WO2018080034A1

WO2018080034A1 - Composition for window film, and flexible window film formed therefrom

Info

Publication number: WO2018080034A1
Application number: PCT/KR2017/010556
Authority: WO
Inventors: 우창수; 김민혜; 임지선; 장승우; 한동일
Original assignee: 삼성에스디아이 주식회사
Priority date: 2016-10-28
Filing date: 2017-09-25
Publication date: 2018-05-03

Abstract

Provided are: a composition for a window film, comprising a first silicone resin represented by chemical formula 1, a second silicone resin represented by chemical formula 2, a crosslinking agent, and an initiator; and a flexible window film formed therefrom.

Description

Composition for window film and flexible window film formed therefrom

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

In the display device, a flexible display device having a flexibility to be folded and unfolded while replacing a glass substrate or a high hardness substrate with a film has been developed. Flexible display devices are thin, light, impact-resistant, and foldable.

Since the window film is located at the outermost side of the display device, it should have good flexibility and hardness when used in the flexible display device. The window film is composed of a base layer and a coating layer. When used in a flexible display device, the window film should be well folded toward the substrate layer or the coating layer. In particular, when the window film is well folded toward the base layer, the display may be said to have a high efficiency compared to the case where the viewer is simultaneously folding the coating layer as well as a plurality of viewers.

The window film is located at the outermost side of the display device. Therefore, when the scratch resistance is low, scratches may occur on the external scratches, thereby degrading the screen quality. In particular, the minute scratches generated by the hand or the like when using the display device may not only degrade the screen quality but also damage the appearance.

On the other hand, the window film is prepared by applying a coating solution on the substrate layer, if the coating solution is not uniformly applied, the surface quality may be poor, which may cause distortion on the display, the display image is not clear or glare Can give

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

The problem to be solved by the present invention is to provide a composition for a window film that can implement a flexible window film excellent in scratch resistance, excellent flexibility when folded for both the substrate layer side and the coating layer side.

Another object of the present invention is to provide a composition for a window film that can implement a window film having excellent surface quality of the window coating layer.

Another problem to be solved by the present invention is to provide a composition for a window film that can implement a flexible window film with high hardness.

Another problem to be solved by the present invention is that there is no separate heat treatment and / or aging after UV curing, the window film can be manufactured so that the degree of curing is not affected by the ambient environment, such as temperature or humidity, so that the processability It is providing the composition for window films which can be heightened.

Another object of the present invention is to provide a composition for a window film that can implement a window film excellent in impact resistance.

Another object of the present invention is to provide a flexible window film including a coating layer formed of the composition for a window film of the present invention.

The composition for a window film of the present invention may include a first silicone resin of Formula 1, a second silicone resin of Formula 2, a crosslinking agent, and an initiator:

(R ¹ SiO _3/2 ) _x (R ² SiO _3/2 ) _y (R ³ SiO _3/2 ) _z (R ⁴ R ⁵ SiO _2/2 ) _w (R ⁶ R ⁷ R ⁸ SiO _1/2 ) _u (SiO _4/2 ) _v

(In Formula 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , x, y, z, w, u, v are as defined in the detailed description of the invention same),

(R ¹¹ SiO _3/2 ) _x (A ³ _b SiO _(4-b) _/ ₂ ) _y1 (SiO _3/2 -A ¹ -T ¹ -A ² -SiO _3/2 ) _y2 (R ¹² SiO ₃ _/ ₂ ) _z (R ¹³ R ¹⁴ SiO _2/2 ) _w (R ¹⁵ R ¹⁶ R ¹⁷ SiO _1/2 ) _u (SiO _4/2 ) _v

In Formula 2, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , A ¹ , T ¹ , A ² , A ³ , x, y1, y2, z, w, u , v, b are as defined in the following detailed description of the invention)

The flexible window film of the present invention includes a base layer and a coating layer formed on the base layer, wherein the flexible window film may have a pencil hardness of 3H or more, a tensile curvature radius of 5.0 mm or less, and a RIQ of 90 or more.

The present invention provides a composition for a window film that is excellent in scratch resistance and can realize a flexible window film having excellent flexibility when folded on both the substrate layer side and the coating layer side.

The present invention provides a composition for a window film that can implement a window film having excellent surface quality of the window coating layer.

The present invention provides a composition for a window film that can implement a flexible window film having a high hardness.

The present invention provides a window film composition which can increase the processability by producing a window film after UV curing without a separate heat treatment and / or aging, the degree of curing is not affected by the ambient environment, such as temperature or humidity Provided.

The present invention provides a composition for a window film that can implement a window film excellent in impact resistance.

The present invention provides a flexible window film comprising a coating layer formed of the composition for a window film of the present invention.

1 is a conceptual diagram of a composite of silica and one embodiment of the silicone resin of Formula 1 according to another embodiment of the present invention.

2 is a cross-sectional view of a flexible window film according to an embodiment of the present invention.

3 is a cross-sectional view of a flexible window film according to another embodiment of the present invention.

4 is a cross-sectional view of a flexible window film according to another embodiment of the present invention.

5 is a cross-sectional view of a flexible display device according to an exemplary embodiment of the present invention.

6 is a cross-sectional view of a flexible display device according to another exemplary embodiment of the present invention.

7 is a cross-sectional view of a flexible display device according to still another embodiment of the present invention.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.

In the present specification, "upper" and "lower" are defined based on the drawings, and according to a viewpoint, "upper" may be changed to "lower" and "lower" to "upper", and "on" or What is referred to as “on” may include not only the above but also intervening other structures in the middle. On the other hand, what is referred to as "directly on" or "directly on" means that there is no intervening structure in between.

As used herein, "(meth) acryl" refers to acrylic and / or methacryl.

In this specification, "substituted" means, unless specifically stated, that at least one hydrogen atom of the functional group is 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 It means substituted with an alkyl group of C1 to C10 substituted with an aryl group of C20, an arylalkyl group of C7 to C20, a C6 to C20 aryl group substituted with an alkyl group of C1 to C10, or an alkoxy group of C1 to C10.

As used herein, an "alkoxyene group" refers to an alkylene group-O- or an alkylene group-O-alkylene group.

As used herein, "halogen" means fluorine, chlorine, bromine or iodine.

In the present specification, "Me" is a methyl group, "Ph" is a phenyl group, "Et" is an ethyl group, "Ety" is an ethylene group, "Pry" is a propylene group, "Buty" is a butylene group, and "X ₁ " is an acrylate group. (* -OC (= O) -CH (CH ₂ ), * is linking site), "X ₂ " is methacrylate group (* -OC (= O) -CCH ₃ (CH ₂ ), * is linking site ) And "X" is a (meth) acrylate group.

As used herein, "Z", "Z ₁ ", and "Z ₂ " are each a moiety of the formulas A, B, and C, derived from pentaerythritol tri (meth) acrylate:

(Wherein * is a linking site)

(Wherein * is a linking site)

(Wherein * is a linking site).

"W" in this specification is a moiety of the formula (D), which is derived from dipentaerythritol penta (meth) acrylate:

(Wherein * is a linking site).

In the present specification, "Fd" is a 1H, 1H, 2H, 2H-perfluorodecyl group, and "Fo" is a 1H, 1H, 2H, 2H-perfluorooctyl group.

In the present specification, a "monoalkylene oxide group or a polyalkylene oxide group" means *-[-OR ^a- ] _n -[-OR ^{a '} -] _m- * (* is a connection portion of an element, R ^a , R ^{a Are} each independently a substituted or unsubstituted C1 to C5 alkylene group, n is an integer of 1 to 5, m is an integer of 0 to 5).

In the present specification, "Ec" is a 2- (3,4-epoxycyclohexyl) ethyl group.

"Reflected Image Quality (RIQ)" herein refers to measuring the sharpness of the reflected image of the surface of the window coating layer. The RIQ is measured by Rhopoint's Rhopoint IQ, and can be a value from 0 to 100. The larger the RIQ value, that is, the closer to 100, the smoother the surface of the window coating layer and the better the surface quality.

In the present specification, the "modulus" of the adhesive layer is a storage modulus, and is used as an auto strain condition at a shear rate of 1 rad / sec and a strain of 1% using ARES (Anton Paar, MCR-501), a dynamic viscoelasticity measuring device. Viscoelasticity was measured. After removing the release film, the pressure-sensitive adhesive layer was laminated to a thickness of 500 μm, and the laminate was punched out using a perforator having a diameter of 8 mm to be used as a specimen. The measurement was performed at a temperature rising rate of 5 ° C./min in a temperature range of −60 ° C. to 90 ° C. using a jig of 8 mm, and modulus was recorded at −20 ° C., 25 ° C., and 80 ° C.

In the present specification, the "average particle diameter" of the organic nanoparticles is a particle size of the organic nanoparticles expressed in Z-average values and the SEM / TEM observations measured in an aqueous or organic solvent with a Zetasizer nano-ZS device manufactured by Malvern. .

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 the present embodiment may include a first silicone resin, a second silicone resin, a crosslinking agent, and an initiator. The 1st silicone resin and the 2nd silicone resin are explained in full detail below.

The first silicone resin comprises at least one first repeating unit comprising a urethane group (urethane bond) and at least one photoreactive functional group. The second silicone resin may comprise at least one first repeating unit comprising at least one photoreactive functional group; And at least one second repeating unit comprising a fluorine or alkylene oxide group. In one embodiment, the photoreactive functional group may include a (meth) acrylate group as a radically reactive functional group as a photocurable functional group.

Therefore, the composition for a window film according to the present embodiment can produce a flexible window film having good quality as long as it has excellent scratch resistance and flexibility, and low reflectance. The window film composition may realize a flexible window film having excellent flexibility when the window film composed of the base layer and the window coating layer formed of the window film composition is folded into both the base layer or the window coating layer. In particular, the composition for the window film by implementing a window film that can be folded well to the base layer as well as the coating layer side, a plurality of viewers can simultaneously view the display can increase the efficiency. Since a predetermined force acts on the window coating layer when the window film is folded toward the base layer, the window coating layer may be broken when flexibility is not good. In addition, the composition for a window film according to the present embodiment can implement a window film having high hardness, low curling and excellent impact resistance.

The composition for the window film containing only the first silicone resin may have a low surface quality due to a low RIQ and may not have a good impact resistance. The composition for a window film containing only the second silicone resin may have poor scratch resistance, poor flexibility and hardness, and poor impact resistance.

In addition, the composition for a window film according to the present embodiment includes the first silicone resin and the second silicone resin, so that the degree of curing is not affected by the ambient environment such as temperature or humidity after UV curing and without additional heat treatment and / or aging. The window film can be manufactured without being affected, thereby improving processability. Usually, a composition for a window film comprising a silicone resin having an epoxy group, for example, an alicyclic epoxy group, requires an aging treatment after UV curing at the time of forming the window coating layer.

Each of the first silicone resin and the second silicone resin may be included alone in the silicone resin composition in the composition for a window film. However, the first silicon resin and the second silicon resin may be included in the composition for a window film by bonding to inorganic particles or organic particles to form a composite, respectively. This is described in more detail below.

Hereinafter, a composition for a window film according to an embodiment of the present invention will be described. The composition for a window film of the present embodiment may include a first silicone resin of formula 1, a second silicone resin of formula 2, a crosslinking agent and an initiator:

Hereinafter, the first silicone resin of the formula (1) will be described. The first silicone resin of Formula 1 may improve the hardness and flexibility of the window film, improve scratch resistance, and improve impact resistance:

(From the above,

R ¹ is a monovalent organic group having one (meth) acrylate group and at least one urethane group,

R ² is a monovalent organic group having two or more (meth) acrylate groups and one or more urethane groups,

R ³ is a non-urethane-based monovalent organic group having one or more (meth) acrylate groups,

Unsubstituted or substituted C1 to C20 alkyl group, unsubstituted or substituted C5 to C20 cycloalkyl group, or unsubstituted or substituted C6 to C30 aryl group,

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are each independently hydrogen, a monovalent organic group having one or more (meth) acrylate groups, an unsubstituted or substituted C1 to C20 alkyl group, an unsubstituted or A substituted C5 to C20 cycloalkyl group, or an unsubstituted or substituted C6 to C30 aryl group,

0≤x≤1, 0≤y≤1, 0≤z <1, 0≤w <1, 0≤u <1, 0≤v <1, x + y ≠ 0, x + y + z + w + u + v = 1).

Specifically, R ¹ is a monovalent organic group having one (meth) acrylate group at the terminal and including one or more urethane groups in the organic group. In one embodiment, R ¹ may be represented by formula i:

* -Y ₁ -NH- (C = O) -OY ₂ -X

(From the above,

* Is the connection site,

Y ₁ , Y ₂ are each independently a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C5 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

X is a (meth) acrylate group).

Preferably, Y ₁ , Y ₂ are each independently a substituted or unsubstituted C1 to C10 alkylene group, more preferably a substituted or unsubstituted C1 to C5 alkylene group such as methylene group, ethylene Group, propylene group, butylene group or pentylene group. For example, R ¹ may be a monovalent organic group having one (meth) acrylate group at the terminal and including one urethane group in the organic group.

Specifically, R ² is a monovalent organic group having two or more (meth) acrylate groups at its terminals and including one or more urethane groups in the organic group. In one embodiment, R ² can be represented by the following formula (ii):

* -Y ₃ -NH- (C = O) -OY _4- (X) n

(From the above,

* Is the connection site,

Y ₃ is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C5 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

Y ₄ is a substituted or unsubstituted branched alkylene group having 3 to 20 carbon atoms; Substituted or unsubstituted branched alkoxy group having 3 to 20 carbon atoms; A cycloalkylene group having 5 to 20 carbon atoms having a substituted or unsubstituted branched alkyl group having 3 to 20 carbon atoms or a substituted or unsubstituted branched carbon group having 3 to 20 carbon atoms; Or a C6-C20 arylene group having a substituted or unsubstituted branched C3-C20 alkylene group or a substituted or unsubstituted branched C3-C20 alkoxyne group,

X is a (meth) acrylate group,

n is an integer of 2 or more).

Preferably, Y ₃ is each independently a substituted or unsubstituted C1 to C10 alkylene group, more preferably a substituted or unsubstituted C1 to C5 alkylene group, for example, a methylene group, an ethylene group, a propylene group , Butylene group or pentylene group.

Preferably, Y ₄ may be a substituted or unsubstituted branched alkylene group having 3 to 20 carbon atoms, or a substituted or unsubstituted branched alkyl group having 3 to 20 carbon atoms. For example, Y ₄ may be, but is not limited to, the following functional groups derived from pentaerythritol or dipentaerythritol:

(Wherein * is a linking site)

Preferably, n may be an integer of 2 or more and 15 or less, more preferably 2 or more and 5 or less. For example, R ² may be a monovalent organic group having two or more (meth) acrylate groups at the terminal and including one urethane group in the organic group.

Specifically, R ³ may be a monovalent organic group having a non-urethane group having no urethane group and having one or more (meth) acrylate groups at its terminals. For example, R ³ may be represented by the following formula (iii):

* -Y _5- (X) n

(From the above,

* Is the connection site,

Y ₅ is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C5 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

X is a (meth) acrylate group,

n is an integer of 1 or more).

Preferably, Y ₅ may be a substituted or unsubstituted C1 to C5 alkylene group, for example, methylene group, ethylene group, propylene group, butylene group or pentylene group. Preferably, n may be an integer of 1 or more and 6 or less.

Or specifically, R ³ may be an unsubstituted or substituted C1 to C20 alkyl group, an unsubstituted or substituted C5 to C20 cycloalkyl group, or an unsubstituted or substituted C6 to C30 aryl group. Preferably, R ³ may be a methyl group, an ethyl group, a phenyl group, or the like.

Specifically, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are each independently hydrogen, a monovalent organic group having one or more (meth) acrylate groups, a substituted or unsubstituted C1 to C10 alkyl group, It may be a substituted or unsubstituted C5 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C10 aryl group. At this time, the monovalent organic group having one or more (meth) acrylate groups may be represented by the formula (i), (ii) or (iii). Preferably, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are each independently a substituted or unsubstituted C1 to C5 alkyl group, for example a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group Can be.

In Formula ^{_{_{1, (R 1 SiO 3/}}} 2), (R 2 SiO 3/2), ^{_{_{(R 3 SiO 3/2)}}} , ^{^{_{_{(R 4 R 5 SiO 2/}}}} 2), (R ⁶ R ⁷ R ⁸ SiO _1/2 ), (SiO _{_{_4/2)}} may also contain two or more different units, respectively. That is, for example, when the resin of Chemical Formula 1 is represented by (R ¹ SiO _3/2 ) _x (R ² SiO _3/2 ) _y as in Chemical Formula 1-1, (R ^1a SiO _3/2 ) _x1 ^{_{_{(R 1b SiO 3/2) x2 (}}} R 2 SiO 3/2) y (R 1a, R 1b are the same as R ¹ defined in formula 1, R ² and R ² are as defined in formula 1, R ^1a , R ^1b is different from each other, and 0 <x 1 <1, 0 <x 2 <1, 0 <y <1, x 1 + x 2 + y = 1) may also be included in the scope of the present invention.

In one embodiment, the first silicone resin of Formula 1 may be a silicone resin of T units and T units represented by the following Formula 1-1:

(R ¹ SiO _3/2 ) _x (R ² SiO _3/2 ) _y

(In the above, R ¹ , R ² are as defined in Formula 1, 0 <x <1, 0 <y <1, x + y = 1)

Specifically, in Chemical Formula 1-1, 0.50 ≦ x ≦ 0.99, 0.01 ≦ y ≦ 0.50, x + y = 1, preferably, 0.70 ≦ x ≦ 0.99, 0.01 ≦ y ≦ 0.30, x + y = 1, More preferably 0.80 ≦ x ≦ 0.99, 0.01 ≦ y ≦ 0.20, and x + y = 1. Within this range, the scratch resistance is excellent, and when the window film is folded into each of the base layer and the window coating layer, the flexibility is excellent, the hardness is excellent, and the impact resistance may be good.

For example, the silicone resin of Chemical Formula 1-1 may include the silicone resin of Chemical Formula 1-1-1 to Chemical Formula 1-1-10.

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x ((ZO- (C = O) NH-Pry) SiO _3/2 ) _y

((X-Buty-O- (C = O) NH-Pry) SiO _3/2 ) _x ((ZO- (C = O) NH-Pry) SiO _3/2 ) _y

((X-Pry-O- (C = O) NH-Pry) SiO _3/2 ) _x ((ZO- (C = O) NH-Pry) SiO _3/2 ) _y

(In the above, 0 <x <1, 0 <y <1, x + y = 1)

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x ((WO- (C = O) NH-Pry) SiO _3/2 ) _y

((X-Buty-O- (C = O) NH-Pry) SiO _3/2 ) _x ((WO- (C = O) NH-Pry) SiO _3/2 ) _y

((X-Pry-O- (C = O) NH-Pry) SiO _3/2 ) _x ((WO- (C = O) NH-Pry) SiO _3/2 ) _y

(In the above, 0 <x <1, 0 <y <1, x + y = 1)

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x1 ((X-Buty-O- (C = O) NH-Pry) SiO _3/2 ) _x2 ((ZO- (C = O) NH-Pry) SiO _3/2 ) _y

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x1 ((X-Pry-O- (C = O) NH-Pry) SiO _3/2 ) _x2 ((ZO- (C = O) NH-Pry) SiO _3/2 ) _y

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x1 ((X-Buty-O- (C = O) NH-Pry) SiO _3/2 ) _x2 ((WO- (C = O) NH-Pry) SiO _3/2 ) _y

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x1 ((X-Pry-O- (C = O) NH-Pry) SiO _3/2 ) _x2 ((WO- (C = O) NH-Pry) SiO _3/2 ) _y

(In the above, 0 <x1 <1, 0 <x2 <1, 0 <y <1, x1 + x2 + y = 1).

In Formulas 1-1-1 to 1-1-6, x and y may have values in Formula 1. Within this range, the scratch resistance is excellent, and when the window film is folded into each of the base layer and the window coating layer, the flexibility is excellent, the hardness is excellent, and the impact resistance may be good.

In Formulas 1-1-7 to 1-1-10, x1, x2, and y may have the following values: 0.25 ≦ x1 ≦ 0.50, 0.25 ≦ x2 ≦ 0.50, 0.01 ≦ y ≦ 0.50, x1 + x2 + y = 1, preferably, 0.30 ≦ x1 ≦ 0.50, 0.30 ≦ x2 ≦ 0.50, 0.01 ≦ y ≦ 0.30, and x1 + x2 + y = 1. Within this range, the scratch resistance is excellent, and when the window film is folded into the base layer and the window coating layer, respectively, the flexibility and the hardness are excellent, and the impact resistance may be good.

In another embodiment, the silicone resin of Chemical Formula 1 may be a silicone resin having a T unit represented by Chemical Formula 1-2 below:

(R ¹ SiO _3/2 ) _x

(Wherein R ¹ is as defined in Formula 1 above, x is 1).

For example, the silicone resin of Formula 1-2 may include a silicone resin of Formula 1-2-1 to Formula 1-2-3.

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 )

((X-Buty-O- (C = O) NH-Pry) SiO _3/2 )

((X-Pry-O- (C = O) NH-Pry) SiO _3/2 )

In another embodiment, the silicone resin of Formula 1 may be a silicone resin of T units, T units, and T units represented by the following Formula 1-3:

(R ¹ SiO _3/2 ) _x (R ² SiO _3/2 ) _y (R ³ SiO _3/2 ) _z

(In the above, R ¹ , R ² , R ³ are as defined in Formula 1,

0 <x <1, 0 <y <1, 0 <z <1, x + y + z = 1).

Specifically, in Formula 1-3, 0.50 ≦ x ≦ 0.95, 0.01 ≦ y ≦ 0.40, 0.01 ≦ z ≦ 0.40, x + y + z = 1, preferably, 0.50 ≦ x ≦ 0.90, 0.01 ≦ y ≦ 0.30, 0.05 ≦ z ≦ 0.30, x + y + z = 1, more preferably 0.50 ≦ x ≦ 0.80, 0.01 ≦ y ≦ 0.20, 0.05 ≦ z ≦ 0.30, and x + y + z = 1. Within this range, the scratch resistance is excellent, and when the window film is folded into the base layer and the window coating layer, respectively, the flexibility and the hardness may be excellent, and the impact resistance may be excellent.

For example, the silicone resin of Chemical Formula 1-3 may include the silicone resin of Chemical Formulas 1-3-1 to Chemical Formula 1-3-10.

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x ((ZO- (C = O) NH-Pry) SiO _3/2 ) _y ((X-Pry) SiO _{3 / 2} ) _z

((X-Buty-O- (C = O) NH-Pry) SiO _3/2 ) _x ((ZO- (C = O) NH-Pry) SiO _3/2 ) _y ((X-Pry) SiO _{3 / 2} ) _z

((X-Pry-O- (C = O) NH-Pry) SiO _3/2 ) _x ((ZO- (C = O) NH-Pry) SiO _3/2 ) _y ((X-Pry) SiO _{3 / 2} ) _z

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x ((ZO- (C = O) NH-Pry) SiO _3/2 ) _y (MeSiO _3/2 ) _z

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x ((ZO- (C = O) NH-Pry) SiO _3/2 ) _y (PhSiO _3/2 ) _z

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x ((WO- (C = O) NH-Pry) SiO _3/2 ) _y ((X-Pry) SiO _{3 / 2} ) _z

((X-Buty-O- (C = O) NH-Pry) SiO _3/2 ) _x ((WO- (C = O) NH-Pry) SiO _3/2 ) _y ((X-Pry) SiO _{3 / 2} ) _z

((X-Pry-O- (C = O) NH-Pry) SiO _3/2 ) _x ((WO- (C = O) NH-Pry) SiO _3/2 ) _y ((X-Pry) SiO _{3 / 2} ) _z

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x ((WO- (C = O) NH-Pry) SiO _3/2 ) _y (MeSiO _3/2 ) _z

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x ((WO- (C = O) NH-Pry) SiO _3/2 ) _y (PhSiO _3/2 ) _z

(In the above, 0 <x <1, 0 <y <1, 0 <z <1, x + y + z = 1).

In another embodiment, the silicone resin of Formula 1 may be a silicone resin of T units, T units, and D units represented by the following Formula 1-4:

(R ¹ SiO _3/2 ) _x (R ² SiO _3/2 ) _y (R ⁴ R ⁵ SiO _2/2 ) _w

(In the above, R ¹ , R ² , R ⁴ , R ⁵ are as defined in Formula 1, 0 <x <1, 0 <y <1, 0 <w <1, x + y + w = 1) .

Specifically, in Formula 1-4, 0.50 ≦ x ≦ 0.95, 0.01 ≦ y ≦ 0.40, 0.01 ≦ w ≦ 0.30, x + y + w = 1, preferably, 0.60 ≦ x ≦ 0.95, 0.01 ≦ y ≦ 0.30, 0.01 ≦ w ≦ 0.20, and x + y + w = 1. Within this range, the scratch resistance is excellent, and when the window film is folded into the base layer and the window coating layer, respectively, the flexibility and the hardness may be excellent, and the impact resistance may be excellent.

In another embodiment, the silicone resin of Formula 1 may be a silicone resin of T units, T units and M units represented by the following Formula 1-5:

(R ¹ SiO _3/2 ) _x (R ² SiO _3/2 ) _y (R ⁶ R ⁷ R ⁸ SiO _1/2 ) _u

(In the above, R ¹ , R ² , R ⁶ , R ⁷ , R ⁸ are the same as defined in Chemical Formula 1, 0 <x <1, 0 <y <1, 0 <u <1, x + y + u = 1).

Specifically, in Formula 1-5, 0.50 ≦ x ≦ 0.95, 0.01 ≦ y ≦ 0.40, 0.01 ≦ u ≦ 0.30, x + y + u = 1, preferably, 0.60 ≦ x ≦ 0.95, 0.01 ≦ y ≦ 0.30, 0.01 ≦ u ≦ 0.20, and x + y + u = 1. Within this range, the scratch resistance is excellent, and when the window film is folded into the base layer and the window coating layer, respectively, the flexibility and the hardness may be excellent, and the impact resistance may be excellent.

In another embodiment, the silicone resin of Formula 1 may be a silicone resin of T units, T units, and Q units represented by the following Formula 1-6:

(R ¹ SiO _3/2 ) _x (R ² SiO _3/2 ) _y (SiO _4/2 ) _v

(In the above, R ¹ , R ² are the same as defined in Formula 1,

0 <x <1, 0 <y <1, 0 <v <1, x + y + v = 1).

Specifically, in Formula 1-6, 0.50 ≦ x ≦ 0.95, 0.01 ≦ y ≦ 0.40, 0.01 ≦ v ≦ 0.30, x + y + v = 1, preferably, 0.60 ≦ x ≦ 0.95, 0.01 ≦ y ≦ 0.30, 0.01 ≦ v ≦ 0.20, and x + y + v = 1. Within this range, the scratch resistance is excellent, and when the window film is folded into the base layer and the window coating layer, respectively, the flexibility and the hardness may be excellent, and the impact resistance may be excellent.

The first silicone resin of Formula 1 may have a weight average molecular weight of 1,000 g / mol to 20,000 g / mol, specifically 1,500 g / mol to 10,000 g / mol, more specifically 2,000 g / mol to 6,000 g / mol have. It is possible to improve the appearance of the window film in the above range and to increase the transparency. The first silicon resin of Formula 1 may have a polydispersity (PDI) of 1.0 to 3.0, specifically 1.0 to 2.0. In the above range, the coating property of the composition is good, there may be a stable coating properties.

In the total of 100 parts by weight of the first silicone resin of Formula 1, the second silicone resin of Formula 2, and the crosslinking agent, the silicone resin of Formula 1 is 10 parts by weight to 80 parts by weight, specifically 20 parts by weight to 80 parts by weight, 30 parts by weight to 80 parts by weight, 40 parts by weight to 80 parts by weight, 50 parts by weight to 80 parts by weight, and 60 parts by weight to 80 parts by weight. Within this range, the scratch resistance and flexibility of the window film may be good, the hardness may be good, and the impact resistance may be good.

Hereinafter, the second silicone resin of the formula (2) will be described.

(From the above,

R ¹¹ is a monovalent organic group having at least one (meth) acrylate group and at least one urethane group, or a non-urethane monovalent organic group having at least one (meth) acrylate group.

R ¹² is an unsubstituted or substituted C1 to C20 alkyl group, an unsubstituted or substituted C5 to C20 cycloalkyl group, or an unsubstituted or substituted C6 to C30 aryl group,

R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ are each independently hydrogen, a monovalent organic group having one or more (meth) acrylate groups, an unsubstituted or substituted C1 to C20 alkyl group, an unsubstituted or A substituted C5 to C20 cycloalkyl group, or an unsubstituted or substituted C6 to C30 aryl group,

A ³ 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 substitution containing at least one fluorine or Unsubstituted C6 to C20 aryl group, b is an integer of 1 to 3

A ¹ and A ² are each independently a single bond or a substituted or unsubstituted C1 to C5 alkylene group,

T ¹ is a monoalkylene oxide group or a polyalkylene oxide group,

0 <x <1, 0 <y1 + y2 <1, 0≤y1 <1, 0≤y2 <1, 0≤z <1, 0≤w <1, 0≤u <1, 0≤v <1, x + y1 + y2 + z + w + u + v = 1).

Specifically, R ¹¹ may represent the structure of Chemical Formula i, ii, or iii.

Specifically, A ³ is C1 to C10 fluoroalkyl group, C1 to C10 perfluoroalkyl group, C1 to C10 alkyl group having C1 to C10 fluoroalkyl group, or C1 to C1 having C1 to C10 perfluoroalkyl group To C10 may be an alkyl group. More specifically, A ³ is a 1H, 1H, 2H, 2H-perfluorodecyl group, 1H, 1H, 2H, 2H-perfluorooctyl group, or 1H, 1H, 2H, 2H-perfluorohexyl group, or the like. This can be

Specifically, A ¹ and A ² are each independently a single bond, ethylene group, n-propylene group, iso-propylene group, 1,2-butylene group, 1,3-butylene group, 1,4-butylene group or 2,3-butylene group.

Specifically, T ¹ may be *-[-OC ₂ H _4- ] _n- * (* is a linking site).

In one embodiment, the second silicone resin of Formula 2 may be represented by the following Formula 2-1:

(R ¹¹ SiO _3/2 ) _x (A ³ _b SiO _{(4-b) / 2} ) _y1 (SiO _3/2 -A ¹ -T ¹ -A ² -SiO _3/2 ) _y2

(From the above,

R ¹¹ , A ³ , A ¹ , A ² , T ¹ , b are the same as defined in Formula 2,

0 <x <1, 0 <y1 + y2 <1, 0 ≦ y1 <1, 0 ≦ y2 <1, x + y1 + y2 = 1).

In Formula 2-1, 0.85 ≦ x ≦ 0.99, 0.01 ≦ y1 ≦ 0.15, y2 = 0, or 0.85 ≦ x ≦ 0.99, 0.01 ≦ y2 ≦ 0.15, y1 = 0, specifically 0.90 ≦ x ≦ 0.99, 0.01 ≦ y1 ≦ 0.10, y2 = 0 or 0.90 ≦ x ≦ 0.99, 0.01 ≦ y2 ≦ 0.10, y1 = 0. In the above range, it is possible to implement a window film having good hardness, surface quality and flexibility.

For example, the silicone resin of Chemical Formula 2-1 may be represented by the following Chemical Formulas 2-1-1 to 2-1-9:

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x (FdSiO _3/2 ) _y1

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x (FoSiO _3/2 ) _y1

((X-Buty-O- (C = O) NH-Pry) SiO _3/2 ) _x (FdSiO _3/2 ) _y1

((X-Buty-O- (C = O) NH-Pry) SiO _3/2 ) _x (FoSiO _3/2 ) _y1

((X-Pry-O- (C = O) NH-Pry) SiO _3/2 ) _x (FdSiO _3/2 ) _y1

((X-Pry-O- (C = O) NH-Pry) SiO _3/2 ) _x (FoSiO _3/2 ) _y1

(In the above, 0 <x <1, 0 <y1 <1, x + y1 = 1)

((X-Ety-O- (C = O) NH-Pry) SiO _3/2 ) _x (SiO _3/2 -C ₂ H ₄ -[-OC ₂ H _4- ] ₄ -SiO _3/2 ) _y2

((X-Buty-O- (C = O) NH-Pry) SiO _3/2 ) _x (SiO _3/2 -C ₂ H ₄ -[-OC ₂ H _4- ] ₄ -SiO _3/2 ) _y2

((X-Pry-O- (C = O) NH-Pry) SiO _3/2 ) _x (SiO _3/2 -C ₂ H ₄ -[-OC ₂ H _4- ] ₄ -SiO _3/2 ) _y2

(In the above, 0 <x <1, 0 <y2 <1, x + y2 = 1)

The second silicone resin of Formula 2 may have a weight average molecular weight of 1,000 g / mol to 20,000 g / mol, specifically 1,500 g / mol to 10,000 g / mol, more specifically 2,000 g / mol to 6,000 g / mol have. It is possible to improve the appearance of the window film in the above range and to increase the transparency. The second silicon resin of Chemical Formula 2 may have a polydispersity (PDI) of 1.0 to 3.0, specifically 1.0 to 2.0. In the above range, the coating property of the composition is good, there may be a stable coating properties.

In the total of 100 parts by weight of the first silicone resin of Formula 1, the second silicone resin of Formula 2, and the crosslinking agent, the second silicone resin of Formula 2 is 0.1 parts by weight to 50 parts by weight, specifically 0.1 parts by weight to 40 parts by weight. 0.1 parts by weight to 30 parts by weight, 0.1 parts by weight to 20 parts by weight, 0.1 parts by weight to 10 parts by weight, 0.1 parts by weight to 5 parts by weight, and 0.1 parts by weight to 1 parts by weight. In the above range, the surface quality of the window film may be good, flexibility and the like.

The crosslinking agent may be cured together with the first silicone resin of Chemical Formula 1 and the second silicone resin of Chemical Formula 2 to improve the hardness and flexibility of the window film. The crosslinking agent may comprise at least one and preferably at least two, for example monomers having from 2 to 15 radically reactive functional groups. The radical reactive functional group can be a (meth) acrylate group.

The (meth) acrylate monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylic Neopentylglycol adipate di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (Meth) acryloxy ethyl isocyanurate, allylated cyclohexyl di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentanedi (meth) acrylate, ethylene oxide modified hexa Hydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentylglycol modified trimethylpropane di (meth) acrylate, adamantane di (meth) Difunctional (meth) acrylates such as t) acrylate or 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene; Trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylay Ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane tri (meth) including tide (6) trimethylolpropane triacrylate, ethoxylated (9) trimethylolpropane triacrylate, and the like Trifunctional (meth) acrylates such as acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethyl isocyanurate; Tetrafunctional (meth) acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; 5-functional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; And dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (ex. Isocyanate monomers and trimethylolpropane tri (meth) acrylate 6 functional type (meth) acrylates, such as a reactant, etc. are mentioned, but it is not limited to these These can be used individually or in mixture of 2 or more types.

Preferably, the (meth) acrylate monomer is an alkylene oxide modified trimethylolpropane containing ethoxylated (6) trimethylolpropane triacrylate, ethoxylated (9) trimethylolpropane triacrylate, or the like. One or more of trifunctional (meth) acrylate monomers, such as triacrylate, can be included.

The (meth) acrylate monomer may include a urethane group or may not contain a urethane group. The (meth) acrylate monomer having a urethane group may be used by using conventional products known to those skilled in the art or by synthesis. For example, the (meth) acrylate-based monomer having a urethane group may include CHTU-9607 (Camton), AN-9696 (Camton), and the like, but is not limited thereto.

The crosslinking agent may further include a monomer having an epoxy group or an oxetane group in addition to the (meth) acrylate monomer. The monomer having an epoxy group or an oxetane group may further increase the flexibility of the coating layer by further including at least one of a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and a hydrogenated aromatic hydrocarbon group. Monomers having an epoxy group or an oxetane group may include at least one of a chain aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated aromatic hydrocarbon epoxy monomer, and an oxetane monomer, which may be included alone or in combination.

Chain aliphatic epoxy monomers include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, and polyethylene glycol diglycol. Cydyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ether; Polyglycidyl ethers of polyether polyols obtained by adding one or two 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 epoxystearate; Octyl epoxystearate; Epoxidized flax oils; Epoxidized polybutadiene etc. are mentioned.

The cyclic aliphatic epoxy monomer is a compound having one or more epoxy groups 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-epoxy-6-methyl 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-3', 4'- Epoxycyclohexanecarboxylate, 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3, 4-epoxycyclohex Acid carboxylate)), 3,4-epoxycyclohexylmethyl (meth) acrylate, bis (3,4-epoxycyclohexylmethyl) adipate, 4-vinylcyclohexenedioxide, vinylcyclohexene monooxide Etc. can be mentioned.

Hydrogenated aromatic hydrocarbon epoxy monomer means a compound obtained by selectively hydrogenating an aromatic epoxy monomer under 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; Novolac type epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, hydroxybenzaldehyde phenol novolac epoxy resins; And polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinyl phenol.

Oxetane monomers include 3-methyloxetane, 2-methyloxetane, 2-ethylhexyl oxetane, 3-oxetanol, 2-methyleneoxetane, 3,3-oxetane dimethanethiol, 4- (3-methyl Oxetan-3-yl) benzonitrile, N- (2,2-dimethylpropyl) -3-methyl-3-oxetanemethaneamine, N- (1,2-dimethylbutyl) -3-methyl-3- Oxetanemethaneamine, (3-ethyloxetan-3-yl) methyl (meth) acrylate, 4-[(3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyl- May comprise one or more of 3-hydroxymethyloxetane, xylenebisoxetane, 3- [ethyl-3 [[(3-ethyloxetan-3-yl)] methoxy] methyl] oxetane, This is not restrictive.

In a total of 100 parts by weight of the first silicone resin of Formula 1, the second silicone resin of Formula 2, and the crosslinking agent, the crosslinking agent is 1 part by weight to 50 parts by weight, specifically 1 part by weight to 40 parts by weight, 1 part by weight to It may be included in 30 parts by weight, 1 to 20 parts by weight. Within this range, the scratch resistance and flexibility of the window film may be good, and the hardness may be good.

The initiator is to cure the first silicone resin of the formula (1), the second silicone resin of the formula (2), the crosslinking agent, and may include an optical radical initiator alone or in mixture of two or more thereof. The photoradical initiator may be one known to those skilled in the art. For example, a hydroxy ketone type, a phosphine oxide type, a benzoin type, an amino ketone type radical photoinitiator etc. can be used as an optical radical initiator. Specifically, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide, benzoin, benzoin methyl ether, benzoin ethyl ether , Benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2,2'-diethoxy acetophenone, 2,2'-dibutoxy Acetophenone, 2-hydroxy-2-methyl propiophenone, pt-butyl trichloro acetophenone, pt-butyl dichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, Acetophenone compounds such as dimethylamino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 2-benzyl-2-dimethyl amino-1- (4-morpholino phenyl) -butan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methyl Thio) phenyl] -2-morpholino-propane-1- On, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4-nonsidiethylaminobenzophenone, dichlorobenzophenone, 2 -Methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4- Dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoic acid ester, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl ) Phenyl] propanone] etc. are mentioned. Preferably, hydroxy ketone initiators, such as 1-hydroxycyclohexyl phenyl ketone, can be used.

The initiator may further comprise conventional photocationic initiators known to those skilled in the art. For example, the photocationic initiator may include an onium salt compound.

The initiator is 0.1 parts by weight to 10 parts by weight, specifically 0.5 parts by weight to 5 parts by weight, 1 part by weight based on 100 parts by weight of the total of the first silicone resin of Formula 1, the second silicone resin of Formula 2 and the crosslinking agent To 3 parts by weight. In this range, the silicone resin can be sufficiently cured and the remaining amount of initiator can be left to prevent the optical properties (transmittance, color, light resistance, etc.) of the window film from being lowered.

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

Nanoparticles may be included in the composition for a window film independently without bonding with the first silicone resin of the formula (1), the second silicone resin of the formula (2). Nanoparticles can further increase the hardness of the window film. Nanoparticles may include, but are not limited to, one or more of silica, aluminum oxide, zirconium oxide, titanium oxide.

Nanoparticles can include nanoparticles that have not been surface treated. Alternatively, the nanoparticles may be surface-treated in part or in whole with a silicone compound for mixing with the silicone resin. Alternatively, the nanoparticles may include nanoparticles surface-treated with a (meth) acrylate group, thereby increasing the hardness of the window film through crosslinking with the first silicone resin of Formula 1 and the second silicone resin of Formula 2. Can be.

Nanoparticles are not limited in shape and size. Specifically, the nanoparticles may include particles having a spherical shape, a plate shape, an amorphous shape, and the like. The nanoparticles may have an average particle diameter (D50) of 100 nm or less, specifically 1 nm to 100 nm, 5 nm to 50 nm, 10 nm to 20 nm, and 10 nm to 15 nm. In the above range, the hardness of the window film can be increased without affecting the surface roughness and transparency of the window film.

The nanoparticles may be included in an amount of 0.1 parts by weight to 60 parts by weight, specifically 1 part by weight to 30 parts by weight, based on 100 parts by weight of the first silicon resin of Formula 1, the second silicon resin of Formula 2, a crosslinking agent, and the nanoparticles. . In the above range, the hardness of the window film can be increased without affecting the surface roughness and transparency of the window film. At this time, the first silicone resin of Formula 1, the second silicone resin of Formula 2, the crosslinking agent may be included in the above-described content range.

The composition for a window film according to the present embodiment may further include an additive. The additive may provide additional functionality to the window film. The additives may include additives that are typically added to the window film. Specifically, the additive includes at least one of a UV absorber, a reaction inhibitor, an adhesion enhancer, a thixotropic imparting agent, a conductivity imparting agent, a color regulator, a stabilizer, an antistatic agent, an antioxidant, a leveling agent, an anti-fingerprint agent, and a surface energy modifier. You can, but are not limited to this. An adhesion promoter may include a silane compound having an epoxy or alkoxysilyl group. The thixotropic agent may include fumed silica and the like. The conductivity providing agent may include metal powder such as silver and copper aluminum. Dye control agents may include pigments, dyes and the like. The UV absorber can increase the light resistance of the window film. UV absorbers can be used 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 of triazine-based, benzimidazole-based, benzophenone-based, and benzotriazole-based. The leveling agent may include a silicone leveling agent, for example, a (meth) acrylate group-containing silicone leveling agent (eg, BYK-3500), and the like, but is not limited thereto.

The additive may be included in an amount of 0.01 parts by weight to 5 parts by weight, specifically 0.05 parts by weight to 2.5 parts by weight, based on 100 parts by weight of the first silicon resin of Formula 1, the second silicon resin of Formula 2, and a crosslinking agent. In the above range can improve the hardness and flexibility of the window film and implement the additive effect.

The composition for a window film according to the present embodiment may further include a solvent in order to facilitate coating, coatability, or processability. The solvent may include one or more of methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, but is not limited thereto.

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 the present embodiment further comprises a nanoparticle, at least a portion of the first silicon resin of the formula (1), the second silicon resin of the formula (2) comprises a composite formed by bonding to the nanoparticles Except, it is substantially the same as the composition for a window film according to an embodiment of the present invention.

At least some of the first silicone resin of Formula 1 and the second silicone resin of Formula 2 are bonded to the nanoparticles. Thus, the window film may further increase the hardness of the window film compared to the case where the first silicon resin of Formula 1, the second silicon resin of Formula 2, and nanoparticles are included in the same amount. Preferably, the composition for a window film may include a mixture of the silicone resin and a composite in which the silicone resin is bonded to nanoparticles. In this case, the hardness and flexibility of the window film can be increased at the same time.

At least one of the first silicon resin of Formula 1, the second silicon resin of Formula 2 (A) and the first silicon resin of Formula 1, at least one of the second silicon resin of Formula 2 is bonded to the nanoparticles The complex (B) in the mixture of the complex (B) may be included in 10% by weight to 60% by weight, specifically 20% by weight to 50% by weight. In the above range, the hardness and flexibility of the window film can be improved and the curling can be improved.

The nanoparticles may comprise the nanoparticles described above.

1 is a conceptual diagram of a composite of the first silicon resin of Formula 1 and silica nanoparticles according to another embodiment of the present invention. Referring to FIG. 1, the OH group on the surface of the silica and the silicon of the first silicone resin of Formula 1 may be bonded to surface-treat the silica with the first silicone resin of Formula 1. Therefore, the nanoparticles and the first silicon resin of the formula (1) can be mixed well to improve the optical transparency of the window film, it is possible to facilitate the manufacture of the window film.

The composition for a window film according to the present embodiment may include a silicone resin having no radical functional group. For example, the composition for a window film according to the present embodiment may include a third silicone resin of Formula 3 below:

(R ²¹ SiO _3/2 ) _x (R ²² SiO _3/2 ) _y (R ²³ R ²⁴ SiO _2/2 ) _z (R ²⁵ R ²⁶ R ²⁷ SiO _1/2 ) _w (SiO _4/2 ) _u

(From the above,

R ²¹ is an epoxy group or an epoxy group-containing functional group,

R ²² is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C10 aryl group,

R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C10 Aryl group, epoxy group, or epoxy group-containing functional group,

0 <x ≦ 1, 0 ≦ y <1, 0 ≦ z <1, 0 ≦ w <1, 0 ≦ u <1, x + y + z + w + u = 1).

The epoxy group may be a C2 to C10 epoxidized cycloalkyl group such as a 3,4-epoxycyclohexyl group or a glycidoxy group as an alicyclic epoxy group. The epoxy group-containing functional group may be a C1 to C10 alkyl group having the epoxy group, for example, a 2- (3,4-epoxycyclohexyl) ethyl group, a 3-glycidoxypropyl group.

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

2, the flexible window film 100 according to an embodiment of the present invention includes a base layer 110 and a coating layer 120, and the coating layer 120 is a window film according to embodiments of the present invention. It may be formed into a composition for.

The base layer 110 may support 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 attached onto the display unit, the touch screen panel, or the polarizer by an adhesive layer. The base layer 110 may be formed of an optically transparent and flexible resin. For example, the resins include polyester resins including polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate and the like, polycarbonate resins, polyimide resins, polystyrene resins, polymethylmethacrylates, and the like. It may include at least one of poly (meth) acrylate resin, cycloolefin polymer resin. The resin may be included in the base layer 110 alone or in combination. The base layer 110 may have a thickness of 10 μm to 200 μm, specifically 20 μm to 150 μm, and more specifically 50 μm to 100 μm. It can be used for 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 and the display unit, the touch screen panel, or the polarizing plate, improve the appearance, and have a high flexibility and high hardness to be used in a flexible display device. can do. The coating layer 120 may have a thickness of 5 μm to 100 μm, specifically 10 μm to 80 μm, and more specifically 10 μm to 50 μm. It can be used for the flexible window film in the above range.

Although not shown in FIG. 2, a functional surface layer such as an anti-reflection layer, an anti-glare layer, a hard coating layer, an anti-fingerprint layer, an antiglare layer, and the like may be further formed on the other surface of the coating layer 120 to provide additional functions to the flexible window film. . In addition, although not shown in FIG. 2, the coating layer 120 may be further formed on the other surface of the substrate layer 110.

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, a wavelength of 400 nm to 800 nm. It can be used as a flexible window film in the said range.

The flexible window film 100 may have a pencil hardness of 3H or more, a tensile direction curvature radius of 5.0 mm or less, and a compression direction curvature radius of 5.0 mm or less. In the above range, good hardness and flexibility can be used as a flexible window film. The "tensile direction radius of curvature" is a radius of curvature measured when the window film is folded toward the base layer after the base layer contacts the jig for measuring the radius of curvature of the window film. The "compression direction curvature radius" is a radius of curvature measured when the window coating layer of the window film is in contact with the jig for measuring the radius of curvature and the window film is folded toward the window coating layer. Specifically, the flexible window film 100 has a pencil hardness of 3H or more, 3H to 9H, the tensile curvature radius of 0mm to 5.0mm, 0mm to 1.0mm, 0mm, compression direction curvature radius of 0mm to 5.0mm, 0mm to It can be 1.0mm.

The flexible window film 100 is placed on the window coating layer with a tip equipped with steel wool (eg Liberon Steel wool # 0000), and then placed on the surface of the window coating layer under a load of 1.5 kg, a speed of 60 mm / sec, and a moving distance of 40 mm. When moved, the number of scratches may be one or less. Within this range, the scratch resistance may be good and the appearance may be good. The flexible window film 100 may have impact resistance of 4.5 cm or more when the PEN DROP TEST is used. In the above range, the impact resistance can be good so that there is no damage to the panel when mounted on the OLED panel. In this case, the OLED panel may include an OELD panel commonly used by those skilled in the art.

The flexible window film 100 may have a RIQ of 90 or more, specifically, 90 to 98. Within this range, the surface quality of the window film is good and the display image can be clear.

The flexible window film 100 may have a thickness of about 5 μm to about 300 μm. It can be used as a flexible window film in the said range.

Hereinafter, a flexible window film according to another embodiment of the present invention will be described with reference to FIG. 3. 3 is a cross-sectional view of a flexible window film according to another embodiment of the present invention.

Referring to FIG. 3, the flexible window film 200 according to another exemplary embodiment of the present invention is excepted that the adhesive layer 130 is further formed on the other surface of the base layer 110. It 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 to facilitate adhesion between the flexible window film and the touch screen panel, the polarizing plate, or the display unit. Except that the adhesive layer is further formed is substantially the same as the flexible window film according to an embodiment of the present invention. Thus, only the adhesive layer 130 will be described below.

The adhesive layer 130 may adhere to a polarizing plate, a touch screen panel, or a display unit that may be disposed below the flexible window film 200, and may be formed of a composition for an adhesive layer.

In one embodiment, the pressure-sensitive adhesive layer 130 may be formed of a pressure-sensitive adhesive layer containing a pressure-sensitive resin, such as (meth) acrylic resin, urethane resin, silicone resin, epoxy resin, curing agent, photoinitiator, 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 a C1 to C10 unsubstituted alkyl group, a (meth) acrylic monomer having a C1 to C10 alkyl group having at least one hydroxyl group, a (meth) acrylic monomer having a C6 to C20 aromatic group , (Meth) acrylic monomer having a carboxylic acid group, (meth) acrylic monomer having a C3 to C20 alicyclic group, C3 to C10 heteroalicyclic having at least one of nitrogen (N), oxygen (O), sulfur (S) It may be formed of a monomer mixture including at least one of the (meth) acrylic monomer having a group.

The curing agent is a polyfunctional (meth) acrylate, such as bifunctional (meth) acrylates such as hexanediol diacrylate; Trifunctional (meth) acrylate of trimethylolpropane tri (meth) acrylate; Tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate; 5-functional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; 6 functional (meth) acrylates, such as dipentaerythritol hexa (meth) acrylate, may be included, but is not limited thereto.

The photoinitiator may include the photoradical initiator described above as a conventional photoinitiator.

The silane coupling agent may include a silane coupling agent having an acrylic group, such as 3-acryloxypropyltrimethoxysilane.

The adhesive layer composition may include 100 parts by weight of the (meth) acrylic resin, 0.1 parts by weight to 30 parts by weight of the curing agent, 0.1 parts by weight to 10 parts by weight of the photoinitiator, and 0.1 parts by weight to 20 parts by weight of the silane coupling agent. In the above range, the flexible window film may be attached well on the display unit, the touch screen panel or the polarizing plate.

In another embodiment, the adhesive layer 130 may be the adhesive layer 110c described below.

The adhesive layer 130 may have a thickness of about 10 μm to about 100 μm. Optical elements, such as a flexible window film and a polarizing plate, can fully be adhere | attached in the said range.

Hereinafter, a window film according to another embodiment of the present invention will be described with reference to FIG. 4. 4 is a cross-sectional view of a window film according to another embodiment of the present invention.

Referring to FIG. 4, the flexible window film 150 is substantially the same as the flexible window film 100 according to the present embodiment except that the substrate window 110 includes a substrate layer 110A instead of the substrate layer 110. .

The base layer 110A includes a first film 110a, a second film 110b, and an adhesive layer 110c formed between the first film 110a and the second film 110b. By including the base layer 110A, the flexible window film may have an effect of excellent flexibility and further improved impact resistance compared to the case of using the base layer 110.

The first film 110a and the second film 110b may respectively support the flexible window film 150. Each of the first film 110a and the second film 110b may be formed of the optically transparent and flexible resin. The first film 110a and the second film 110b may be formed of the same or different resins. For example, the first film 110a and the second film 110b are each formed of at least one resin of polyester resin, polycarbonate resin, polyimide resin, poly (meth) acrylate resin, and cyclic olefin polymer resin. It may be a film.

The first film 110a and the second film 110b may have different thicknesses or the same. The first film 110a and the second film 110b may each have a thickness of 10 μm to 100 μm, preferably 30 μm to 50 μm. In the above range, there may be an excellent effect of flexibility and impact resistance.

The base layer 110A may have a thickness of 10 μm to 275 μm, specifically 20 μm to 200 μm, and more specifically 50 μm to 110 μm. It can be used for the flexible window film in the above range.

4 illustrates a case in which the coating layer 120 is directly formed on the second film 110b, but in the case in which the coating layer 120 is directly formed on the first film 110a, that is, the second film 110b and the adhesive layer ( 110c), the case where the first film 110a and the coating layer 120 are sequentially formed may also be included in the scope of the present invention.

The adhesive layer 110c may be formed between the first film 110a and the second film 110b to adhere them to each other. The adhesive layer 110c may increase the bending reliability when repeatedly folding the window film, and may increase the impact strength of the window film.

The adhesive layer 110c may have a modulus of 10 kPa to 1000 kPa at 25 ° C. In the above range, the impact resistance of the window film can be increased, and reliability may be good even once or repeatedly folding the window film at room temperature. Preferably, the adhesive layer 120 may have a modulus of 10 kPa to 800 kPa at 25 ° C.

The adhesive layer 110c may have a modulus of 10 kPa to 1000 kPa at 80 ° C. In the above range, the impact resistance of the window film can be increased, and reliability may be good even once or repeatedly folding the window film at high temperature and high humidity. Preferably, the adhesive layer 110c may have a modulus of 10 kPa to 800 kPa at 80 ° C.

The adhesive layer 110c may have a modulus of 10 kPa to 1000 kPa at -20 ° C. In the above range, the impact resistance of the window film can be increased, and reliability may be good even once or repeatedly folding the window film at a low temperature. Preferably, the adhesive layer 110c may have a modulus of 10 kPa to 500 kPa at -20 ° C.

The adhesive layer 110c may have a modulus at 25 ° C .: modulus at −20 ° C. of 1: 1 to 1: 4, specifically 1: 1 to 1: 3.5, and more particularly 1: 1 to 1: 2.8. have. In the above range, the adhesive layer reduces the stress of the adherend in the wide temperature range (-20 to 25 ° C.) due to the change in temperature, and reduces the stress of the adherend, and does not cause peeling or bubbles in the foldable test, which is flexible. Can be used for (flexible) optical members.

The adhesive layer 110c may have a modulus of modulus: 80 ° C. at −20 ° C. of 1: 1 to 1:10, specifically 1: 1 to 1: 8, and more specifically 1: 1 to 1: 5. have. In the above range, the adhesive layer does not fall off the adhesive strength between the adhesives in a wide temperature range (-20 to 80 ℃), it can be used in a flexible (flexible) optical member.

The adhesive layer 110c may have a thickness of about 10 μm to about 75 μm. In the above range, there may be an excellent effect of flexibility and impact resistance. Preferably, the adhesive layer 110c may have a thickness of 10 μm to 50 μm and 10 μm to 30 μm.

The adhesive layer 110c may have a haze of 5% or less, specifically 3% or less, and more specifically 1% or less in the visible light region at a thickness of 100 μm. In the above range, excellent transparency is exhibited when the adhesive layer is used in an optical display device.

The adhesive layer 110c may have a glass transition temperature (Tg) of 0 ° C or less, for example, -150 ° C to 0 ° C, specifically -150 ° C to -20 ° C, and more specifically -150 ° C to -30 ° C. have. In the above range, the adhesive layer is excellent in viscoelastic properties at low and normal temperatures.

The adhesive layer 110c may be formed of an optical clear adhesive (OCA). The adhesive layer 110c may include a monomer mixture for a (meth) acrylic copolymer having a hydroxyl group; Initiator; And it may be formed of a composition for pressure-sensitive adhesive layer comprising one or more of macromonomer and organic nanoparticles. The monomer mixture may be included in the pressure-sensitive adhesive composition in a state in which the monomer mixture is not polymerized at all, but the monomer mixture may be included as a partially polymerized partial polymer. Preferably, the composition for pressure-sensitive adhesive layer is a monomer mixture for a (meth) acrylic copolymer having a hydroxyl group; Initiator; And organic nanoparticles.

The monomer mixture may be composed of hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) acrylate.

The hydroxyl group-containing (meth) acrylate can provide the adhesive force of the adhesive layer. The hydroxyl group-containing (meth) acrylate may be a (meth) acrylate containing one or more hydroxyl groups. For example, the hydroxyl group-containing (meth) acrylate is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydrate Oxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Neopentylglycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4- Hydroxycyclopentyl (meth) acrylate Y, 4-hydroxycyclohexyl (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate. The hydroxyl group-containing (meth) acrylate is 5% to 40% by weight, for example, 8% to 30% by weight, 10% to 30% by weight of the total of the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate. It may be included in weight percent. In the above range, the adhesion and durability of the pressure-sensitive adhesive layer can be further improved.

The alkyl group-containing (meth) acrylate can be a copolymer to form a matrix of the adhesive layer. The alkyl group-containing (meth) acrylate may include an unsubstituted linear or branched alkyl (meth) acrylic acid ester having 1 to 20 carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, iso-butyl (meth) acrylic Latex, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) And at least one of acrylate, decyl (meth) acrylate, lauryl (meth) acrylate and isobornyl (meth) acrylate. The alkyl group-containing (meth) acrylate is 60% to 95% by weight, for example, 65% to 92%, 68% to 90% by weight of the total of the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate. It may be included in the weight percent, 70% to 90% by weight. In the above range, the adhesion and durability of the pressure-sensitive adhesive layer can be further improved.

The monomer mixture may further include a copolymerizable monomer. The copolymerizable monomer may be included in the (meth) acrylic copolymer to provide additional effects to the (meth) acrylic copolymer, the pressure-sensitive adhesive composition, or the pressure-sensitive adhesive layer. The copolymerizable monomer is a monomer different from the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate, and includes a monomer having ethylene oxide, a monomer having propylene oxide, a monomer having an amine group, a monomer having an alkoxy group and a monomer having a phosphoric acid group. , A monomer having a sulfonic acid group, a monomer having a phenyl group, a monomer having a silane group, a monomer having a carboxylic acid group, and an amide group-containing (meth) acrylate.

Monomers having ethylene oxide may be at least one (meth) acrylate monomer containing an ethylene oxide group (-CH _₂ CH ₂ O-). For example, polyethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide monoethyl ether (meth) acrylate, polyethylene oxide monopropyl ether (meth) acrylate, polyethylene oxide monobutyl ether (meth) acrylate, polyethylene oxide mono Pentyl ether (meth) acrylate, polyethylene oxide dimethyl ether (meth) acrylate, polyethylene oxide diethyl ether (meth) acrylate, polyethylene oxide monoisopropyl ether (meth) acrylate, polyethylene oxide monoisobutyl ether (meth) It may be a polyethylene oxide alkyl ether (meth) acrylate, such as acrylate, polyethylene oxide monotertbutyl ether (meth) acrylate, but is not necessarily limited thereto.

Monomers with propylene oxide include polypropylene oxide monomethyl ether (meth) acrylate, polypropylene oxide monoethyl ether (meth) acrylate, polypropylene oxide monopropyl ether (meth) acrylate, polypropylene oxide monobutyl ether (meth ) Acrylate, polypropylene oxide monopentyl ether (meth) acrylate, polypropylene oxide dimethyl ether (meth) acrylate, polypropylene oxide diethyl ether (meth) acrylate, polypropylene oxide monoisopropyl ether (meth) acrylic Polypropylene oxide alkylether (meth) acrylates, such as latex, polypropylene oxide monoisobutyl ether (meth) acrylate, polypropylene oxide monotertbutyl ether (meth) acrylate, but are not necessarily limited thereto. no All.

Monomers having an amine group include monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth Amine group containing (meth), such as an acrylate, diethylaminoethyl (meth) acrylate, N-tert- butylaminoethyl (meth) acrylate, and (meth) acryloxyethyl trimethylammonium chloride (meth) acrylate It may be an acrylic monomer, but is not necessarily limited thereto.

Monomers having an alkoxy group include 2-methoxy ethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 2-butoxypropyl (meth) acrylate, 2 -Methoxypentyl (meth) acrylate, 2-ethoxypentyl (meth) acrylate, 2-butoxyhexyl (meth) acrylate, 3-methoxypentyl (meth) acrylate, 3-ethoxypentyl (meth ), 3-butoxyhexyl (meth) acrylate, but is not necessarily limited thereto.

Monomers having a phosphoric acid group include 2-methacryloyloxyethyldiphenyl phosphate (meth) acrylate, trimethacryloyloxyethyl phosphate (meth) acrylate, triacryloyloxyethyl phosphate (meth) acrylate, and the like. It may be an acrylic monomer having a phosphoric acid group, but is not necessarily limited thereto.

The monomer having a sulfonic acid group may be an acrylic monomer having a sulfonic acid group such as sodium sulfopropyl (meth) acrylate, sodium 2-sulfoethyl (meth) acrylate and sodium 2-acrylamido-2-methylpropane sulfonate. However, the present invention is not limited thereto.

The monomer having a phenyl group may be an acrylic vinyl monomer having a phenyl group such as p-tert-butylphenyl (meth) acrylate, o-biphenyl (meth) acrylate, phenoxyethyl (meth) acrylate, but is not limited thereto. It doesn't happen.

The monomer having a silane group is 2-acetoacetoxyethyl (meth) acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxyethyl) silane, vinyltriacetoxysilane, (meth) acrylic It may be a vinyl monomer having a silane group such as royloxypropyl trimethoxysilane, but is not necessarily limited thereto.

Monomers having a carboxylic acid group include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, itaconic acid, crotonic acid, maleic acid, and fumaric acid. And maleic anhydride, and the like, but are not necessarily limited thereto.

Amide group-containing (meth) acrylates include (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N, N-methylene Bis (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide.

The copolymerizable monomer may be included in an amount of 15 parts by weight or less, specifically 10 parts by weight or less, and more specifically 0.05 parts by weight to 8 parts by weight, based on 100 parts by weight of the total of the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate. Can be. The pressure-sensitive adhesive composition in the above range can further improve the adhesion and recovery of the adhesive film.

The initiator can be used to cure (partial polymerization) the monomer mixture into a (meth) acrylic copolymer or to cure a viscous liquid into a film. The initiator may comprise one or more of a photopolymerization initiator and a thermal polymerization initiator. As a photoinitiator, as long as it can induce the polymerization reaction of the radically polymerizable compound mentioned above in the hardening process by light irradiation etc., any can be used. For example, a benzoin type, a hydroxy ketone type, an amino ketone type, or a phosphine oxide type photoinitiator can be used. Specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylanino acetophenone, 2,2-dimethone Methoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1one, 1-hydroxycyclohexylphenylketone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone , p-phenylbenzophenone, 4,4-nondidiaminoaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methyl Thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoic acid ester , Hitting [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane paddy] and 2,4,6-trimethylbenzoyl-phosphine oxide, etc. may be mentioned - diphenyl. The thermal polymerization initiator is not particularly limited as long as it has the above-described physical properties. For example, a common initiator such as an azo compound, a peroxide compound, or a redox compound can be used. Examples of the azo compound in the above are 2,2-azobis (2-methylbutyronitrile), 2,2-triazobis (isobutyronitrile), 2,2-triazobis (2,4-dimethyl Valeronitrile), 2,2-nitazobis-2-hydroxymethylpropionitrile, dimethyl-2,2-methylazobis (2-methylpropionate) and 2,2-piazobis (4- Methoxy-2,4-dimethylvaleronitrile) and the like, and examples of the peroxide-based compound include inorganic peroxides such as potassium peroxide, ammonium persulfate or hydrogen peroxide; Or diacyl peroxide, peroxy dicarbonate, peroxy ester, tetramethylbutylperoxy neodecanoate, bis (4-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxy carbonate, butylper Oxy neodecanoate, dipropyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, diethoxyethyl peroxy dicarbonate, diethoxyhexyl peroxy dicarbonate, hexyl peroxy dicarbonate, dimethoxybutyl peroxy dicarbonate , Bis (3-methoxy-3-methoxybutyl) peroxy dicarbonate, dibutyl peroxy dicarbonate, dicetyl peroxy dicarbonate, dimyristyl peroxy dicarbonate, 1,1 , 3,3-tetramethylbutyl peroxypivalate, hexyl peroxy pivalate, butyl peroxy pivalate, trimethyl hexanoyl peroxide, dimethyl hydroxybutyl peroxy Odecanoate, amyl peroxyneodecanoate, butyl peroxyneodecanoate, t-butylperoxy neoheptanoate, amylperoxy pivalate, t-butylperoxy pivalate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate, lauryl peroxide, dilauuroyl peroxide, didecanoyl peroxide, benzoyl peroxide or dibenzoyl peroxide, and the like. Examples of the compound include, but are not limited to, a mixture using a peroxide compound and a reducing agent in combination.

The initiator is 0.0001 parts by weight to 5 parts by weight, specifically 0.001 parts by weight to 3 parts by weight based on 100 parts by weight of the total of the hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) acrylate constituting the (meth) acrylic copolymer. May be included. In this range, the curing reaction can proceed completely, remaining amount of initiator can remain to prevent the transmittance from decreasing, and also it is possible to lower the bubble generation and have excellent reactivity.

Macromonomers have functional groups curable by active energy rays and can be polymerized with hydroxyl group-containing (meth) acrylates and alkyl group-containing (meth) acrylates. Specifically, the macromonomer may be represented by the following Chemical Formula 4:

(In Formula 4, R ₁ is hydrogen or methyl, X is a single bond or a divalent bond, Y is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl Polymer chain obtained by polymerizing one or two or more selected from (meth) acrylate, t-butyl (meth) acrylate, styrene and (meth) acrylonitrile).

The macromonomer may have a number average molecular weight of 2,000 to 20,000, specifically 2,000 to 10,000, more specifically 4,000 to 8,000. In the said range, sufficient adhesive strength can be obtained, it is excellent in heat resistance, and the fall of the workability by the viscosity raise of an adhesive composition can be suppressed. Macromonomer may have a glass transition temperature of 40 ℃ to 150 ℃, specifically 60 ℃ to 140 ℃, more specifically 80 ℃ to 130 ℃. In the above range, the pressure-sensitive adhesive layer can exhibit sufficient cohesion, and can suppress a decrease in stickiness or adhesion.

The divalent bond group is C1 to C10 alkylene group, C7 to C13 arylalkylene group, C6 to C12 arylene group, -NR ^2- (wherein R ² is hydrogen or C1 to C5 alkyl group), COO-,- O-, -S-, -SO ₂ NH-, -NHSO _2- , -NHCOO-, -OCONH, or a group derived from a heterocycle.

In addition, the divalent linking group may be represented by the following formula (4a) to (4d):

(In Formulas 4a to 4d, * is a linking site of the element)

Macromonomer can use a commercial item. For example, a macromonomer whose terminal is a methacryloyl group and the segment corresponding to Y is methyl methacrylate, the macromonomer where the segment corresponding to Y is the styrene segment, and the segment of the segment Y is the styrene / acryl The macromonomer which is ronitrile, the macromonomer whose segment is butylacrylate, etc. can be used.

The macromonomer is 20 parts by weight or less, specifically 0.1 parts by weight to 20 parts by weight, 0.1 parts by weight to 10 parts by weight, 0.5 parts by weight based on 100 parts by weight of the total of the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate. It may be included from 5 parts by weight. In the above range, the viscoelasticity and modulus of the pressure-sensitive adhesive layer and the restoring force can be balanced, and the haze of the pressure-sensitive adhesive layer can be prevented from rising.

The organic nanoparticles may have an average particle diameter of 10 nm to 400 nm, specifically 10 nm to 300 nm, more specifically 30 nm to 280 nm, and more specifically 50 nm to 280 nm. In the above range, the folding of the pressure-sensitive adhesive layer is not affected, and the transparency of the pressure-sensitive adhesive layer may be good as the total light transmittance is 90% or more in the visible light region.

The organic nanoparticles may have a refractive index difference of 0.1 or less, specifically 0 or more and 0.05 or less, specifically 0 or more and 0.02 or less, with a (meth) acrylic copolymer having a hydroxyl group. In the above range, the transparency of the pressure-sensitive adhesive layer may be excellent. The organic nanoparticles may have a refractive index of 1.35 to 1.70, specifically 1.40 to 1.60. In the above range, the transparency of the pressure-sensitive adhesive layer may be excellent.

The organic nanoparticles may include, but are not limited to, simple nanoparticles such as a bead type as well as a core-shell type. In the case of the core-shell type, the core and the shell may satisfy the following Equation 1: That is, both the core and the shell may be nanoparticles which are organic materials. When having a particle form as described above, the adhesion of the adhesive layer is good, it may be effective in the balance physical properties of elasticity and flexibility.

Tg (c) <Tg (s)

(In Formula 1, Tg (c) is the glass transition temperature (unit: ° C) of the core, Tg (s) is the glass transition temperature (unit: ° C) of the shell).

As used herein, "shell" refers to the outermost layer of organic nanoparticles. The core may be one spherical particle. However, the core may further comprise an additional layer surrounding the spherical particles if it has the above glass transition temperature.

Specifically, the glass transition temperature of the core may be -150 ℃ to 10 ℃, specifically -150 ℃ to -5 ℃, more specifically -150 ℃ to -20 ℃. In the above range may have a low temperature and / or room temperature viscoelastic effect of the adhesive layer. The core may include at least one of polyalkyl (meth) acrylate, polysiloxane or polybutadiene having the above glass transition temperature.

Polyalkyl (meth) acrylates are polymethylacrylate, polyethylacrylate, polypropylacrylate, polybutylacrylate, polyisopropylacrylate, polyhexyl acrylate, polyhexyl methacrylate, polyethylhexyl acrylate And polyethylhexyl methacrylate, polysiloxane, but are not necessarily limited thereto.

The polysiloxane can be, for example, an organosiloxane (co) polymer. The organosiloxane (co) polymer may be one which is not crosslinked, or a crosslinked (co) polymer may be used. Crosslinked organosiloxane (co) polymers can be used for impact resistance and colorability. This is a crosslinked organosiloxane, specifically, crosslinked dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane or a mixture of two or more thereof may be used. The refractive index of 1.41 to 1.50 can be adjusted by using a form in which two or more organosiloxanes are copolymerized.

The crosslinking state of the organosiloxane (co) polymer can be judged with the degree of dissolution by various organic solvents. The deeper the crosslinking state, the smaller the degree of dissolution by the solvent. Acetone or toluene may be used as a solvent for determining the crosslinking state. Specifically, the organosiloxane (co) polymer may have a portion which is not dissolved by acetone or toluene. The insoluble component of the organosiloxane copolymer to toluene may be 30% or more.

Additionally, the organosiloxane (co) polymer may further include an alkylacrylate crosspolymer. As the alkyl acrylate crosspolymer, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the like can be used. For example, n-butyl acrylate or 2-ethylhexyl acrylate having a low glass transition temperature can be used.

Specifically, the glass transition temperature of the shell may be 15 ℃ to 150 ℃, specifically 35 ℃ to 150 ℃, more specifically 50 ℃ to 140 ℃. In the above range, the dispersibility of the organic nanoparticles in the (meth) acrylic copolymer may be excellent. The shell may comprise a polyalkyl methacrylate having the glass transition temperature. For example, polymethyl methacrylate (PMMA), polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate and polycyclohexyl methacrylate It may include one or more of the rate, but is not necessarily limited thereto.

The core may be included in 30 to 99% by weight, specifically 40 to 95% by weight, more specifically 50 to 90% by weight of the organic nanoparticles. In the above range, the folding property of the adhesive layer in a wide temperature range may be good. The shell may comprise 1% to 70% by weight, specifically 5% to 60% by weight, more specifically 10% to 50% by weight of the organic nanoparticles. In the above range, the folding property of the adhesive layer in a wide temperature range may be good.

The organic nanoparticles are 0.1 parts by weight to 20 parts by weight, specifically 0.5 parts by weight to 10 parts by weight, specifically 0.5 parts by weight to 100 parts by weight of the total amount of the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate. It may be included in 8 parts by weight. Within this range, the modulus of the pressure-sensitive adhesive layer at high temperature can be increased, the folding properties at normal temperature and high temperature of the pressure-sensitive adhesive layer can be improved, and the low-temperature and / or normal temperature viscoelasticity of the pressure-sensitive adhesive layer can be made excellent.

Organic nanoparticles can be prepared by conventional emulsion polymerization, suspension polymerization, solution polymerization method.

The pressure-sensitive adhesive layer composition may further include a silane coupling agent. Silane coupling agents can be used conventionally known to those skilled in the art. For example, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane, 3-glycidoxy propylmethyl dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Silicon compounds having an epoxy structure such as methoxysilane; Polymerizable unsaturated group-containing silicon compounds such as vinyl trimethoxy silane, vinyl triethoxy silane, and (meth) acryloxy propyl trimethoxysilane; Amino group-containing silicon compounds such as 3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyl dimethoxysilane ; And 3-chloro propyl trimethoxysilane and the like may include one or more selected from the group consisting of, but is not limited thereto. The silane coupling agent may be included in an amount of 0.01 to 3 parts by weight, specifically 0.01 to 1 part by weight, based on 100 parts by weight of the total of the hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) acrylate. In the above range, reliability can be ensured in the bending state at the high temperature and high humidity described above, and the difference in peeling force between low temperature, room temperature, and high temperature can be low.

The adhesive layer composition may further include a crosslinking agent. A crosslinking agent can raise the degree of crosslinking of the composition for adhesion layers, and can raise the mechanical strength of an adhesion layer. The crosslinking agent may include a polyfunctional (meth) acrylate capable of curing with an active energy ray, for example, a bifunctional (meth) acrylate such as hexanediol diacrylate, or a trifunctional to 6 functional (meth) acrylate. Can be. The crosslinking agent is 0.001 to 5 parts by weight, specifically 0.003 to 3 parts by weight, specifically 0.005 to 1 part by weight based on 100 parts by weight of the total of the hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) acrylate. It can be included as a wealth. There is an effect of excellent adhesion and increased reliability in the above range.

4 illustrates a case where the base layer is a film laminate in which the first film 110a and the second film 110b are laminated by the adhesive layer 110c. However, the case where the base material layer includes three or more films and at least two or more of them is a film laminate laminated with each other by the adhesive layer 110c may also be included in the scope of the present invention.

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

Referring to FIG. 5, the flexible display device 300 according to an exemplary embodiment of the present invention may include a display unit 350a, an adhesive layer 360, a polarizer 370, a touch screen panel 380, and a flexible window film 390. ), And the flexible window film 390 may include a flexible window film according to embodiments of the present invention.

The display unit 350a is for driving the flexible display apparatus 300 and may include an optical element including a substrate and an OLED, an LED, or an LCD element formed on the substrate. The display unit 350a may include a conventional structure known to those skilled in the art, and may include a lower substrate, a thin film transistor, an organic light emitting diode, a planarization layer, a protective film, and an insulating film.

The lower substrate supports the display unit, and the lower substrate may include a thin film transistor and an organic light emitting diode. The lower substrate may be formed with a flexible printed circuit board for driving the touch screen panel. The flexible printed circuit board may further include a timing controller, a power supply, and the like for driving the organic light emitting diode array.

The lower substrate may include a substrate formed of a flexible resin. Specifically, the lower substrate may include a flexible substrate such as a silicon substrate, a polyimide substrate, a polycarbonate substrate, a polyacrylate substrate, but is not limited thereto.

In the display area of the lower substrate, a plurality of pixel areas are defined by crossing a plurality of driving wires (not shown) and sensor wires (not shown), and each pixel area includes a thin film transistor and an organic light emitting diode connected to the thin film transistor. An organic light emitting diode array may be formed. In the non-display area of the lower substrate, a gate driver for applying an electrical signal to the driving line may be formed in the form of a gate in panel. The gate-in panel circuit unit may be formed on one side or both sides of the display area.

The thin film transistor may control the current flowing through the semiconductor by applying an electric field perpendicular thereto, and may be formed on the lower substrate. The thin film transistor may include a gate electrode, a gate insulating film, a semiconductor layer, a source electrode, and a drain electrode. The thin film transistor may be an oxide thin film transistor using an oxide of indium gallium zinc oxide (IGZO), ZnO, or TiO as a semiconductor layer, an organic thin film transistor using an organic material as a semiconductor layer, an amorphous silicon thin film transistor using amorphous silicon as a semiconductor layer, Or a polycrystalline silicon thin film transistor using polycrystalline silicon as the semiconductor layer.

The planarization layer may cover the thin film transistor and the circuit part to planarize the top surface of the thin film transistor and the circuit part so that the organic light emitting diode is formed. The planarization layer may be formed of a spin-on-glass (SOG) film, a polyimide polymer, a polyacrylic polymer, or the like, but is not limited thereto.

The organic light emitting diode implements a display by emitting light by itself, and may include a first electrode, an organic light emitting layer, and a second electrode which are sequentially stacked. Adjacent organic light emitting diodes may be distinguished through an insulating film. The organic light emitting diode may include a bottom light emitting structure in which light generated in the organic light emitting layer is emitted through the lower substrate, or a top light emitting structure in which light generated in the organic light emitting layer is emitted upward.

The protective film may cover the organic light emitting diode to protect the organic light emitting diode. The protective film may be formed of inorganic materials such as SiOx, SiNx, SiC, SiON, SiONC, and amorphous carbon (aC), (meth) acrylate, epoxy polymer, and imide polymer. It may be formed of an organic material such as. Specifically, the passivation layer 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.

Referring to FIG. 5 again, the adhesive layer 360 adheres the display unit 350a and the polarizing plate 370 and is formed of an adhesive composition including a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent. Can be.

The polarizer 370 may implement polarization of internal light or prevent reflection of external light to implement a display or increase a contrast ratio of the display. The polarizing plate may be composed of a polarizer alone. Alternatively, the polarizer may include a polarizer and a protective film formed on one or both sides of the polarizer. Alternatively, the polarizing plate may include a polarizer and a protective coating layer formed on one or both surfaces of the polarizer. The polarizer, the protective film, and the protective coating layer may use a conventional one known to those skilled in the art.

The touch screen panel 380 detects a change in capacitance generated when a human body or a conductor such as a stylus touches to generate an electrical signal. The display unit 350a may be driven by the signal. The touch screen panel 380 is formed by patterning a flexible and conductive conductor, and may include a second sensor electrode formed between the first sensor electrode and the first sensor electrode to cross 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 on the outermost side of the flexible display device 300 to protect the display device.

Although not shown in FIG. 5, 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, and a flexible display panel. The bond between the window films can be strengthened. The adhesive layer may be formed of an adhesive composition including a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent. In addition, although not shown in FIG. 3, a polarizer may be further formed below the display unit 350a to implement polarization of the internal light.

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

Referring to FIG. 6, the flexible display device 400 according to another embodiment of the present invention includes a display 350a, a touch screen panel 380, a polarizer 370, and a flexible window film 390. The window film 390 may include a flexible window film according to embodiments of the present invention. Flexible display according to an embodiment 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. It is substantially the same as the device. In this case, the touch screen panel 380 may be formed together with the display 350a. In this case, since the touch screen panel 380 is formed together with the display unit 350a on the display unit 350a, the display panel 350a may be thinner and brighter than the flexible display device according to the exemplary embodiment of the present invention, and thus may have good visibility. In addition, in this case, the touch screen panel 380 may be formed by deposition, but is not limited thereto. Although not shown in FIG. 6, between the display unit 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. The pressure-sensitive adhesive layer is further formed therein to increase the mechanical strength of the display device. The adhesive layer may be formed of an adhesive composition including a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent. In addition, although not shown in FIG. 6, a polarizing plate is further formed below the display unit 350a to induce polarization of internal light to improve a display image.

Hereinafter, a flexible display device according to still another embodiment of the present invention will be described with reference to FIG. 7. 7 is a cross-sectional view of a flexible display device according to still another embodiment of the present invention. Referring to FIG. 7, the flexible display device 500 according to another embodiment of the present invention includes a display unit 350b, an adhesive layer 360, and a flexible window film 390, and a flexible window film 390. May include a flexible window film according to embodiments of the present invention. It is substantially the same as the flexible display device according to the exemplary embodiment of the present invention except that the device may be driven only by the display unit 350b and the polarizer and the touch screen panel are excluded.

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

Hereinafter, a method for preparing the first silicone resin of formula 1 according to an embodiment of the present invention.

A silicone resin of formula (1) is of silicon to provide a (R ¹ SiO _{_{_3/2)}} a silicon ^{_{_{_{monomer, (R 2 SiO 3/2}}}} ) silicone monomer, or a mixture with (R ^₃ SiO ^_{_3/2)} to provide that service ^{^{_{monomer, (R 4 R 5 SiO 2/2}}} ) silicone monomer that ^{^{^{provides, (R 6 R 7 R 8}}} SiO 1/2) a silicon monomer, to provide one or more of the silicone monomers to provide a (SiO _4/2) It can be prepared by the hydrolysis and condensation reaction of the mixture comprising a.

Silicone monomers to provide a (R ¹ SiO _{_{_3/2)}} may be used for products that are sold commercially and synthesized by a conventional method, or known to those skilled in the art. For example, it can manufacture by the condensation reaction of the silicone monomer which has an isocyanate group (NCO) and an alkoxysilane group, and the (meth) acrylic-type monomer which has a hydroxyl group and one (meth) acrylate group. The silicone monomer having the isocyanate group and the alkoxysilane group may include 3-isocyanatopropyltriethoxysilane and the like. Examples of the (meth) acrylic monomer having a hydroxyl group and a (meth) acrylate group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. It may include. In the condensation reaction, the reaction rate may be increased by using a catalyst. For example, tin catalysts, such as dibutyl dilaurate, an amine catalyst, etc. can be included.

Silicone monomers to provide a (R ^₂ SiO ^_{_3/2)} may be used for products that are sold commercially and synthesized by a conventional method, or known to those skilled in the art. For example, it can manufacture by the condensation reaction of the silicone monomer which has an isocyanate group (NCO) and an alkoxysilane group, and the (meth) acrylic-type monomer which has a hydroxyl group and two or more (meth) acrylate groups. The silicone monomer having the isocyanate group and the alkoxysilane group may include 3-isocyanatopropyltriethoxysilane and the like. The (meth) acrylic monomer having a hydroxyl group and two or more (meth) acrylate groups may include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. In the condensation reaction, the tin catalyst, the amine catalyst and the like may be included.

(R ^₃ SiO ^_{_3/2)} to provide a silicon monomer is a (meth) acrylate monomer having a silicon to one oxy-trimethoxysilane, 3- (meth) acrylic as 3- (meth) acryloxy-propyltriethoxysilane Ethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, and the like. ^{^{_{_{(R 4 R 5 SiO 2/}}}} 2) for the silicon monomer may include dimethyldimethoxysilane. Silicone monomers for ^{^{^{(R 6 R 7 R 8 SiO}}} 1/2) may include such as hexamethyldisiloxane. Silicone monomers for (SiO _4/2 ) may include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and the like.

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

Hereinafter, a method of preparing a second silicone resin of formula 2 according to an embodiment of the present invention.

The second silicone resin of formula (2) may be prepared in a similar manner to the first silicone resin of formula (1).

Silicone monomers providing (A ³ _b SiO _{(4-b) /} ₂ ) include 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltrimeth Methoxysilane, 1H, 1H, 2H, 2H-perfluorohexyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyl Liethoxysilane, 1H, 1H, 2H, 2H-perfluorohexyltriethoxysilane, and the like.

_{_{^{(SiO 3/2 -A 1 -T}}} 1 -A 2 -SiO 3/2) silicone monomers may be made by a hydrosilylation reaction (hydrosilylation) reactions between a divinyl ether monomer and a trialkoxysilane to provide, The divinyl ether monomer comprises at least one of ethylene glycol divinyl ether, di (ethylene glycol) divinyl ether, tri (ethylene glycol) divinyl ether, tetra (ethylene glycol) divinyl ether, and the trialkoxysilane It may comprise one or more of oxysilane, trimethoxysilane, tripropoxysilane. The hydrosilylation reaction may include a conventional platinum catalyst to speed up the reaction.

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

The flexible window film 100 may 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 base layer 110.

The method of coating the composition for the window film on the base layer 110 may be bar coating, spin coating, dip coating, roll coating, flow coating, die coating, or the like, but is not limited thereto. The composition for a window film may be coated on the base layer 110 to a thickness of 5㎛ to 100㎛. It is possible to secure the desired coating layer in the above range and may have an excellent effect of hardness and flexibility. Curing is to form a coating layer by curing the composition for a window film, may include photocuring. Photocuring may involve irradiation with light amount of 10 mJ / cm ² to 1,000mJ / cm ² at a wavelength of 400nm or less. In the above range, the composition for a window film may be sufficiently cured. As described above, the composition for a window film of the present invention can produce a window film of sufficient hardness only by photocuring without further heat treatment or aging after photocuring, thereby improving processability. The method may further include drying the composition for a window film before the composition for a window film is coated on the base layer 110 and then cured. By curing after drying, it is possible to prevent the surface roughness of the coating layer from increasing due to prolonged photocuring. Drying may be performed at 40 ° C. to 200 ° C. for 1 minute to 30 hours, but is not limited thereto.

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

제조예 1: 제1실리콘 수지Preparation Example 1 First Silicone Resin

1.0 equivalent of 3-isocyanatopropyltriethoxysilane (KBE-9007, Shin-Etsu), 0.9 equivalent of 2-hydroxyethyl acrylate (TCI) 0.1, pentaerythritol triacrylate (Sigma-Aldrich) 0.1 A total of 100 g of a mixture of monomers, 0.3 g of dibutyltin dilaurate (Sigma-Aldrich) and 100 g of toluene were added to a 500 mL 3-neck flask in an equivalent ratio. After stirring for 5 hours at room temperature, 20 g of 0.1N HCl aqueous solution was added thereto. It heated up at 50 degreeC and stirred for 8 hours. After cooling to room temperature, 400 g of toluene was added and diluted. 200 g of distilled water was added thereto, followed by stirring and standing to remove the aqueous layer, and the process was repeated four times in total. 0.04 g of 4-methoxyphenol (Sigma-Aldrich Co., Ltd.) was added to the organic layer, and the organic layer was removed by a distillation apparatus under reduced pressure to obtain a solid content of 90%. Silicone resin identified by gel permeation chromatography (GPC) ((X ₁ -Ety-O- (C = O) NH-Pry) SiO _3/2 ) _0.9 ((Z ₁ -O- (C = O) NH-Pry) The weight average molecular weight of SiO _3/2 ) _0.1 was about 3,000 g / mol.

제조예 2: 제1실리콘 수지Preparation Example 2 First Silicone Resin

100 g of a mixture of monomers at a ratio of 1.0 equivalent of 3-isocyanatopropyltriethoxysilane (KBE-9007, Shin-Etsu) and 1.0 equivalent of 2-hydroxyethyl acrylate (TCI), dibutyltin di 0.3 g of laurate (Sigma-Aldrich) and 100 g of toluene were placed in a 500 mL 3-neck flask. After stirring for 5 hours at room temperature, 20 g of 0.1N HCl aqueous solution was added thereto. It heated up at 50 degreeC and stirred for 8 hours. After cooling to room temperature, 400 g of toluene was added and diluted. 200 g of distilled water was added thereto, followed by stirring and standing to remove the aqueous layer, and the process was repeated four times in total. 0.04 g of 4-methoxyphenol (Sigma-Aldrich Co., Ltd.) was added to the organic layer, and the organic layer was removed by a distillation apparatus under reduced pressure to obtain a solid content of 90%. Silicone resin confirmed by _{GPC ((X 1 -Ety-O-} (C = O) NH-Pry) SiO 3/2) of the weight average molecular weight was about 3,000g / mol.

제조예 3: 제2실리콘 수지Preparation Example 2 Second Silicone Resin

100 g of a mixture of monomers at a ratio of 1.0 equivalent of 3-isocyanatopropyltriethoxysilane (KBE-9007, Shin-Etsu) and 1.0 equivalent of 2-hydroxyethyl acrylate (TCI), dibutyltin di 0.3 g of laurate (Sigma-Aldrich) and 100 g of toluene were placed in a 500 mL 3-neck flask. After stirring for 5 hours at room temperature, 0.05 equivalent of 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane (Sigma Aldrich) and 20 g of 0.1N HCl aqueous solution were added thereto. It heated up at 50 degreeC and stirred for 8 hours. After cooling to room temperature, 400 g of toluene was added and diluted. 200 g of distilled water was added thereto, followed by stirring and standing to remove the aqueous layer, and the process was repeated four times in total. 0.04 g of 4-Methoxyphenol (Sigma-Aldrich Co., Ltd.) was added to the organic layer, and the organic layer was removed by a distillation apparatus under reduced pressure to obtain a solid content of 90%. The weight average molecular weight of the silicone resin ((X ₁ -Ety-O- (C = O) NH-Pry) SiO _3/2 ) _0.95 (FdSiO _3/2 ) _0.05 as determined by gel permeation chromatography (GPC) was about 3,000 g / mol.

제조예 4: 제2실리콘 수지Preparation Example 2 Second Silicone Resin

100 g of a mixture of monomers at a ratio of 1.0 equivalent of 3-isocyanatopropyltriethoxysilane (KBE-9007, Shin-Etsu) and 1.0 equivalent of 2-hydroxyethyl acrylate (TCI), dibutyltin di 0.3 g of laurate (Sigma-Aldrich) and 100 g of toluene were added to a 500 mL 3-neck flask and stirred at room temperature for 5 hours to form a reactant solution X.

In a 250 mL flask under nitrogen atmosphere, 35 ppm of tri (ethylene glycol) divinyl ether (Aldrich), toluene, and 150 ppm of platinum catalyst (Umicore, PT-CS-1.8CS) were added and stirred. 70 mmol of triethoxysilane was added thereto and reacted with stirring at 45 ° C. for 2 hours. Reactant Y was synthesized by removing the platinum catalyst using activated carbon.

0.05 equivalent of reactant Y and 20 g of 0.1N HCl aqueous solution were added to the reactant solution X. It heated up at 50 degreeC and stirred for 8 hours. After cooling to room temperature, 400 g of toluene was added and diluted. 200 g of distilled water was added thereto, followed by stirring and standing to remove the aqueous layer, and the process was repeated four times in total. 0.04 g of 4-methoxyphenol (Sigma-Aldrich Co., Ltd.) was added to the organic layer, and the organic layer was removed by a distillation apparatus under reduced pressure to obtain a solid content of 90%. Silicone resin identified by gel permeation chromatography (GPC) ((X ₁ -Ety-O- (C = O) NH-Pry) SiO _3/2 ) _0.95 (SiO _3/2 -C ₂ H ₄ -[-OC ₂ H _4- ] ₄ -SiO _3/2 ) _0.05 The weight average molecular weight was about 3,000 g / mol.

Specific specifications of the components used in the following Examples and Comparative Examples are as follows.

(A) 1st silicone resin: (A1) manufacture example 1, (A2) manufacture example 2

(B) 2nd silicone resin: (B1) manufacture example 3, (B2) manufacture example 4

(C) Crosslinking agent: (C1) SR-499 (Sartomer), (C2) SR-502 (Sartomer),

(D) Nanoparticles: SST-550U (Ranco, Silica containing, Solid content: 50% by weight)

(E) Initiator: Irgacure 184 as a photoinitiator (BASF)

(F) organic binder: CHTU-9607 (Camton) as a urethane acrylate resin that does not contain silicone

실시예 1Example 1

To 1 parts by weight of Table 1, the total weight of the total weight of the first silicone resin, the second silicone resin, the crosslinking agent and the initiator was mixed to 5.0 g, and 5.0 g of solvent methyl ethyl ketone was added to prepare a composition for a coating layer.

The coated coating composition was applied to a polyimide film (Samsung SDI Co., Ltd., thickness: 80 μm), dried at 80 ° C. for 4 minutes, and irradiated with UV of 500 mJ / cm ² under a nitrogen atmosphere to provide a window having a thickness of 10 μm. A film was prepared.

실시예 2 내지 실시예 3, 실시예 5Examples 2 to 3, 5

A window film was manufactured in the same manner as in Example 1 except for changing the type and content (unit: parts by weight) of the silicone resin as shown in Table 1 below.

실시예 4Example 4

A window film was manufactured in the same manner as in Example 1, except that the type, content, and nanoparticles (solid content basis) of the silicone resin were changed as in Table 1 below.

비교예 1 내지 비교예 2Comparative Example 1 to Comparative Example 2

A window film was manufactured in the same manner as in Example 1 except for changing the type and content of the resin as shown in Table 1 below.

참조예 1Reference Example 1

A window film was manufactured in the same manner as in Example 1 except for changing the type and content of silicone resins as shown in Table 1 below.

		실시예1Example 1	실시예2Example 2	실시예3Example 3	실시예4Example 4	실시예5Example 5	실시예6Example 6	비교예1Comparative Example 1	비교예2Comparative Example 2	참조예1Reference Example 1
(A)제1실리콘 수지(A) First Silicon Resin	(A1)(A1)	7979	7979	7979	6969	--	7979	--	--	8080
(A)제1실리콘 수지(A) First Silicon Resin	(A2)(A2)	--	--	--	--	7979	--	--	--	--
(B)제2실리콘 수지(B) the second silicone resin	(B1)(B1)	1One	--	1One	--	1One	1One	--	--	--
(B)제2실리콘 수지(B) the second silicone resin	(B2)(B2)	--	1One	--	1One	--	--	--	--	--
(C)가교제 (C) Cross-linking system	(C1)(C1)	2020	2020	--	--	2020	2020	--	2020	2020
(C)가교제 (C) Cross-linking system	(C2)(C2)	--	--	2020	2020	--	--	--	--	--
(D)나노입자(D) nanoparticles		--	--	--	1010	--	--	--	--	--
(E)개시제(E) Initiator		22	22	22	22	22	22	22	22	22
(F)유기계바인더(F) organic binder		--	--	--	--	--	--	100100	8080	--
기재층Substrate layer		PI 필름PI film	PI 필름PI film	PI 필름PI film	PI 필름PI film	PI 필름PI film	필름 적층체Film laminate	PI 필름PI film	PI 필름PI film	PI 필름PI film

The physical properties of the window films prepared in Examples and Comparative Examples were measured and shown in Table 2 below.

(1) Scruff test: Using a Scuff tester, a steel wool (Lenon # 0000) -mounted tip (diameter: 11 mm) was placed on the window coating layer of the window film, and the load was 1.5 kg. The coating layer was moved on the surface of the coating layer at 60 mm / sec and 40 mm moving distance. Record the number of scratches that occurred after this 10 iterations. The lower the number, the better the scratch resistance. In case of less than 1, Pass is evaluated. In case of more than 1, it is evaluated as Fail.

(2) Curvature radius: Wind the window film (width x length, 3cmx15cm) to the curvature test JIG (CFT-200R, COVOTECH Co., Ltd.), hold the wound state for 5 seconds or more, and then crack in the film when unwinding in JIG Whether or not it was visually evaluated. What was measured so that a base material layer might contact JIG was called the tension direction curvature radius. The radius of curvature was measured by gradually decreasing the diameter of the JIG, starting from the maximum radius of the JIG, and measuring the minimum radius of the JIG without cracking.

(3) RIQ: 16 points were measured by Rhopoint IQ of Rhopoint for the window coating layer in the window film. Among the 16 values obtained, the average value was obtained except for the minimum of two and the maximum of two. Higher RIQ means better surface quality of the window coating layer.

(4) Pencil hardness: It measured by JIS K5400 using the pencil hardness tester (Heidon) about the coating layer of a window film. In measuring the pencil hardness, a pencil of 6B to 9H manufactured by Mitsubishi Corporation was used. The load of the pencil on the coating layer was 1 kg, the angle at which the pencil was drawn was 45 °, and the speed at which the pencil was drawn was 60 mm / min. If the scratch occurs more than one time to evaluate five times, the pencil hardness is measured using the pencil of the step below, the five times the five times the maximum pencil hardness value when there is no scratch.

(5) Impact Resistance (PEN DROP TEST): Adhesion film (thickness: 50 mu m, 3M OCA 8146) is attached to the window films of Examples and Comparative Examples, and the window film is a polyethylene terephthalate (PET) film (thickness: 2500 mu m) Mitsubishi Co., Ltd.) was fixed so that the window coating layer was on top. An aluminum foil and a stainless plate (SUS plate) were sequentially placed on the lower surface of the PET film to prepare a specimen. Of the specimens, a pen with a weight of 5.8 g at a predetermined height and a ball size (diameter) of PEN of 0.7 mm was dropped from the window coating layer to evaluate the initial height of visually discernible marks on the surface of the aluminum foil and the window coating layer. The average value was obtained by repeating five times. The higher the initial height, the higher the impact resistance of the window film. According to PEN DROP TEST, if the initial height of the marks is 4.5cm or more, there is no impact even if the OLED panel is mounted.

	실시예1Example 1	실시예2Example 2	실시예3Example 3	실시예4Example 4	실시예5Example 5	실시예6Example 6	비교예1Comparative Example 1	비교예2Comparative Example 2	참조예 1Reference Example 1
내스크래치성(scuff test)Scratch resistance	PassPass	PassPass	PassPass	PassPass	PassPass	PassPass	FailFail	PassPass	PassPass
인장 방향 곡률반경(mm)Tensile Direction Curvature Radius (mm)	1One	1One	1One	1One	1One	1One	66	55	1One
RIQRIQ	9292	9494	9393	9494	9393	9292	7878	7979	8989
연필경도Pencil hardness	3H3H	3H3H	3H3H	4H4H	3H3H	3H3H	2H2H	2H2H	3H3H
내충격성(cm)Impact resistance (cm)	66	66	88	77	77	1010	33	33	22

As shown in Table 2, the composition for a window film of the present invention has excellent scratch resistance, excellent flexibility when folded toward the base layer, excellent surface quality, high pencil hardness, and excellent impact resistance film. It was. In addition, Example 6 including the film laminate as the substrate layer significantly improved the impact resistance compared to Example 1.

On the other hand, Comparative Examples 1 and 2, which do not include both the first silicone resin and the second silicone resin of the present invention, have poor scratch resistance or poor surface quality and poor hardness. Reference Example 1, which does not contain the second silicone resin of the present invention, had poor surface quality.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims

A composition for a window film, comprising a first silicone resin of formula 1, a second silicone resin of formula 2, a crosslinking agent and an initiator:

<Formula 1>

(R 1 SiO 3/2 ) x (R 2 SiO 3/2 ) y (R 3 SiO 3/2 ) z (R 4 R 5 SiO 2/2 ) w (R 6 R 7 R 8 SiO 1/2 ) u (SiO 4/2 ) v

(From the above,

R 1 is a monovalent organic group having one (meth) acrylate group and at least one urethane group,

R 2 is a monovalent organic group having two or more (meth) acrylate groups and one or more urethane groups,

R 3 is a non-urethane-based monovalent organic group having one or more (meth) acrylate groups,

Unsubstituted or substituted C1 to C20 alkyl group, unsubstituted or substituted C5 to C20 cycloalkyl group, or unsubstituted or substituted C6 to C30 aryl group,

R 4 , R 5 , R 6 , R 7 , R 8 are each independently hydrogen, a monovalent organic group having one or more (meth) acrylate groups, an unsubstituted or substituted C1 to C20 alkyl group, an unsubstituted or A substituted C5 to C20 cycloalkyl group, or an unsubstituted or substituted C6 to C30 aryl group,

0≤x≤1, 0≤y≤1, 0≤z <1, 0≤w <1, 0≤u <1, 0≤v <1, x + y ≠ 0, x + y + z + w + u + v = 1),

<Formula 2>

(R 11 SiO 3/2 ) x (A 3 b SiO (4-b) / 2 ) y1 (SiO 3/2 -A 1 -T 1 -A 2 -SiO 3/2 ) y2 (R 12 SiO 3 / 2 ) z (R 13 R 14 SiO 2/2 ) w (R 15 R 16 R 17 SiO 1/2 ) u (SiO 4/2 ) v

(From the above,

R 11 is a monovalent organic group having at least one (meth) acrylate group and at least one urethane group, or a non-urethane monovalent organic group having at least one (meth) acrylate group.

R 12 is an unsubstituted or substituted C1 to C20 alkyl group, an unsubstituted or substituted C5 to C20 cycloalkyl group, or an unsubstituted or substituted C6 to C30 aryl group,

R 13 , R 14 , R 15 , R 16 , R 17 are each independently hydrogen, a monovalent organic group having one or more (meth) acrylate groups, an unsubstituted or substituted C1 to C20 alkyl group, an unsubstituted or A substituted C5 to C20 cycloalkyl group, or an unsubstituted or substituted C6 to C30 aryl group,

A 3 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 substitution containing at least one fluorine or Unsubstituted C6 to C20 aryl group, b is an integer of 1 to 3

A 1 and A 2 are each independently a single bond or a substituted or unsubstituted C1 to C5 alkylene group,

T 1 is a monoalkylene oxide group or a polyalkylene oxide group,

0 <x <1, 0 <y1 + y2 <1, 0≤y1 <1, 0≤y2 <1, 0≤z <1, 0≤w <1, 0≤u <1, 0≤v <1, x + y1 + y2 + z + w + u + v = 1).
The composition for a window film of claim 1, wherein the first silicone resin of Chemical Formula 1 is a silicone resin having a T unit and a T unit represented by the following Chemical Formula 1-1:

<Formula 1-1>

(R 1 SiO 3/2 ) x (R 2 SiO 3/2 ) y

(Wherein R 1 , R 2 are as defined in Formula 1 above, 0 <x <1, 0 <y <1, x + y = 1).
The composition for a window film according to claim 2, wherein 0.80 ≦ x ≦ 0.99, 0.01 ≦ y ≦ 0.20, and x + y = 1.
The composition for a window film of claim 1, wherein the silicone resin of Chemical Formula 1 is a silicone resin having a T unit represented by the following Chemical Formula 1-2:

<Formula 1-2>

(R 1 SiO 3/2 ) x

(Wherein R 1 is as defined in Formula 1 above, x is 1).
The composition of claim 1, wherein the first silicone resin is represented by any one of the following Chemical Formulas 1-1-1 to 1-1-10, and the following Chemical Formulas 1-2-1 to 1-2-3. :

<Formula 1-1-1>

((X-Ety-O- (C = O) NH-Pry) SiO 3/2 ) x ((ZO- (C = O) NH-Pry) SiO 3/2 ) y

<Formula 1-1-2>

((X-Buty-O- (C = O) NH-Pry) SiO 3/2 ) x ((ZO- (C = O) NH-Pry) SiO 3/2 ) y

<Formula 1-1-3>

((X-Pry-O- (C = O) NH-Pry) SiO 3/2 ) x ((ZO- (C = O) NH-Pry) SiO 3/2 ) y

(In the above, 0 <x <1, 0 <y <1, x + y = 1)

<Formula 1-1-4>

((X-Ety-O- (C = O) NH-Pry) SiO 3/2 ) x ((WO- (C = O) NH-Pry) SiO 3/2 ) y

<Formula 1-1-5>

((X-Buty-O- (C = O) NH-Pry) SiO 3/2 ) x ((WO- (C = O) NH-Pry) SiO 3/2 ) y

<Formula 1-1-6>

((X-Pry-O- (C = O) NH-Pry) SiO 3/2 ) x ((WO- (C = O) NH-Pry) SiO 3/2 ) y

(In the above, Ety is an ethylene group, Pry is a propylene group, Buty is a butylene group, X is a (meth) acrylate group, Z is each of the following formula A,

<Formula A>

(In the above, * is a linking site, X is a (meth) acrylate group)

W is represented by the following formula D,

<Formula D>

(In the above, * is a linking site, X is a (meth) acrylate group),

0 <x <1, 0 <y <1, x + y = 1)

<Formula 1-1-7>

((X-Ety-O- (C = O) NH-Pry) SiO 3/2 ) x1 ((X-Buty-O- (C = O) NH-Pry) SiO 3/2 ) x2 ((ZO- (C = O) NH-Pry) SiO 3/2 ) y

<Formula 1-1-8>

((X-Ety-O- (C = O) NH-Pry) SiO 3/2 ) x1 ((X-Pry-O- (C = O) NH-Pry) SiO 3/2 ) x2 ((ZO- (C = O) NH-Pry) SiO 3/2 ) y

<Formula 1-1-9>

((X-Ety-O- (C = O) NH-Pry) SiO 3/2 ) x1 ((X-Buty-O- (C = O) NH-Pry) SiO 3/2 ) x2 ((WO- (C = O) NH-Pry) SiO 3/2 ) y

<Formula 1-1-10>

((X-Ety-O- (C = O) NH-Pry) SiO 3/2 ) x1 ((X-Pry-O- (C = O) NH-Pry) SiO 3/2 ) x2 ((WO- (C = O) NH-Pry) SiO 3/2 ) y

(In the above, Ety is an ethylene group, Pry is a propylene group, Buty is a butylene group, X is a (meth) acrylate group, Z is each of the following formula A,

<Formula A>

(In the above, * is a linking site, X is a (meth) acrylate group)

W is represented by the following formula D,

<Formula D>

(In the above, * is a linking site, X is a (meth) acrylate group),

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

<Formula 1-2-1>

((X-Ety-O- (C = O) NH-Pry) SiO 3/2 )

<Formula 1-2-2>

((X-Buty-O- (C = O) NH-Pry) SiO 3/2 )

<Formula 1-2-3>

((X-Pry-O- (C = O) NH-Pry) SiO 3/2 )

(In the above, Ety is an ethylene group, Pry is a propylene group, Buty is a butylene group, X is a (meth) acrylate group).
The composition of claim 1, wherein the second silicone resin is represented by the following Chemical Formula 2-1:

<Formula 2-1>

(R 11 SiO 3/2 ) x (A 3 b SiO (4-b) / 2 ) y1 (SiO 3/2 -A 1 -T 1 -A 2 -SiO 3/2 ) y2

(From the above,

R 11 , A 3 , A 1 , A 2 , T 1 , b are the same as defined in Formula 2,

0 <x <1, 0 <y1 + y2 <1, 0 ≦ y1 <1, 0 ≦ y2 <1, x + y1 + y2 = 1).
The composition for a window film of claim 6, wherein the second silicone resin is represented by the following Chemical Formula 2-1-1 to 2-1-9:

<Formula 2-1-1>

((X-Ety-O- (C = O) NH-Pry) SiO 3/2 ) x (FdSiO 3/2 ) y1

<Formula 2-1-2>

((X-Ety-O- (C = O) NH-Pry) SiO 3/2 ) x (FoSiO 3/2 ) y1

<Formula 2-1-3>

((X-Buty-O- (C = O) NH-Pry) SiO 3/2 ) x (FdSiO 3/2 ) y1

<Formula 2-1-4>

((X-Buty-O- (C = O) NH-Pry) SiO 3/2 ) x (FoSiO 3/2 ) y1

<Formula 2-1-5>

((X-Pry-O- (C = O) NH-Pry) SiO 3/2 ) x (FdSiO 3/2 ) y1

<Formula 2-1-6>

((X-Pry-O- (C = O) NH-Pry) SiO 3/2 ) x (FoSiO 3/2 ) y1

(In the above, Ety is ethylene group, Pry is propylene group, Buty is butylene group, X is (meth) acrylate group, Fd is 1H, 1H, 2H, 2H-perfluorodecyl group, Fo is 1H, 1H, 2H, 2H-perfluorooctyl group, 0 <x <1, 0 <y1 <1, x + y1 = 1),

<Formula 2-1-7>

((X-Ety-O- (C = O) NH-Pry) SiO 3/2 ) x (SiO 3/2 -C 2 H 4 -[-OC 2 H 4- ] 4 -SiO 3/2 ) y2

<Formula 2-1-8>

((X-Buty-O- (C = O) NH-Pry) SiO 3/2 ) x (SiO 3/2 -C 2 H 4 -[-OC 2 H 4- ] 4 -SiO 3/2 ) y2

<Formula 2-1-9>

((X-Pry-O- (C = O) NH-Pry) SiO 3/2 ) x (SiO 3/2 -C 2 H 4 -[-OC 2 H 4- ] 4 -SiO 3/2 ) y2

(In the above, Ety is an ethylene group, Pry is a propylene group, Buty is a butylene group, X is a (meth) acrylate group, 0 <x <1, 0 <y2 <1, x + y2 = 1).
The composition of claim 6, wherein in Formula 2-1, 0.85 ≦ x ≦ 0.99, 0.01 ≦ y1 ≦ 0.15, y2 = 0 or 0.85 ≦ x ≦ 0.99, 0.01 ≦ y2 ≦ 0.15, y1 = 0.
The composition for a window film according to claim 1, wherein the crosslinking agent comprises a (meth) acrylate monomer.
The method of claim 8, wherein the total amount of the first silicon resin of the general formula (1), the second silicon resin of the general formula (2) and the crosslinking agent, the first silicone resin of the general formula (1) is 10 parts by weight to 80 parts by weight, The second silicone resin of the formula (2) is 0.1 parts by weight to 50 parts by weight, the crosslinking agent is a composition for a window film containing 1 part by weight to 50 parts by weight.
The composition of claim 1, wherein the composition for the window film further comprises nanoparticles.
The composition for a window film according to claim 11, wherein the nanoparticles are surface treated with a (meth) acrylate group.
The composition of claim 11, wherein at least some of the silicone resin of Formula 1 is bonded to the nanoparticles to form a composite.
The composition for window films according to claim 11, wherein the nanoparticles have an average particle diameter (D50) of 100 nm or less.
The composition of claim 11, wherein the nanoparticles comprise silica.
The composition for a window film according to claim 1, wherein the composition for window film further comprises an alicyclic epoxy resin having an epoxy group.
The composition for a window film according to claim 1, wherein the composition for a window film is a UV absorber, a reaction inhibitor, an adhesion enhancer, a thixotropic imparting agent, a conductivity imparting agent, a color regulator, a stabilizer, an antistatic agent, an antioxidant, a leveling agent, an anti-fingerprint agent, a surface Further comprising at least one additive of the energy regulator, the composition for a window film.
A base material layer and a coating layer formed on the base material layer, wherein the flexible window film has a pencil hardness of 3H or more, tensile direction curvature radius is 5.0mm or less, RIQ is 90 or more, flexible window film.
The flexible window film of claim 18, wherein the coating layer is formed of the composition for a window film of claim 1.
The method of claim 18, wherein the substrate layer comprises a film laminate,

The said film laminated body is a flexible window film in which two or more films are laminated | stacked by the adhesion layer.
The flexible window film according to claim 18, wherein the film laminate has a first film, a second film, and the first film and the second film laminated by the adhesive layer.
22. The method of claim 21, wherein the first film and the second film is a film formed of at least one of polyester resin, polycarbonate resin, polyimide resin, poly (meth) acrylate resin, and cyclic olefin polymer resin, respectively. Flexible window film.
The method of claim 20, wherein the pressure-sensitive adhesive layer is a monomer mixture for the (meth) acrylic copolymer having a hydroxyl group; Initiator; And a composition for a pressure-sensitive adhesive layer comprising at least one of macromonomers and organic nanoparticles.
The flexible window film of claim 23, wherein the monomer mixture comprises a hydroxyl group-containing (meth) acrylate and an alkyl group-containing (meth) acrylate.
25. The flexible window film of claim 24, wherein the monomer mixture further comprises a comonomer.
The flexible window film of claim 23, wherein the organic nanoparticles include core-shell particles satisfying Formula 1 below.

<Equation 1>

Tg (c) <Tg (s)

(In Formula 1, Tg (c) is the glass transition temperature (unit: ° C) of the core, Tg (s) is the glass transition temperature (unit: ° C) of the shell).
The flexible window film of claim 23, wherein the organic nanoparticles have an average particle diameter of 10 nm to 400 nm.
The flexible window film of claim 21, wherein each of the first film and the second film has a thickness of 10 μm to 100 μm, and the adhesive layer has a thickness of 10 μm to 75 μm.