxy group-containing functional group, 0≤x1≤1, 0≤x2≤1, x1 + x2 = 1, x1 + x2 ≠ 0, R 1a and R ^1b is Different from each other)

&Lt; Formula (2-2)

(R ^1a SiO _3/2 ) _{x 1} (R ^1b SiO _3/2 ) _{x 2} (SiO _4/2 ) _w

(In the above formula 2-2, R ^1a, R ^1b is an epoxy group or the epoxy group-containing functional group, 0 <x1 <1, 0 <x2 <1, 0 <w <1, x1 + x2 + w = 1, R 1a and R ^1b are different).

X1 < 1, 0 < x2 < 0.20, . Alternatively, in formula (2-1), x1 may be 1, and x2 may be 0. In the formula (2-2), 0.30? X1 <1.0, 0 <x2? 0.50, 0 <w? 0.40 More specifically, 0.40? X1 <1.0, 0 <x2? 0.40, 0? W? x1? 0.95, 0.01? x2? 0.40, and 0.01? w? 0.20. Within this range, flexibility and hardness of the window film can be improved. In formulas (2-1) and (2-2), R ^1a may be a C1 to C20 alkyl group having an epoxidized C4 to C20 cycloalkyl group, and R ^1b may be a C1 to C20 alkylene group having a glycidyl group or a glycidoxy group Alkyl group.

More specifically, the second silicone resin may be represented by the following general formulas (2-1-1) and (2-1-2):

&Lt; Formula (2-1-1)

(EcSiO3 / ₂ ) _x1 (GpSiO3 / ₂ ) _x2

(In the formula 2-1-1, 0? X1? 1, 0? X2? 1, x1 + x2 = 1, x1 + x2? 0).

<Formula 2-1-2>

(EcSiO3 / ₂ ) _x1 (GpSiO3 / ₂ ) _x2 (SiO4 / ₂ ) _w

(0 <x1 <1, 0 <x2 <1, 0 <w <1, x1 + x2 + w = 1 in the formula 2-1-2).

The second silicone resin may have a weight average molecular weight of 2,000 to 20,000, specifically 4,000 to 10,000, more specifically 4,500 to 7,000. Within this range, there is an effect of supporting the coating layer of the window film in the above range. The second silicone resin may have a polydispersity (PDI) of 1.0 to 3.0, specifically 1.5 to 2.5, and an epoxy equivalent of 0.1 to 100 mol, particularly 0.3 mol / 100 g to 0.8 mol / 100 g . Within the above range, coating properties of the composition are good and coating properties may be stable. The second silicone resin may be included in the total amount of the first fluorine-containing silicone resin and the second silicone resin in an amount of 50% by weight to 99.9% by weight, specifically 70% by weight to 99.8% by weight, more specifically 80% by weight to 99.5% have. In the above range, flexibility and hardness of the window film are improved, and the RIQ of the window film is increased to improve the appearance.

The initiator is used to cure the first fluorine-containing silicone resin and the second silicone resin. One or more of a photocationic initiator and a photoradical initiator may be used, or they may be used alone or in combination. As the Gwangyang ionic initiator, any one ordinarily known to those skilled in the art can be used, and onium salts including cations and anions can be used. Specifically, the cation is at least one selected from the group consisting of diphenyl iodonium, 4-methoxydiphenyl iodonium, bis (4-methylphenyl) iodonium, bis (4-tert- butylphenyl) iodonium, bis (dodecylphenyl) Triarylsulfonium such as diaryliodonium such as [methylphenyl] [4- (2-methylpropyl) phenyl] iodonium, triphenylsulfonium and diphenyl-4-thiophenoxyphenylsulfonium, bis [4 - (diphenylsulfonio) phenyl] sulfide, and the anions include hexafluorophosphate, tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate, hexachloroantimonate, etc. . The initiator may be included in an amount of 0.1 to 10 parts by weight, specifically 0.5 to 5 parts by weight per 100 parts by weight of the total amount of the first fluorine-containing silicone resin and the second silicone resin. In this range, the silicone resin can be sufficiently cured and the remaining amount of the initiator remains, thereby preventing the optical characteristics (transmittance, hue, and light reliability) of the window film from being lowered.

The composition for a window film according to this embodiment may further include nanoparticles.

Nanoparticles can further increase the hardness of the window film. The nanoparticles may include, but are not limited to, one or more of silica, aluminum oxide, zirconium oxide, and titanium oxide. The nanoparticles may be surface treated with some or all of the surface of the silicone compound for mixing with the silicone resin. Nanoparticles are not limited in shape and size. Specifically, the nanoparticles may include spherical, plate-like, amorphous, etc. particles. The nanoparticles may have an average particle diameter (D50) of 1 nm to 200 nm, specifically 10 nm to 50 nm. The hardness of the window film can be increased without affecting the surface roughness and transparency of the window film in the above range. The nanoparticles may be contained in an amount of 0.1 to 60 parts by weight, specifically 10 to 50 parts by weight, based on 100 parts by weight of the total amount of the first fluorine-containing silicone resin and the second silicone resin. The hardness of the window film can be increased without affecting the surface roughness and transparency of the window film in the above range.

The composition for a window film according to this embodiment may further include an additive. The additive may provide additional functionality to the window film. The additive may include an additive typically added to the window film. Specifically, the additive may include, but is not limited to, at least one of a UV absorber, a reaction inhibitor, an adhesion improver, a thixotropic agent, a conductivity-imparting agent, a colorant-adjusting agent, a stabilizer, an antistatic agent and an antioxidant. The reaction inhibitor may include ethynylcyclohexane. The adhesion improver may include a silane compound having an epoxy or alkoxysilyl group. The thixotropic agent may include pyrous silica and the like. The conductivity-imparting agent may include a metal powder such as silver, copper aluminum and the like. The colorant-adjusting agent may include a pigment, a dye, and the like. The UV absorber can increase the light reliability of the window film. The UV absorbers can be conventional absorbents known to those skilled in the art. Specifically, the UV absorber may include, but is not limited to, one or more UV absorbers based on triazine, benzimidazole, benzophenone, and benzotriazole. The additive may be included in an amount of 0.01 to 5 parts by weight, specifically 0.1 to 2.5 parts by weight based on 100 parts by weight of the total amount of the first fluorine-containing silicone resin and the second silicone resin. In this range, the hardness and flexibility of the window film can be improved and the additive effect can be realized.

The composition for a window film according to this embodiment may further include a solvent to facilitate coating, coating or processability. The solvent may include, but is not limited to, one or more of methyl ethyl ketone (MEK, methylethylketone), methyl isobutyl ketone, and propylene glycol monomethyl ether acetate.

Hereinafter, a composition for a window film according to another embodiment of the present invention will be described.

The composition for a window film according to this embodiment is substantially the same as the composition for a window film according to an embodiment of the present invention, except that it further includes a crosslinking agent. By further including a crosslinking agent, the hardness and flexibility of the window film can be improved.

The crosslinking agent contains a crosslinkable functional group to cure the first fluorine-containing silicone resin and the second silicone resin, thereby increasing the hardness of the window film and improving flexibility. The crosslinking agent may further include at least one of a chain-like aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and a hydrogenated aromatic hydrocarbon group to further increase the flexibility of the coating layer. The crosslinking agent may include at least one of a chain type aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated aromatic hydrocarbon epoxy monomer, and an oxetane monomer, and these may be included singly or in combination.

The chain type aliphatic epoxy monomer may be 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, Cidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ether; Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Diglycidyl esters of aliphatic long chain dibasic acids; Monoglycidyl ethers of aliphatic higher alcohols; Glycidyl ethers of higher fatty acids; Epoxidized soybean oil; Butyl stearate; Octyl stearate; Epoxidized linseed oil; Epoxylated polybutadiene, and the like.

The cyclic aliphatic epoxy monomer is a compound having at least one epoxy group in the alicyclic group, and may specifically include an alicyclic epoxy carboxylate, an alicyclic epoxy (meth) acrylate, and the like. More specifically, (3,4-epoxycyclohexyl) methyl-3 ', 4'-epoxycyclohexanecarboxylate, diglycidyl 1,2-cyclohexanedicarboxylate, 2- (3,4- Epoxycyclohexyl) -5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxy-6-methylcyclohexyl) adipate, 3,4- Cyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, trimethyl Caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl- Epoxycyclohexanecarboxylate, 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3, 4-epoxycyclohexane (3,4-epoxycyclohexylmethyl) adipate, 4-vinylcyclohexene-oxide, vinylcyclohexene monoxide (vinylcyclohexylmethoxide) And the like.

The hydrogenated aromatic hydrocarbon epoxy monomer means a compound obtained by selectively hydrogenating an aromatic epoxy monomer under a pressure in the presence of a catalyst. Aromatic epoxy monomers include, for example, bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S and the like; Novolak type epoxy resins such as phenol novolak epoxy resin, cresol novolak epoxy resin, and hydroxybenzaldehyde phenol novolak epoxy resin; Glycidyl ethers of tetrahydroxyphenylmethane, glycidyl ethers of tetrahydroxybenzophenone, and epoxy polyvinylphenols, and the like.

The oxetane monomer may be selected from the group consisting of 3-methyloxetane, 2-methyloxetane, 2-ethylhexyloxetane, 3-oxethanol, 2-methylene oxetane, Methyl-3-oxetanemethanamine, N- (1,2-dimethylbutyl) -3-methyl-3- (3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyloxetane- May include at least one of 3-hydroxymethyloxetane, xylene bisoxetane and 3- [ethyl-3 [[(3-ethyloxetan-3-yl)] methoxy] methyl] oxetane, But is not limited thereto.

The crosslinking agent may be included in an amount of 1 part by weight to 50 parts by weight, specifically 1 part by weight to 40 parts by weight, based on 100 parts by weight of the total amount of the first fluorine-containing silicone resin and the second silicone resin. In the above range, the flexibility, hardness, curl and optical properties of the coating layer can be secured.

Hereinafter, a composition for a window film according to another embodiment of the present invention will be described.

The composition for a window film according to this embodiment is substantially the same as the composition for a window film according to an embodiment of the present invention, except that it further comprises a crosslinking agent and a fluorine-based (meth) acrylate resin.

The crosslinking agent is as described above.

The fluorine-based (meth) acrylate resin can improve the hardness and appearance of the window film by complementing the decrease in hardness of the window film due to the first fluorine-containing silicone resin. The fluorine-based (meth) acrylate resin has a surface energy of 25 mN / m or less, for example, 23 mN / m to 25 mN / m at 25 ° C, 90 DEG or less, for example, 85 DEG to 89 DEG. Within this range, there may be a surface quality improvement effect. The fluorine-based (meth) acrylate resin may include commercially available products such as RS-75, KY-1203, and the like. The fluorine-based (meth) acrylate resin may be a non-silicon-based resin containing no silicon. The fluorine-based (meth) acrylate resin is used in an amount of 1 part by weight to 20 parts by weight, specifically 1 part by weight to 10 parts by weight, more specifically 1 part by weight 5 parts by weight. The hardness and appearance of the window film can be simultaneously improved in the above range. In one embodiment, the first fluorine-containing silicone resin may be included in the total amount of the first fluorine-containing silicone resin and the second silicone resin in an amount of 0.5 wt% to 2 wt%, specifically 0.5 wt% to 1.5 wt%. Within this range, the appearance and hardness of the window film can be simultaneously improved.

Hereinafter, a flexible window film according to an embodiment of the present invention will be described with reference to FIG. 1 is a cross-sectional view of a flexible window film according to an embodiment of the present invention.

1, a flexible window film 100 according to an exemplary embodiment of the present invention includes a base layer 110 and a coating layer 120, And the like.

The substrate layer 110 supports the flexible window film 100 and the coating layer 120 to increase the mechanical strength of the flexible window film 100. The base layer 110 may be adhered to a display portion, a touch screen panel, or a polarizing plate by an adhesive layer or the like. The substrate layer 110 may be formed of an optically transparent and flexible resin. For example, the resin includes a polyester resin including a polyethylene terephthalate, a polyethylene naphthalate, a polybutylene terephthalate, a polybutylene naphthalate, etc., a polycarbonate resin, a polyimide resin, a polystyrene resin, polymethylmethacrylate (Meth) acrylate resin. &Lt; / RTI &gt; The resin may be contained in the base layer 110 alone or in combination. The base layer 110 may have a thickness of 10 占 퐉 to 200 占 퐉, specifically, 20 占 퐉 to 150 占 퐉, more specifically, 50 占 퐉 to 100 占 퐉. Can be used in the flexible window film in the above range.

The coating layer 120 is formed on the base layer 110 to protect the base layer 110, the display portion, the touch screen panel or the polarizing plate, improve the appearance, have high flexibility and high hardness and can be used in a flexible display device can do. The thickness of the coating layer 120 may be 5 占 퐉 to 100 占 퐉, specifically 10 占 퐉 to 80 占 퐉. Can be used in the flexible window film in the above range. Although not shown in FIG. 1, a functional surface layer such as an antireflection layer, an antiglare layer, or a hard coating layer may be further formed on the other surface of the coating layer 120 to provide additional functions to the flexible window film. 1, a coating layer 120 may be further formed on the other surface of the substrate layer 110. [

The flexible window film 100 may have a RIQ of 85 or more, specifically 85 to 98, and a reflectivity at a wavelength of 550 nm may be 2% or less, specifically 1.5% or less, more specifically 0.8% to 1.2% . Within this range, the appearance of the window film is good and the display image can be clear.

The flexible window film 100 may have a light transmittance of 88% or more and specifically 88% to 100% in a visible light region specifically at a wavelength of 400 nm to 800 nm. It can be used as a flexible window film in the above range. The flexible window film 100 may have a pencil hardness of 4H or more and a radius of curvature of 5.0 mm or less. In the above range, the film can be used as a flexible window film with good hardness and flexibility. Specifically, the flexible window film 100 may have a pencil hardness of 4H to 9H and a radius of curvature of 0.1 mm to 5.0 mm. The flexible window film 100 may have a thickness of 5 占 퐉 to 300 占 퐉. It can be used as a flexible window film in the above range.

Hereinafter, a flexible window film according to another embodiment of the present invention will be described with reference to FIG. 2 is a cross-sectional view of a flexible window film according to another embodiment of the present invention.

2, the flexible window film 200 according to another embodiment of the present invention includes a flexible window film 200 according to an exemplary embodiment of the present invention, except that an adhesive layer 130 is further formed on the other surface of the substrate layer 110. As shown in FIG. Is substantially the same as the flexible window film (100). The adhesive layer 130 is further formed on the other surface of the base layer 110, so that adhesion between the flexible window film and the touch screen panel, the polarizing plate, or the display portion can be facilitated. Is substantially the same as the flexible window film according to an embodiment of the present invention, except that an adhesive layer is further formed. Hereinafter, only the adhesive layer 130 will be described.

The adhesive layer 130 adheres to a polarizing plate, a touch screen panel, or a display unit that can be disposed under the flexible window film 200, and may be formed of a composition for a pressure-sensitive adhesive layer. Specifically, the adhesive layer 130 may be formed of a composition for a pressure-sensitive adhesive layer including a pressure-sensitive adhesive resin such as a (meth) acrylic resin, a urethane resin, a silicone resin, and an epoxy resin, a curing agent, a photoinitiator 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 photoinitiator may include the above-described photoinitiator as a conventional 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 flexible window film can be adhered well onto the display portion, the touch screen panel or the polarizing plate.

The thickness of the adhesive layer 130 may be 10 占 퐉 to 100 占 퐉. In the above range, the optical element such as the flexible window film and the polarizing plate can be sufficiently adhered.

Hereinafter, a flexible display device according to an embodiment of the present invention will be described with reference to FIGS. 3 and 4. FIG. FIG. 3 is a cross-sectional view of a flexible display device according to an embodiment of the present invention, and FIG. 4 is a cross-sectional view of an exemplary embodiment of the display unit of FIG.

3, the flexible display device 300 according to an exemplary embodiment of the present invention includes a display portion 350a, an adhesive layer 360, a polarizing plate 370, a touch screen panel 380, a flexible window film 390 , And the flexible window film 390 may comprise a flexible window film according to embodiments of the present invention.

The display unit 350a is for driving the flexible display device 300 and may include an optical element including an OLED, an LED, or an LCD device formed on a substrate and a substrate. 4 is a cross-sectional view according to an embodiment of the display unit of FIG. 4, the display portion 350a may include a lower substrate 310, a thin film transistor 316, an organic light emitting diode 315, a planarization layer 314, a protection layer 318, and an insulation layer 317 have.

The lower substrate 310 supports the display portion 350a and the lower substrate 310 may have a thin film transistor 316 and an organic light emitting diode 315 formed thereon. A flexible printed circuit board for driving the touch screen panel 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. Specifically, the lower substrate 310 may include, but is not limited to, a flexible substrate such as a silicon substrate, a polyimide substrate, a polycarbonate substrate, and a polyacrylate substrate.

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. In a non-display area of the lower substrate, a gate driver for applying an electrical signal to the driving wiring may be formed in the form of a gate in panel. 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 emits light by self-emission, and may include a first electrode 315a, an organic light emitting layer 315b, and a second electrode 315c stacked in that order. 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 lower substrate or a top emission structure in which light generated in the organic emission layer 315b is emitted upward.

The passivation layer 318 may cover the organic light emitting diode 315 to protect the organic light emitting diode 315. The passivation layer 318 may be formed of an inorganic material such as SiOx, SiNx, SiC, SiON, SiONC, and aC (amorphous carbon) Methacrylate, epoxy-based polymer, imide-based polymer, and the like. Specifically, the protective layer 318 may include an encapsulation layer in which a layer formed of an inorganic material and a layer formed of an organic material are sequentially stacked one or more times.

3, the adhesive layer 360 is formed of a pressure-sensitive adhesive composition comprising a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent to adhere the display portion 350a and the polarizing plate 370 .

The polarizing plate 370 can implement polarizing of the inner light or prevent reflection of the external light to realize the display or to increase the contrast ratio of the display. The polarizing plate may be composed of a polarizer alone. Or the polarizing plate may include a polarizing film and a protective film formed on one or both sides of the polarizing film. Or the polarizing plate 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 touch screen panel 380 senses a change in capacitance generated when a conductor such as a human body or a stylus touches, and generates an electrical signal. The display unit 350a can be driven by this signal. The touch screen panel 380 is formed by patterning a flexible conductive conductive material. The touch screen panel 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 touch screen panel 380 may include, but is not limited to, metal nanowires, conductive polymers, carbon nanotubes, and the like.

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

3, an adhesive layer is further formed between the polarizing plate 370 and the touch screen panel 380 and / or between the touch screen panel 380 and the flexible window film 390 to form a polarizing plate, a touch screen panel, a flexible It is possible to strengthen the bonding between the window films. 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. Further, although not shown in FIG. 3, a polarizing plate is further provided under the display unit 350a, so that polarized light can be realized.

Hereinafter, a flexible display device according to another embodiment of the present invention will be described with reference to FIG. 5 is a cross-sectional view of a flexible display device according to another embodiment of the present invention.

5, the flexible display device 400 according to another embodiment of the present invention includes a display portion 350a, a touch screen panel 380, a polarizer 370, and a flexible window film 390, The window film 390 may comprise a flexible window film according to embodiments of the present invention. Except that the touch screen panel 380 is not directly formed on the flexible window film 390 but the touch screen panel 380 is formed below the polarizer 370. In this case, Device. At this time, the touch screen panel 380 may be formed together with the display portion 350a. In this case, since the touch screen panel 380 is formed on the display unit 350a together with the display unit 350a, the thickness of the touch screen panel 380 can be thinner and brighter than that of the flexible display device according to an embodiment of the present invention. In this case, the touch screen panel 380 can be formed by deposition or the like, but is not limited thereto. Although not shown in FIG. 5, a gap between the display portion 350a and the touch screen panel 380 and / or between the touch screen panel 380 and the polarizer 370 and / or between the polarizer 370 and the flexible window film 390 An adhesive layer is further formed, thereby increasing the mechanical strength of the 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. Although not shown in FIG. 5, a polarizing plate is further provided under the display unit 350a to thereby guide polarized light to improve the display image.

Hereinafter, a flexible display device according to another embodiment of the present invention will be described with reference to FIG. 6 is a cross-sectional view of a flexible display device according to another embodiment of the present invention. 6, the flexible display device 500 according to another exemplary embodiment of the present invention includes a display portion 350b, an adhesive layer 360, and a flexible window film 390. The flexible window film 390 includes a flexible window film 390, May comprise a flexible window film according to embodiments of the present invention. Is substantially the same as the flexible display device according to an embodiment of the present invention, except that only the display portion 350b is capable of driving the device and the polarizing plate and the touch screen panel are excluded.

The display portion 350b may include an LCD, an OLED, or an optical element including an LED element formed on the substrate, and the display portion 350b may have a touch screen panel formed therein.

Hereinafter, a method for producing the first fluorine-containing silicone resin and the second silicone resin according to one embodiment of the present invention will be described.

The first fluorine-containing silicone resin of the formula (I) according to this embodiment is _{(R a SiO (4-a} ) / 2) silicone monomer and _{(X b SiO (4-b} ) / 2) to provide a silicone monomer that provides the &Lt; RTI ID = 0.0 &gt; and / or &lt; / RTI &gt; Specifically, the silicone monomers that provide (R _a SiO _{(4-a) / 2} ) are 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyl Dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyltriethoxysilane, and the like, but are not limited thereto. More _{specifically, (X b SiO (4-} b) / 2) to provide a silicone monomer is 1H, 1H, 2H, 2H- perfluoro-decyl trimethoxysilane, 1H, 1H, 2H, 2H- perfluoro-octanoic 1H, 1H, 2H, 2H-perfluorohexyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, Octyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorohexyltriethoxysilane, and the like, but are not limited thereto. In one embodiment, the monomer mixture _{(R a SiO (4-a} ) / 2) silicone monomer 0.01mol% to 99.99mol%, specifically, 80mol% to 99.99mol%, 90mol% to 99.5mol more specifically to provide a , Specifically 0.01 mol% to 20 mol%, more specifically 0.5 mol% to 10 mol%, of the silicon monomers providing the (X _b SiO _{(4-b) / 2} ). Within this range, the appearance of the window film may be improved and the glare may be less.

A second silicone resin is silicone monomer to provide a silicon monomer alone, or (R ¹ SiO _3/2) to provide (R ¹ SiO _3/2) according to the embodiment; And _{^{(R 2 R 3 SiO 2/}} 2) a silicon monomer, to provide a ^{(R 4 R 5 R 6 SiO} 1/2) to provide the silicon monomer, (SiO _4/2) at least one mixture of the silicone monomers to provide for &Lt; / RTI &gt; (R ¹ SiO _3/2) to provide a silicone monomer is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl triethoxysilane, 3- doksi glycidyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like can be the doksi propyl _{^{triethoxysilane, (R 2 R 3 SiO 2}} /2) to provide a silicon monomer include dimethyl dimethoxysilane, dimethyl diethoxysilane (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyltriethoxysilane and the like, and SiO _{2 / 2} ) may be, but not limited to, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and the like. In one embodiment, the monomer mixture (R ¹ SiO _3/2) silicone monomer 100mol% which provides, in particular 85mol% to about 99mol%, 1mol% to about 15mol%, 40mol% to about 95mol%, 1mol% to about 40mol%, It can be a (SiO _4/2) silicone monomer 0mol%, 1mol% to about 20mol% to service. Within this range, the hardness and flexibility of the window film can be improved.

The hydrolysis and condensation reaction of the monomer mixture can be carried out according to a conventional method for producing a silicone resin. Hydrolysis may comprise reacting the monomer mixture with water and a mixture of one or more of the desired acids and bases. Specifically, the acid may be HCl, HNO ₃ , acetic acid or the like, and the base may be NaOH, KOH, or the like. The hydrolysis is carried out at 20 ° C to 100 ° C for 10 minutes to 10 hours, and the condensation reaction can be carried out at 20 ° C to 100 ° C for 10 minutes to 12 hours under the same conditions as the hydrolysis. The production yield of the silicone resin in the above range may be high.

Hereinafter, a method of manufacturing a window film according to an embodiment of the present invention will be described.

The flexible window film 100 can be manufactured by a method of manufacturing a flexible window film including coating and curing a composition for a window film according to embodiments of the present invention on a substrate layer 110. [

The method for coating the composition for a window film on the base layer 110 may be, but not limited to, bar coating, spin coating, dip coating, roll coating, flow coating, die coating and the like. A composition for a window film can be coated on the base layer 110 to a thickness of 5 to 100 mu m. It is possible to secure a desired coating layer within the above range, and to have an excellent hardness and flexibility. Curing is a process of curing the composition for a window film to form a coating layer, which may include at least one of light curing and heat curing. Photocuring may involve irradiation with light amount of 10 mJ / cm ² to 1,000mJ / cm ² at a wavelength of 400nm or less. Thermal curing may include treating at 40 占 폚 to 200 占 폚 for 1 hour to 30 hours. Within this range, the composition for a window film can be sufficiently cured. For example, it is possible to photo-cure and then thermally cure, resulting in a higher hardness of the coating layer. The method may further include drying the composition for the window film before coating the composition for the window film on the substrate layer 110 and then curing the composition. By drying and curing, it is possible to prevent the surface roughness of the coating layer from becoming high due to long-time light curing and thermal curing. The drying may be performed at 40 캜 to 200 캜 for 1 minute to 30 hours, but is not limited thereto.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Manufacturing example  1-1: First fluorine-containing silicone resin

95 mol% of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, Shin-Etsu), 5 mol of 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane % Of monomer mixture was placed in a 500 mL 3-neck flask. To the mixture was added 0.5 mol% of KOH and 1.5 mol% of water based on the monomer mixture and stirred at 70 DEG C for 2 hours. The solvent was removed by a vacuum distillation apparatus to obtain a first fluorine-containing silicone resin (gel permeation chromatography was prepared in a _{5,000) (EcSiO 3/2)} 0.95 (FdSiO 3/2) 0 .05: GPC) weight average molecular weight by. Methyl ethyl ketone was added to adjust the solids content to 90% by weight.

Manufacturing example  1-2 Manufacturing example  1-4: First Fluorine  Containing silicone resin

A first fluorine-containing silicone resin was prepared in the same manner as in Production Example 1-1 except that the kind and / or content of the silicone monomer was changed as shown in Table 1 below.

Manufacturing example  2: Second silicon  Suzy

95 mol% of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, ShinYeatsu) and 5 mol% of (3-glycidoxypropyl) trimethoxysilane (KBM- Was placed in a 1 L 3-neck flask. 0.1 mol% of KOH was added to the silicone monomer mixture and 1 equivalent of water was added to the total silicone monomer. The mixture was stirred at 65 DEG C for 8 hours, washed with toluene and concentrated to obtain a second silicone resin molecular weight: was prepared _{5,500) (EcSiO 3/2)} 0.95 (GpSiO 3/2) 0 .05.

Manufacturing example  3: Second silicon  Suzy

Except that 50 mol% of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, Shinrytsha), (3-glycidoxypropyl) trimethoxysilane (KBM-403, ) a second silicone resin in the same manner except that the 30mol% and tetra with silicone monomer mixture comprising a silane _{20mol% (EcSiO 3/2)} 0.50 (GpSiO 3/2) 0 .30 (SiO 4/2 ) _0.20 .

Manufacturing example  4: Second silicone resin

50 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, Shin-Yatsu) was placed in a 200 mL 3-neck flask. 0.5 mol% of KOH and 1.5 mol% of water were added to the above 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the mixture was stirred at 70 ° C for 2 hours. Then, the mixture was washed with toluene and concentrated to obtain 2 silicone resin (weight average molecular weight by GPC: 5000) (EcSiO _3/2 ) was prepared.

The composition of the silicone resin of the production example is shown in Table 1 below.

Silicon monomer (mol%) Production Example 1-1 Production Example 1-2 Production Example 1-3 Production Example 1-4 Production Example 2 Production Example 3 Production Example 4 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 95 94 90 95 95 50 100 3-glycidoxypropyltrimethoxysilane - 5 - - 5 30 - Dimethyldimethoxysilane - - 5 - - - - Tetraethoxysilane - - - - - 20 - 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane 5 One 5 - - - - 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane - - - 5 - - - Weight average molecular weight 5,000 5,300 4,700 5,100 5,500 5,600 5,000

Example  One

0.5 g of the first fluorine-containing silicone resin of Production Example 1-1, 99.5 g of the second silicone resin of Production Example 2, 25 g of the crosslinking agent CELLOXIDE 2021P (daicel), 25 g of the diluting agent MEK (Daejeon Chemical), 25 g of the initiator Diphenyliodonium hexafluorophosphate Were mixed to prepare a composition for a window coating layer. The composition for the coating layer was applied to a PI film (polyimide film, SDI, thickness: 80 탆), dried at 100 캜 for 5 minutes, exposed to ultraviolet rays of 1000 mJ to prepare a coating film having a thickness of 50 탆, The window film was prepared by postcuring in an oven for 24 hours.

Examples 2 to 10

A window film was prepared in the same manner as in Example 1, except that the kind and content of the first fluorine-containing silicone resin, the content of the second silicone resin, the content of the crosslinking agent, and / or the thickness of the coating layer were changed as shown in Table 2 .

Example 11

0.5 g of the first fluorine-containing silicone resin of Production Example 1-1, 99.5 g of the second silicone resin of Production Example 4, 40 g of the crosslinking agent CY-179 (Ciba), 60 g of the diluting agent MEK (Daejung Chemical), 60 g of the initiator Diphenyliodonium hexafluorophosphate ) Were mixed to prepare a composition for a window coating layer. The composition for the coating layer was applied to a PI film (polyimide film, SDI, thickness: 80 μm), dried at 80 ° C. for 5 minutes, exposed to ultraviolet light of 1000 mJ / cm ² to prepare a coating film having a thickness of 50 μm , And postcure was carried out in a 100 ° C oven for 24 hours to prepare a window film.

Example  12 - Example  14

A window film was produced in the same manner as in Example 11 except that the contents of the first fluorine-containing silicone resin of Production Example 1-1, the second silicone resin of Production Example 4, the crosslinking agent, and the initiator were changed as shown in Table 3 below Respectively.

Example 15

1 g of the first fluorine-containing silicone resin of Production Example 1-1, 99 g of the second silicone resin of Production Example 4, 40 g of the crosslinking agent CY-179 (Ciba), 2 g of the fluorine-containing acrylate resin RS-75, 30 g of the diluting agent MEK , And 1 g of initiator Diphenyliodonium hexafluorophosphate (TCI) were mixed to prepare a composition for a window coating layer. A window film was prepared in the same manner as in Example 1 using the composition for the coating layer.

Example  16

A window film was prepared in the same manner as in Example 15 except that 5 g of the fluorine-based acrylate resin RS-75 was used.

Comparative Example 1

A composition for a window coating layer was prepared by mixing 20.0 g of the second silicone resin of Production Example 2, 5.0 g of the cross-linking agent CELLOXIDE 2021P (Daicel), 25 g of diluting agent MEK (Daejeong Chemical) and 0.2 g of initiator diphenyliodonium hexafluorophosphate (TCI). The composition for the window coating layer was applied to a PI film (polyimide film, SDI, thickness: 80 탆), dried at 100 캜 for 5 minutes, exposed to ultraviolet rays of 1000 mJ to prepare a coating layer having a thickness of 10 탆, Postcure was performed in the oven for 24 hours.

Comparative Example  2

25 g of Epoxy hybrimer (Solip), and 20 g of a diluting agent MEK (Daejeong Chemical) were mixed to prepare a composition for a window coating layer. The composition for the window coating layer was applied to a PI film (polyimide film, SDI, thickness: 80 탆), dried at 100 캜 for 5 minutes, exposed to ultraviolet rays of 1000 mJ to prepare a coating layer having a thickness of 10 탆, Postcure was performed in the oven for 24 hours.

Comparative Example 3

A mixture of 20.0 g of the silicone resin of Production Example 2, 5.0 g of the crosslinking agent CELLOXIDE 2021P (daicel), 25 g of a diluting agent MEK (Daejeong Chemical), 0.2 g of initiator diphenyliodonium hexafluorophosphate (TCI) and 0.5 g of a fluorine-containing leveling agent RS75 To prepare a composition for a window coating layer. The composition for the window coating layer was applied to a PI film (polyimide film, SDI, thickness: 80 탆), dried at 100 캜 for 5 minutes, exposed to ultraviolet rays of 1000 mJ to prepare a coating layer having a thickness of 10 탆, Postcure was performed in the oven for 24 hours.

The following properties (1) to (5) of the window films prepared in Examples and Comparative Examples were measured and shown in Tables 2, 3 and 4 below.

(1) RIQ: The window coating layer of the window film was measured with a Rhopoint IQ of Rhopoint.

(2) Reflectance: The film was measured for a window film using a Lambda 1050 UV spectrometer (Perkin Elmer) at a wavelength of 550 nm.

(3) Pencil hardness: Measured by the JIS K5400 method using a pencil hardness meter (Heidon) for the coating layer of the window film. In the pencil hardness measurement, a pencil was used from Mitsubishi's 6B to 9H pencil. The load of the pencil on the coating layer was 1 kg, the angle of drawing the pencil was 45 °, and the drawing speed of the pencil was 60 mm / min. 5 times, and when a scratch occurs more than once, it is measured by using a pencil of the pencil hardness level, and when it is 5 times of the evaluation, it is the maximum pencil hardness value when there is no scratch.

(4) Curvature radius: A window film (width x length, 1 cm x 10 cm) was visually evaluated for crack occurrence with a vernier caliper for curvature test. At this time, the direction of compression was such that the coating layers were in contact with each other in a direction in which the coating layer was not bent, and the tensile direction was in contact with the base layer in the direction of curving. The radius of curvature was measured by decreasing the radius from the larger value to the smaller value in the compression direction. The radius of curvature was determined as the minimum radius of the JIG without cracking.

(5) Appearance: Whether orange peel or wavy pattern was formed on the surface of the coating layer in the window film was visually evaluated. The formation of the wavy pattern was judged to be irregular shading on the black sheet surface when light was transmitted to the surface after placing the coating layer on the upper side of 10 cm from the A4 paper. '2' for the formation of either '3', moire pattern or orange peel, '1' for both the moire pattern and orange peel were evaluated when the appearance was favorable without forming a wavy pattern or orange peel.

(6) Surface energy and water contact angle: The window coating layer of the window film was measured at 25 ° C using a contact angle analyzer (Phoenix 300) manufactured by Surface Electro Optics.

Example One 2 3 4 5 6 7 8 9 10 The first fluorine-containing silicone resin
(Parts by weight) Production Example 1-1 0.5 One 5 10 5 5 - - - 5 Production Example 1-2 - - - - - - 5 - - - Production Example 1-3 - - - - - - - 5 - - Production Example 1-4 - - - - - - - - 5 - The second silicone resin
(Parts by weight)
Production Example 2 99.5 99 95 90 95 95 95 95 95 - Production Example 3 - - - - - - - - - 95 Cross-linking agent
(Parts by weight) 25 25 25 25 25 25 25 25 25 25 Initiator
(Parts by weight) One One One One One One One One One One Coating layer thickness
(탆) 50 50 50 50 10 50 50 50 50 50 RIQ 88.4 91.2 92.5 91.1 91.8 87 91.7 90.8 90.1 89.7 I reflectance
(%, @ 550 nm) 1.108 0.990 0.943 0.925 0.984 0.907 0.979 0.984 0.99 0.947 Pencil hardness 8H 8H 8H 8H 4H 8H 8H 8H 8H 8H Radius of curvature (mm) 0.38 0.42 0.36 0.42 0.24 0.44 0.67 0.41 0.57 0.51 Exterior 2 3 3 3 3 2 3 3 3 3

Example 11 12 13 14 15 16 The first fluorine-containing silicone resin
(Parts by weight) Production Example 1-1 0.5 One 5 10 One One Production Example 1-2 - - - - - - Production Example 1-3 - - - - - - Production Example 1-4 - - - - - - The second silicone resin
(Parts by weight) Production Example 4 99.5 99 95 90 99 99 Cross-linking agent
(Parts by weight) 40 40 40 40 40 40 Fluorine-based (meth) acrylate-based resin (parts by weight) - - - - 2 5 Initiator
(Parts by weight) One One One One One One Coating layer thickness
(탆) 50 50 50 50 50 50 RIQ 88.1 91.3 93.5 94.0 93.6 94.2 Pencil hardness 6H 6H 5H 5H 7H 8H Exterior 3 3 3 3 3 3 Surface energy (mN / m, @ 25 ℃) 28.999 27.154 24.767 23.340 24.292 23.276 Water contact angle (°, @ 25 ℃) 82.18 84.30 87.14 88.90 87.72 88.98

Comparative Example 1 Comparative Example 2 Comparative Example 3 The second silicone resin (parts by weight) Production Example 2 100 - 100 Epoxy hybrimer (parts by weight) - 100 - Crosslinking agent (parts by weight) 25 - 25 Initiator (parts by weight) One - One Fluorine-containing leveling agent (parts by weight) - - 2.5 Coating layer thickness (탆) 10 10 10 RIQ 76.6 83.7 79.8 I reflectance (%, @ 550 nm) 2.109 1.361 1.179 Pencil hardness 9H 9H 4H Radius of curvature (mm) 0.39 0.38 0.14 Exterior One One One

As shown in Tables 2 and 3, the flexible window film of the present invention had an excellent RIQ of 85 or more and a low reflectance of 2% or less, and was excellent in appearance and less in glare. Further, the flexible window film of the present invention has a pencil hardness of 4H or more and a high hardness, a radius of curvature of 5.0 mm or less, flexibility, and can be used as a flexible window film. As shown in Table 3, the window film containing the fluorine-containing acrylate resin has a higher hardness than the window film containing the same amount of the first fluorine-containing silicone resin and improves the appearance of the window film.

However, as shown in Table 4, the comparative example not containing the first fluorine-containing silicone resin had a poor appearance due to the RIQ of less than 85.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (12)

A composition for a window film comprising a first fluorine-containing silicone resin of the following formula (1), a second silicone resin having an epoxy group or an epoxy group-containing functional group,
&Lt; Formula 1 >
(R _a SiO _{(4-a) / 2} ) _x (X _b SiO _{(4-b) / 2} ) _y
(Wherein R represents an epoxy group, an epoxy group-containing functional group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C5 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
X is a substituted or unsubstituted C1 to C30 alkyl group containing at least one fluorine, a substituted or unsubstituted C5 to C20 cycloalkyl group containing at least one fluorine, or a substituted or unsubstituted group containing at least one fluorine A substituted or unsubstituted C6 to C20 aryl group,
a is an integer of 0 to 3, b is an integer of 1 to 3, 0? x <1, 0 <y? 1, x + y = 1).
The composition for a window film according to claim 1, wherein the second silicone resin comprises a silicone resin represented by the following formula (2)
(2)
(R ¹ SiO _3/2 ) _x (R ² R ³ SiO _2/2 ) _y (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _z (SiO _4/2 ) _w
(Wherein R ¹ represents an epoxy group or an epoxy group-containing functional group,
R ² and R ³ are each independently hydrogen, a crosslinkable functional group, an unsubstituted or substituted C 1 to C 20 alkyl group, or an unsubstituted or substituted C 5 to C 20 cycloalkyl group,
R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of hydrogen, a crosslinkable functional group, an unsubstituted or substituted C 1 to C 20 alkyl group, an unsubstituted or substituted C 5 to C 20 cycloalkyl group, An aryl group of C30,
0 < y &lt; 1, 0? Y <1, 0? Z <1, 0? W <1, x + y + z + w = 1).
The composition for a window film according to claim 1, wherein the first fluorine-containing silicone resin comprises the silicone resin of the following formulas 1-1-1 to 1-1-10:
&Lt; Formula 1-1-1-1 &
(EcSiO3 / ₂ ) _x (FdSiO3 / ₂ ) _y
(1-1-2)
(EcSiO _3/2 ) _x (FoSiO _3/2 ) _y
&Lt; Formula 1-1-3 &
(GpSiO _3/2 ) _x (FdSiO _3/2 ) _y
&Lt; Formula 1-1-4 &
(GpSiO _3/2 ) _x (FoSiO _3/2 ) _y
<Formula 1-1-5>
_{(EcSiO 3/2) x1 ((Me} ) 2 SiO 2/2) x2 (FdSiO 3/2) y
<Formula 1-1-6>
_{(EcSiO 3/2) x1 ((Me} ) 2 SiO 2/2) x2 (FoSiO 3/2) y
&Lt; Formula 1-1-7 &
_{(GpSiO 3/2) x1 ((Me} ) 2 SiO 2/2) x2 (FdSiO 3/2) y
&Lt; Formula 1-1-8 &
_{(GpSiO 3/2) x1 ((Me} ) 2 SiO 2/2) x2 (FoSiO 3/2) y
&Lt; Formula 1-1-9 &
(EcSiO3 / ₂ ) _x1 (GpSiO3 / ₂ ) _x2 (FdSiO3 / ₂ ) _y
<Formula 1-1-10>
(EcSiO3 / ₂ ) _x1 (GpSiO3 / ₂ ) _x2 (FoSiO3 / ₂ ) _y
In the above formulas 1-1-1 to 1-1-10, Ec represents a 2- (3,4-epoxycyclohexyl) ethyl group, Gp represents a 3-glycidoxypropyl group, Me represents a methyl group, Fd represents 1H, 1 &gt;, 0 &lt; y < 1, x + y = 1, 0 < x1 < 1, 1, 0 <x2 <1, 0 <y <1, x1 + x2 + y = 1).
The composition for a window film according to claim 1, wherein the second silicone resin comprises a silicone resin represented by the following formula (2-1-1) or (2-1-2):
&Lt; Formula (2-1-1)
(EcSiO3 / ₂ ) _x1 (GpSiO3 / ₂ ) _x2
(3-glycidoxypropyl group, 0? X1? 1, 0? X2? 1, x1 + x2 = 1, x1 + x2 &lt;&gt; 0).
<Formula 2-1-2>
(EcSiO3 / ₂ ) _x1 (GpSiO3 / ₂ ) _x2 (SiO4 / ₂ ) _w
1, 0 <x <1, 0 <w <1 (in the formula 2-2, Ec is a 2- (3,4-epoxycyclohexyl) ethyl group, Gp is a 3-glycidoxypropyl group, , x1 + x2 + w = 1).
The composition for a window film according to claim 1, wherein the first fluorine-containing silicone resin is contained in an amount of 0.1 wt% to 50 wt% of the total amount of the first fluorine-containing silicone resin and the second silicone resin.
The composition for a window film according to claim 1, wherein the composition for a window film further comprises a crosslinking agent.
The composition for a window film according to claim 6, wherein the crosslinking agent comprises at least one of a chain aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated aromatic hydrocarbon epoxy monomer, and an oxetane monomer.
The composition for a window film according to claim 6, wherein the composition for a window film further comprises a fluorine-based (meth) acrylate resin.
The composition for a window film according to claim 6, wherein the fluorine-containing (meth) acrylate resin is contained in an amount of 1 to 20 parts by weight per 100 parts by weight of the total of the first fluorine-containing silicone resin and the second silicone resin .
Wherein the flexible window film has a RIQ of 85 or more, a pencil hardness of 4H or more, and a radius of curvature of 5.0 mm or less.
The flexible window film of claim 10, wherein the coating layer is formed from the composition for a window film of any one of claims 1 to 9.
The flexible window film according to claim 10, wherein the coating layer has a surface energy at 25 캜 of 30 mN / m or less.

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