WO2019240408A1 - Siloxane oligomer having organic metal, method for preparation of siloxane oligomer, hard coating composition containing siloxane oligomer, hard coating film, and display device - Google Patents

Abstract

The present invention relates to a siloxane oligomer formed by reaction of three different kinds of siloxane monomers with an organic metal, a preparation method therefor, a hard coating composition containing the siloxane oligomer, a hard coating film resulting from curing of the hard coating composition, and a display device. The hard coating film composed of the cured siloxane oligomer according to the present invention has excellent properties such as scratch resistance, etc. The hard coating film derived from the siloxane oligomer according to the present invention can be applied to an optical film, for example, a window film such as a cover window, to achieve a display device having excellent properties.

Description

Siloxane oligomers with organometals, methods for preparing siloxane oligomers, hard coating compositions comprising siloxane oligomers, hard coating films and display devices

The present invention relates to a siloxane oligomer, and more particularly, to a siloxane oligomer containing an organic metal and improved physical properties, a method for preparing the same, a hard coating composition, a hard coating film and a display device.

Recently, with the development of information communication technology and display technology, display devices for processing and displaying a large amount of information are rapidly developing. Accordingly, a flat panel display device represented by a liquid crystal display (LCD) or an organic light emitting diode (OLED) display is widely used in TVs, computer monitors, mobile phone screens, and the like. Recently, a touch type display device that allows a user to manipulate a display screen by touching a panel has been widely used.

A touch type display device commonly touches the outermost surface of the display device using a user or touch-pen. Therefore, since the outermost surface of the touch type display device needs to control the light incident on the display device and at the same time have a certain hardness, it adopts an optical film such as a hard coat film.

Conventionally, although tempered glass is used for a hard coating film applied to a display device, the tempered glass may be damaged even with slight bending because the tempered glass has a very low elasticity. In particular, when applied to a flexible or foldable display, the problem of breaking the hard coating film made of tempered glass becomes more serious. Plastic covers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI) have been proposed in place of tempered glass in order to secure the flexibility and impact resistance of the hard coating film. However, these plastic covers do not have sufficient impact resistance, resulting in a problem that surface hardness and scratch resistance are lower than that of tempered glass.

Thus, a hard coating film made of a binder of a polymer in place of the tempered glass has been proposed. The polymer binder adds a polymerization initiator to the hard coating composition present in the monomer or oligomer form to apply heat or irradiate ultraviolet rays to form a polymer to impart hard coating properties.

The hard coat film positioned on the surface of the conventional display device lacked physical properties such as impact resistance and surface strength. Various methods have been proposed for solving the physical properties lacking in the hard coating film made of a binder resin. For example, International Publication No. WO 2013/187699 proposes a high hardness siloxane resin composition containing an alicyclic epoxy group, a method for producing the same, and an optical film including the cured product. Although the optical film according to the international patent achieves a high hardness of 9H, using a single monomer and a cationic initiator, weather resistance may be a problem, there is still a problem that curling may occur. Therefore, there is a need to develop a hard coating film having improved durability to be applied to a display device.

It is an object of the present invention to provide a siloxane oligomer having improved physical properties such as impact resistance, surface hardness and scratch resistance, a method for preparing the same, a hard coating composition comprising the same, a hard coating film and a display device manufactured therefrom.

According to an aspect of the present invention having the above object, the present invention provides a siloxane oligomer represented by the following formula (1).

Formula 1

(R ¹ SiO _3/2 ) _x (SiO _4/2 ) _y (SiO _3/2 -R ² -SiO _3/2 ) _z (M (acac) _o ) _m

(Formula 1, R ¹ is directly connected to a silicon atom or silicon via a C ₁ to C ₁₀ aliphatic linking group, C ₃ to C ₁₀ cycloaliphatic linking group, C ₆ to C ₂₀ aromatic linking group or C ₆ to C ₂₀ heteroaromatic linking group Silicon directly connected to a glycidoxy group or silicon atom linked to an atom, or via a C ₁ to C ₁₀ aliphatic linking group, a C ₃ to C ₁₀ cycloaliphatic linking group, a C ₆ to C ₂₀ aromatic linking group or a C ₆ to C ₂₀ heteroaromatic linking group An alicyclic epoxy group connected to an atom; R ² is an unsubstituted or substituted C ₁ to C ₁₀ alkylene group or an unsubstituted or substituted C ₅ to C ₃₀ arylene group, which may be substituted with the alkylene group and the arylene group Substituents include C ₁ to C ₃₀ straight or branched chain alkyl groups, C ₁ to C ₂₀ alkoxy groups, amino groups, acrylic groups, methacryl groups, halogens, mercapto groups, allyl groups, ether groups, ester groups, carbonyl groups, carboxyl groups, vinyl groups , Nitro , Sulfen group, hydroxy group, C ₃ to C ₈ cycloalkyl group, alkyd group, urethane group, oxetane group, C ₅ to C ₃₀ aryl group, C ₅ to C ₃₀ arylalkyl group, C ₅ to C ₃₀ aryloxy group And combinations thereof; M is a metal atom selected from the group consisting of aluminum, titanium, zirconium, zinc, and combinations thereof, and acac is unsubstituted or a C ₁ to C ₁₀ straight or branched chain alkyl group. Substituted acetylacetone ligand, o is an integer from 2 to 4; 0.25 ≦ x ≦ 0.979, 0.01 ≦ y ≦ 0.35, 0.01 ≦ z ≦ 0.35; 0.001 ≦ m ≦ 0.05, x + y + z + m = 1)

In exemplary embodiments, in Chemical Formula 1, 0.32 ≦ x ≦ 0.919, 0.04 ≦ y ≦ 0.32, 0.04 ≦ z ≦ 0.32, 0.001 ≦ m ≦ 0.04, and x + y + z + m = 1.

Preferably, in Chemical Formula 1, 0.43 ≦ x ≦ 0.839, 0.08 ≦ y ≦ 0.27, 0.08 ≦ z ≦ 0.27, 0.001 ≦ m ≦ 0.03, and x + y + z + m = 1.

For example, in Formula 1, R ¹ may be a gamma-glycidoxy group, a gamma-glycidoxy group-containing functional group, 2- (3,4-epoxycyclohexyl group), and / or 2- (3,4-epoxycyclohex). It may be selected from the group consisting of a group) -containing alicyclic epoxy group.

In addition, M (acac) _o of Formula 1 may be selected from the group consisting of aluminum acetyl acetone, titanium acetyl acetone, titanium ethyl acetyl acetone, zirconium monoacetyl acetone, zirconium tetraacetyl acetone, zinc acetyl acetone and combinations thereof have.

For example, the weight average molecular weight of the siloxane oligomer may be 1,000 to 100,000.

According to another aspect of the invention, the present invention is a method for producing a siloxane oligomer represented by the following formula (1), the first siloxane monomer represented by the formula (2), the second siloxane monomer represented by the formula (3), It provides a method comprising the step of reacting the third siloxane monomer represented by and the organic metal represented by the formula (5).

Formula 1

(R ¹ SiO _3/2 ) _x (SiO _4/2 ) _y (SiO _3/2 -R ² -SiO _3/2 ) _z (M (acac) _o ) _m

Formula 2

R ¹ Si (OR ³ ) _a (R ⁴ ) _b

Formula 3

Si (OR ⁵ ) ₄

Formula 4

(Si (OR ⁶ ) ₃ -R ² -Si (OR ⁷ ) ₃ ) _z

Formula 5

(M (acac) _o )

In Formula 1 and Formula 2, R ¹ is directly connected to a silicon atom or is C ₁ ~ C ₁₀ aliphatic linking group, C ₃ ~ C ₁₀ cycloaliphatic linking group, C ₆ ~ C ₂₀ aromatic linking group or C ₆ ~ C ₂₀ heteroaromatic linking group Glycidoxy or C ₁ to C ₁₀ aliphatic linking group, C ₃ to C ₁₀ cycloaliphatic linking group, C ₆ to C ₂₀ aromatic linking group or C ₆ to C ₂₀ heteroaromatic linking group directly connected to silicon atom or silicon atom via an alicyclic that is connected to a silicon atom through an epoxy group being; formula (I) and the formula from 4 R ² is unsubstituted or substituted C ₁ ~ C ₁₀ alkyl group or unsubstituted or substituted C ₅ ~ C as ₃₀ aryl group, said alkyl Substituents which may be substituted with the ethylene group and the arylene group may be C ₁ to C ₃₀ straight or branched alkyl group, C ₁ to C ₂₀ alkoxy group, amino group, acryl group, methacryl group, halogen, mercapto group, allyl group, ether group, Ester group, Carr Group, a carboxyl group, a vinyl group, a nitro group, an alcohol peongi, hydroxyl group, C ₃ ~ C ₈ cycloalkyl group, an alkyd group, a urethane group, an oxetane group, a C ₅ ~ C ₃₀ aryl group, C ₅ ~ C ₃₀ aryl group Selected from the group consisting of C ₅ to C ₃₀ aryloxy groups and combinations thereof; in Formulas 1 and 5, M is a metal atom selected from the group consisting of aluminum, titanium, zirconium, zinc and combinations thereof, acac is an acetylacetone ligand which is unsubstituted or substituted with a C ₁ to C ₁₀ straight or branched alkyl group, o is an integer from 2 to 4; R ³ in Formula 2 and R ⁴ , R ⁵ in Formula 3, R in Formula 5 ⁶ and R ⁷ are each independently a straight or branched C ₁ to C ₁₀ alkyl group; in Formula 2, a is an integer of 2 or 3, b is an integer of 0 or 1, and a + b = 3; At 0.25 ≤ x ≤ 0.979, 0.01 ≤ y ≤ 0.35, 0.01 ≤ z ≤ 0.35; 0.001 ≤ m ≤ 0.05; x + y + z + m = 1)

For example, the siloxane oligomer may be synthesized by a hydrocondensation reaction under an acid catalyst or a base catalyst in the reacting step.

In one exemplary embodiment, the first siloxane monomer represented by Formula 2 is gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl methyldimeth Methoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- It can be selected from the group consisting of (3,4-epoxycyclohexyl) ethyltripropoxysilane and combinations thereof.

In addition, the second siloxane monomer represented by the formula (3) is tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetrabutyl orthosilicate And C ₁ ~ C ₄ tetraalkyl orthosilicate of straight or branched chain selected from the group consisting of a combination thereof may be included.

In addition, the third siloxane monomer represented by the formula (4) is 1,2-bis (triethoxysilyl) ethane (1,2-bis (triethoxysilyl) ethane), 1,2-bis (trimethoxysilyl) ethane (1,2-bis (trimethoxysilyl) ethane), 1,6-bis (triethoxysilyl) hexane (1,6-bis (triethoxysilyl) hexane), 1,6-bis (trimethoxysilyl) hexane (1 , 6-bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) octane (1,8-bis (triethoxysilyl) octane), 1,8-bis (trimethoxysilyl) octane (1,8 -bis (trimethoxysilyl) octane), 1,4-bis (triethoxysilyl) benzene (1,4-bis (triethoxysilyl) benzene) and combinations thereof.

According to another aspect of the present invention, the present invention provides a hard coating composition comprising a siloxane oligomer represented by the above formula (1).

For example, the hard coating composition may further include a crosslinking agent.

The crosslinking agent may be selected from the group consisting of a chain aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated hydrocarbon epoxy monomer, a monomer having an oxetane group, and a combination thereof.

For example, the said chain aliphatic epoxy monomer is 1, 4- butanediol diglycidyl ether, 1, 6- hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl Ethers, polyethylene glycol diglycidyl ethers, glycerin triglycidyl ethers, polypropylene glycol diglycidyl ethers, polyglycidyl ethers of polyether polyols, and diglycidyl esters of aliphatic dibasic acids; Monoglycidyl ethers of aliphatic alcohols and glycidyl ethers of fatty acids; Epoxidized soybean oil. Butyl epoxy stearate, octyl epoxy stearate, epoxidized amine oil, epoxidized polybutadiene, and combinations thereof.

The cyclic aliphatic epoxy monomers are 4-vinylcyclohexene dioxide, cyclohexene vinyl monooxide, (3,4-epoxycyclohexyl) methyl, 3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexyl Methylmethacrylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) -1,3-dioxolane and It can be selected from the group consisting of a combination of these.

In addition, the monomer which has the said oxetane group is 3-methyl oxetane, 2-methyl oxetane, 3-oxetanol, 2-methylene oxetane, 3, 3- oxetane dimethane thiol, 4- (3-methyl Oxetan-3-yl) benzonitrile,-(2,2-dimethylpropyl) -3-methyl-3-oxetanemethaneamine, N- (1,2-dimethylbutyl) -3-methyl-3-jade Cetanemethaneamine, (3-ethyloxetan-3-yl) methylmethacrylate, and 4-[(3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyl-3- Hydroxymethyloxetane, 2-ethylhexyl oxetane, xylylene bis oxetane, 3-ethyl-3 [[[3-ethyloxetan-3-yl] methoxy] methyl] oxetane and combinations thereof It may be selected from the group.

Optionally, the hard coating composition may include a solvent, a polymerization initiator, a photosensitizer, a photosensitizer, a polymerization inhibitor, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, It may further comprise at least one component selected from the group consisting of a silane coupling agent, an inorganic filler, an antifoaming agent, and an antifouling agent.

According to another aspect of the invention, the present invention is a substrate; It is formed on the substrate, and provides a hard coating film comprising a hard coating layer made of a cured product of the above-described hard coating composition.

For example, the base material may be polyester resin, cellulose resin, polycarbonate resin, acrylic resin, styrene resin, polyolefin resin, polyimide resin, polyether sulfone resin, sulfone resin, and air thereof It may be made of a material selected from the group consisting of coalescence.

According to another aspect of the invention, the present invention is a display panel; And a hard coating film positioned on one surface of the display panel.

The present invention proposes a siloxane oligomer produced by reacting three different siloxane monomers with an organic metal, a hard coating composition comprising the siloxane oligomer, a hard coat film and a display device which are cured products of the composition.

The organometallic compound chemically bonds with the silane of the siloxane, and contains metal atoms in the molecular structure, thereby further securing the intermolecular space. Accordingly, the curling phenomenon can be dramatically reduced by minimizing the curing shrinkage. The hard coat film to which the siloxane oligomer according to the present invention is applied may have improved physical properties such as flexibility and scratch resistance, and thus may be utilized as an optical film of a display device.

1 is a schematic cross-sectional view of a hard coat film according to an exemplary embodiment of the present invention.

2 is a schematic cross-sectional view of a display device to which a hard coat film is applied to a cover window according to an exemplary embodiment of the present invention.

The present invention will be described in more detail with reference to the accompanying drawings.

[Siloxane oligomer and preparation method thereof]

In the hard coating layer made of a binder material, forming a tight intermolecular network to improve the surface hardness of the hard coating layer, the shrinkage is increased, the flexibility is reduced, and the curl phenomenon and hard to stretch in one direction back and forth, which does not maintain a flat state A crack phenomenon occurs in which a part of the coating layer is broken. On the other hand, increasing the flexibility of the hard coating layer can solve the curl phenomenon and crack phenomenon, but the problem is that the surface hardness is lowered. Therefore, the development of a high hardness coating material having excellent flexibility, no curling phenomenon and ease of processing is urgently needed for wider application of the polymer film.

One of the coating agents generally used for hard coating is a light or thermosetting coating agent. Photocurable coatings can be cured in a short time, as well as room temperature can be used as a surface protective coating of various plastic products. In order for the coating to be usefully used for the optical, the hardness and adhesion to the film should be excellent, and there should be no curling or rainbow phenomenon.

In particular, when a curl occurs, it may act as a big disadvantage in the roll to roll process, which is a mass production, and may cause problems in future durability even after the product is provided. In addition, the display industry is moving into the era of flexible displays, which requires a highly flexible hard coating film.

In order to solve this problem, the present invention provides a siloxane oligomer obtained by reacting three different siloxane monomers with an organic metal. Another siloxane oligomer in one aspect of the invention may be represented by the formula (1).

Formula 1

(R ¹ SiO _3/2 ) _x (SiO _4/2 ) _y (SiO _3/2 -R ² -SiO _3/2 ) _z (M (acac) _o ) _m

(Formula 1, R ¹ is directly connected to a silicon atom or silicon via a C ₁ to C ₁₀ aliphatic linking group, C ₃ to C ₁₀ cycloaliphatic linking group, C ₆ to C ₂₀ aromatic linking group or C ₆ to C ₂₀ heteroaromatic linking group Silicon directly connected to a glycidoxy group or silicon atom linked to an atom, or via a C ₁ to C ₁₀ aliphatic linking group, a C ₃ to C ₁₀ cycloaliphatic linking group, a C ₆ to C ₂₀ aromatic linking group or a C ₆ to C ₂₀ heteroaromatic linking group An alicyclic epoxy group connected to an atom; R ² is an unsubstituted or substituted C ₁ to C ₁₀ alkylene group or an unsubstituted or substituted C ₅ to C ₃₀ arylene group, which may be substituted with the alkylene group and the arylene group Substituents include C ₁ to C ₃₀ straight or branched chain alkyl groups, C ₁ to C ₂₀ alkoxy groups, amino groups, acrylic groups, methacryl groups, halogens, mercapto groups, allyl groups, ether groups, ester groups, carbonyl groups, carboxyl groups, vinyl groups , Nitro , Sulfen group, hydroxy group, C ₃ to C ₈ cycloalkyl group, alkyd group, urethane group, oxetane group, C ₅ to C ₃₀ aryl group, C ₅ to C ₃₀ arylalkyl group, C ₅ to C ₃₀ aryloxy group And combinations thereof; M is a metal atom selected from the group consisting of aluminum, titanium, zirconium, zinc, and combinations thereof, and acac is unsubstituted or a C ₁ to C ₁₀ straight or branched chain alkyl group. Substituted acetylacetone ligand, o is an integer from 2 to 4; 0.25 ≦ x ≦ 0.979, 0.01 ≦ y ≦ 0.35, 0.01 ≦ z ≦ 0.35; 0.001 ≦ m ≦ 0.05, x + y + z + m = 1)

In Formula 1, the (R ¹ SiO _3/2 ) moiety is derived from the first siloxane monomer described below, and in Formula 1, R ¹ is directly connected to a silicon atom or a C ₁ to C ₁₀ aliphatic linking group, C ₃ to C ₁₀ cycloaliphatic linking group, C ₆ ~ C ₂₀ aromatic linking group or a C ₆ ~ C ₂₀ heteroaromatic through a bonding group directly to the glycidyl sidok group or a silicon atom connected to a silicon atom or C ₁ ~ C ₁₀ aliphatic linking group, C ₃ ~ It has a functional group R ¹ which may be an alicyclic epoxy group connected to a silicon atom through a C ₁₀ cycloaliphatic linking group, a C ₆ to C ₂₀ aromatic linking group or a C ₆ to C ₂₀ heteroaromatic linking group. Since it has an epoxy group like a group epoxy group, excellent surface hardness and low hardening shrinkage rate can be achieved and a curling phenomenon can be prevented.

For example, R ¹ may be a glycidoxy group or an alicyclic epoxy group which is unsubstituted or has a C ₁ to C ₁₀ straight or branched alkyl group. More specifically, R ¹ may be selected from the group consisting of glycidoxypropyl group, epoxycyclohexylethyl group, and epoxycyclohexylmethyl group, but the present invention is not limited thereto.

In the siloxane oligomer represented by the formula (1), x, which is a mole fraction of the (R ¹ SiO _3/2 ) moiety derived from the first siloxane monomer, is 0.25 ≦ x ≦ 0.979, preferably 0.32 ≦ x ≦ 0.919, more preferably Is 0.43 ≦ x ≦ 0.839. When the mole fraction x of the (R ¹ SiO _3/2 ) moiety having an epoxy group satisfies the above-mentioned range, a siloxane oligomer having excellent surface hardness and low cure shrinkage can be obtained.

In Formula 1, the (SiO _4/2 ) moiety is derived from the second siloxane monomer described later, and the (SiO _3/2 -R ² -SiO _3/2 ) moiety is derived from the third siloxane monomer described later. Including these components, the flexibility of the siloxane oligomer represented by the formula (1) can be improved. For this purpose, the mole fraction y of the (SiO _4/2 ) moiety in the siloxane oligomer represented by Formula 1 is 0.01 ≦ y ≦ 0.35, preferably 0.04 ≦ y ≦ 0.32, more preferably 0.08 ≦ y ≦ 0.27 In the siloxane oligomer represented by the formula (1), the mole fraction z of the (SiO _3/2 -R ² -SiO _3/2 ) moiety is 0.01 ≦ z ≦ 0.35, preferably 0.04 ≦ z ≦ 0.32, more preferably 0.08 ≦ z <0.27.

In one exemplary embodiment, they may be substituted with a C ₁ -C ₁₀ alkylene group or a C ₅ -C ₃₀ arylene group constituting R ² of the (SiO _3/2 -R ² -SiO _3/2 ) moiety Substituents include C ₁ to C ₃₀ straight or branched chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group; C ₁ -C ₂₀ alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group and pentoxy group; Amino group; Acrylic group; Methacryl group; Halogen such as fluoro, bromine and chlorine; Mercapto group; Allyl group; Ether group; Ester group; Carbonyl group; Carboxyl groups; Vinyl group; Nitro group; Sulfun groups; Hydroxyl group; C ₃ -C ₈ cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; Alkyd groups; Urethane group and oxetane group; Phenyl group, biphenyl group, terphenyl group, tetraphenyl group, naphthyl group, anthracenyl group, indenyl group, penalenyl group, phenanthrenyl group, azulenyl group, pyrenyl group, fluorenyl group, tetrasenyl group, indasenyl group, flu Homo aryl or pyrrolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, tetrazinyl, imidazolyl, pyrazolyl, indolyl, carbazolyl groups such as orenyl groups , Benzocarbazoleyl group, dibenzocarbazoleyl group, indolocarbazoleyl group, indenocarbazoleyl group, benzofuranocarbazolyl group, benzothienocarbazolyl group, quinolinyl group, isoquinolinyl group, phthalazinyl Group, quinoxalinyl group, cynolinyl group, quinazolinyl group, phthalazinyl group, quinoxalinyl group, cynolinyl group, quinazolinyl group, benzoquinolinyl group, benzoisoquinolinyl group, benzoquinazolinyl group, benzoquinoxalin Neyl group, acridinyl group, phenanthrolinyl group, fura Group, pyranyl group, oxazinyl group, oxazolyl group, oxadizolyl group, triazolyl group, dioxyyl group, benzofuranyl group, dibenzofuranyl group, thiopyranyl group, thiazinyl group, thiophenyl group or N- C ₅ -C ₃₀ aryl groups such as uncondensed or condensed hetero aryl groups such as substituted spiro fluorenyl groups; C ₅ -C ₃₀ arylalkyl group; It may be selected from the group consisting of C ₅ ~ C ₃₀ aryloxy group and combinations thereof.

On the other hand, the siloxane oligomer according to the present invention includes an organometallic moiety defined as (M (acac) _o . The organometallic inclusions can ensure a space between the molecular structure, and thus the siloxane represented by the formula (1) The flexibility and processing properties of the oligomers can be improved In this regard, the mole fraction m of the organometallic (M (acac) moiety) is 0.001 ≦ m ≦ 0.05, preferably 0.001 ≦ m ≦ 0.04, more preferably 0.001 ≤ m ≤ 0.03.

In one exemplary embodiment, the organometallic component (M (acac) _o in Formula 1 is aluminum acetylacetone, titanium acetylacetone, titanium ethyl acetylacetone, zirconium monoacetylacetone, zirconium tetraacetylacetone, zinc acetylacetone and these For example, these organic metals may be selected from the group consisting of metal alkylenes (eg, C ₁ -C ₁₀ alkylenes such as ethylene / octylene) glycolate, ammonium metal lactate salt, metal Although it can be prepared from trialcohol aluminate and the like, the present invention is not limited thereto.

In one exemplary embodiment, the weight average molecular weight of the siloxane oligomer represented by Formula 1 may range from 1,000 to 100,000, preferably 1,000 to 50,000, more preferably 1,500 to 20,000. When the weight average molecular weight of the siloxane oligomer satisfies the above-mentioned range, high flexibility, low cure shrinkage rate, high surface hardness, and excellent processing characteristics can be ensured.

Next, the method of manufacturing the siloxane oligomer represented by General formula (1) is demonstrated. According to another aspect of the invention, the present invention is a method for producing a siloxane oligomer represented by the following formula (1), the first siloxane monomer represented by the formula (2), the second siloxane monomer represented by the formula (3), It provides a method comprising the step of reacting the third siloxane monomer represented by and the organic metal represented by the formula (5).

Formula 1

(R ¹ SiO _3/2 ) _x (SiO _4/2 ) _y (SiO _3/2 -R ² -SiO _3/2 ) _z (M (acac) _o ) _m

Formula 2

R ¹ Si (OR ³ ) _a (R ⁴ ) _b

Formula 3

Si (OR ⁵ ) ₄

Formula 4

(Si (OR ⁶ ) ₃ -R ² -Si (OR ⁷ ) ₃ ) _z

Formula 5

(M (acac) _o )

In Formula 1 and Formula 2, R ¹ is directly connected to a silicon atom or is C ₁ ~ C ₁₀ aliphatic linking group, C ₃ ~ C ₁₀ cycloaliphatic linking group, C ₆ ~ C ₂₀ aromatic linking group or C ₆ ~ C ₂₀ heteroaromatic linking group Glycidoxy or C ₁ to C ₁₀ aliphatic linking group, C ₃ to C ₁₀ cycloaliphatic linking group, C ₆ to C ₂₀ aromatic linking group or C ₆ to C ₂₀ heteroaromatic linking group directly connected to silicon atom or silicon atom via an alicyclic that is connected to a silicon atom through an epoxy group being; formula (I) and the formula from 4 R ² is unsubstituted or substituted C ₁ ~ C ₁₀ alkyl group or unsubstituted or substituted C ₅ ~ C as ₃₀ aryl group, said alkyl Substituents which may be substituted with the ethylene group and the arylene group may be C ₁ to C ₃₀ straight or branched alkyl group, C ₁ to C ₂₀ alkoxy group, amino group, acryl group, methacryl group, halogen, mercapto group, allyl group, ether group, Ester group, Carr Group, a carboxyl group, a vinyl group, a nitro group, an alcohol peongi, hydroxyl group, C ₃ ~ C ₈ cycloalkyl group, an alkyd group, a urethane group, an oxetane group, a C ₅ ~ C ₃₀ aryl group, C ₅ ~ C ₃₀ aryl group Selected from the group consisting of C ₅ to C ₃₀ aryloxy groups and combinations thereof; in Formulas 1 and 5, M is a metal atom selected from the group consisting of aluminum, titanium, zirconium, zinc and combinations thereof, acac is an acetylacetone ligand which is unsubstituted or substituted with a C ₁ to C ₁₀ straight or branched alkyl group, o is an integer from 2 to 4; R ³ in Formula 2 and R ⁴ , R ⁵ in Formula 3, R in Formula 5 ⁶ and R ⁷ are each independently a straight or branched C ₁ to C ₁₀ alkyl group; in Formula 2, a is an integer of 2 or 3, b is an integer of 0 or 1, and a + b = 3; At 0.25 ≤ x ≤ 0.979, 0.01 ≤ y ≤ 0.35, 0.01 ≤ z ≤ 0.35; 0.001 ≤ m ≤ 0.05; x + y + z + m = 1)

By using the first siloxane monomer of the formula (2) which is a siloxane monomer having an epoxy group, it is possible to ensure excellent surface hardness and low curing shrinkage of the siloxane oligomer represented by the formula (1). Meanwhile, the flexibility of the siloxane oligomer represented by the formula (1) can be improved by using the second siloxane monomer of the formula (3) and the third siloxane monomer of the formula (4). In addition, by using the organometallic compound of Formula 5, the intermolecular space of the siloxane oligomer represented by Formula 1 may be further secured to improve flexibility and processing characteristics.

In one exemplary embodiment, the first siloxane monomer represented by Formula 2 is gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl methyldimethoxysilane , Gamma-glycidoxypropyl methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltripropoxysilane and combinations thereof, but the present invention is not limited thereto.

On the other hand, the second siloxane monomer represented by the formula (3) includes a straight or branched C ₁ ~ C ₄ tetraalkyl orthosilicate. Such tetraalkylorthosilicates consist of tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylorthosilicate, tetraisopropylorthosilicate, tetrabutylorthosilicate and combinations thereof Although it may be selected from the group, the present invention is not limited thereto.

The third siloxane monomer represented by the formula (4) is 1,2-bis (triethoxysilyl) ethane (1,2-bis (triethoxysilyl) ethane), 1,2-bis (trimethoxysilyl) ethane (1 , 2-bis (trimethoxysilyl) ethane), 1,6-bis (triethoxysilyl) hexane (1,6-bis (triethoxysilyl) hexane), 1,6-bis (trimethoxysilyl) hexane (1,6 -bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) octane (1,8-bis (triethoxysilyl) octane), 1,8-bis (trimethoxysilyl) octane (1,8-bis (trimethoxysilyl) octane), 1,4-bis (triethoxysilyl) benzene (1,4-bis (triethoxysilyl) benzene) and combinations thereof, but the present invention is not limited thereto. .

To prepare the siloxane oligomer represented by Formula 1, an acidic catalyst or a basic catalyst capable of promoting the hydrolysis and condensation reaction of three different siloxane monomers represented by Formulas 2 to 4 and the organic metal represented by Formula 5 Suitable catalysts, such as these, can be used. In addition, in order to promote the reaction, it may be stirred for 1 hour to 120 hours at 50 ℃ to 120 ℃.

Specific catalysts that can promote the hydrolysis and condensation reactions of three different siloxane monomers and organic metals include acid catalysts such as hydrochloric acid, acetic acid, hydrogen fluoride, nitric acid, and iodide sulfate, ammonia, potassium hydroxide, sodium hydroxide and barium hydroxide. , Base catalysts such as imidazole, and ion exchange resins such as Amberite may be used. These catalysts may be used alone, but may be used in combination. The amount of the catalyst is not particularly limited, but may be added in an amount of about 0.0001 to about 10 parts by weight based on 100 parts by weight of the total components of the siloxane monomer and the organic metal represented by Formula 2 to Formula 5 described above.

[Hard Coating Composition, Hard Coating Film and Display Device]

The present invention also provides a hard coating composition comprising a siloxane oligomer represented by Formula 1, a hard coating film including a cured product of the hard coating composition, and a display device to which the hard coating film is applied as a kind of optical film.

The hard coat film includes a siloxane oligomer represented by Formula 1 as an essential component, and includes a crosslinking agent, a polymerization initiator, a solvent, a surfactant, a leveling agent, an antioxidant, and the like, as necessary.

Cross-linkers for promoting crosslinking of siloxane oligomers include, but are not particularly limited to, at least one of chained aliphatic epoxy monomers, cyclic aliphatic epoxy monomers, hydrogenated aromatic hydrocarbon epoxy monomers, and oxetane monomers. These may be included alone or in combination.

Chain aliphatic epoxy monomers include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol Diglycidyl ether (neopentylglycoldiglycidyl ether), trimethylolpropane triglycidyl ether, polyethyleneglycol diglycidylether, glycerin triglycidyl ether, glycerintriglycidyl ether Polypropyleneglycol 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 (C ₅ ~ C ₂₀ ) dibasic acids; Monoglycidyl ethers of aliphatic higher alcohols (C ₅ to C ₃₀ ); Glycidyl ethers of higher fatty acids (C ₅ to C ₃₀ ); Epoxidized soybean oil; Butyl epoxystearate; Octyl epoxystearate; Epoxidized flax oils; Although at least one compound selected from epoxidized polybutadiene and the like is included, the present invention is not limited thereto.

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, the cyclic aliphatic epoxy monomer is (3,4-epoxycyclohexyl) methyl-3 ', 4'-epoxycyclohexanecarboxylate (3,4-epoxycyclohexyl) methyl-3', 4'-epoxycyclohexanecarboxylate) , Diglycidyl 1,2-cyclohexanedicarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- Meta-dioxane (2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metha-dioxane), bis (3,4-epoxycyclohexylmethyl) adipate (bis (3 , 4-epoxycyclohexylmethyl) adipate), bis (3,4-epoxy-6-methylcyclohexyl) adipate (bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate), 3,4-epoxy-6-methylcyclo Hexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate (3,4-epoxy-6-methylcyclohexylmethyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate), ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (ε-caprolact onemodified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxy-cyclohexanecarboxylate), trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate (trimethylcaprolactonemodified 3,4-epoxycyclohexylmethyl -3 ', 4'-epoxy-cyclohexanecarboxylate), β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate (β-methyl-δ- valerolactonemodified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate), 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate) (1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate) ), Di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol (ethyleneglycol di (3,4-epoxycyclohexylmethyl) ether), ethylenebis (3,4-epoxycyclohexanecarboxylate)) (ethylenebis (3, 4-epoxycyclohexanecarboxylate)), 3,4-epoxycyclohexylmethyl (meth) acrylate (3,4-epoxycyclohexylmethyl (meth) acryl ate), bis (3,4-epoxycyclohexylmethyl) adipate (bis (3,4-epoxycyclohexylmethyl) adipate), 4-vinylcyclohexen dioxide, vinylcyclohexene monooxide ( vinylcyclohexen monoxide), and the like, but the present invention is not limited thereto.

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; One or more compounds selected from glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and polyfunctional epoxy resin such as epoxidized polyvinyl phenol, and the like, but the present invention is limited thereto. It doesn't work.

In addition, the monomer which has an oxetane group is 3-methyl oxetane, 2-methyl oxetane, 3-oxetanol, 2-methylene oxetane, 3, 3- oxetane dimethane thiol, 4- (3-methyl jade Cetane-3-yl) benzonitrile,-(2,2-dimethylpropyl) -3-methyl-3-oxetanemethaneamine, N- (1,2-dimethylbutyl) -3-methyl-3-oxetane Methanamine, (3-ethyloxetan-3-yl) methylmethacrylate, and 4-[(3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyl-3-hydro Consisting of oxymethyloxetane, 2-ethylhexyl oxetane, xylylene bis oxetane, 3-ethyl-3 [[[3-ethyloxetan-3-yl] methoxy] methyl] oxetane and combinations thereof Although it may be selected from the group, the present invention is not limited thereto.

The crosslinking agent may be included in an amount of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the siloxane oligomer represented by Formula 1 being cured with a siloxane resin. When the content of the crosslinking agent satisfies the aforementioned range, physical properties such as hardness, flexibility, scratch resistance, and the like of the hard coat film to be manufactured may be improved.

Meanwhile, the hard coating composition may further include at least one component selected from the group consisting of a solvent, a polymerization initiator, and a functional additive.

In one example, the hard coating composition includes a suitable solvent capable of dispersing solid components such as the siloxane oligomers described above. The solvent may be an organic solvent. The organic solvent is preferably a polar, nonpolar and / or aprotic solvent. In one example, the organic solvent may be C ₁ to C ₆ aliphatic alcohols, in particular methanol, ethanol and lower alcohols such as n- and I-propanol and butanol; Polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, diethylene glycol and triethylene glycol; Ketones such as acetone, methyl ethyl ketone and butanone; Esters such as ethyl acetate; Ethers such as diethyl ether, detrahydrofuran and tetrahydropyran; Amides such as dimethylacetamide and dimethylformamide; Sulfoxides and sulfones such as sulfolane and dimethyl sulfoxide; Aliphatic (optionally halogenated) hydrocarbons such as pentane, hexane and cyclohexane; And mixtures thereof.

Preferably, the solvent has a boiling point that can be easily removed by distillation, and for example, the boiling point is preferably 200 ° C. or lower, particularly 150 ° C. or lower. The solvents exemplified above may be included in the ratio of 50 to 95 parts by weight in the hard coating composition. If the content of the solvent is less than 50 parts by weight, it is difficult to coat the thin film due to the high viscosity, and if it exceeds 95 parts by weight, it takes a long time in the curing process and there is a problem of low economic efficiency.

The hard coating composition may include a polymerization initiator. An optical radical polymerization initiator, a photoion polymerization initiator, a thermal polymerization initiator, etc. can be used as a polymerization initiator, These can be used individually or in mixture of 2 or more types. Preferably it is a photoion polymerization initiator.

As the radical photopolymerization initiator, 1-hydroxycyclohexylphenyl ketone, 2,2'-dimethoxy-2-phenylacetophenone, xanthone, fluorene, fluorenone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, mihiraketone, benzoylpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1 -(4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone, diethyl thioxanthone , 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2 -Hydroxy-2-methylpropan-1-one and the like can be used. Commercially available products include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, and Esacure KIP 100F.

A photocationic polymerization initiator can be used as a photoion polymerization initiator. Examples of the photocationic polymerization initiator may include, but are not limited to, onium salts and / or organometallic salts. For example, a diaryl iodonium salt, a triarylsulfonium salt, an aryldiazonium salt, an iron-arene complex, etc. can be used as a photoion polymerization initiator.

More specifically, the photocationic polymerization initiator is an aryl sulfonium hexafluoro antimony salt, an aryl sulfonium hexafluoro phosphate salt, diphenyl iodonium hexafluoro antimony salt, diphenyl iodonidon Um hexafluorophosphate salts, ditoryl iodonium hexafluorophosphate salts, 9- (4-hydroxyethoxyphenyl) cyanrenium hexafluorophosphate salts, and the like, and the antimony salts are environmental Since there is a contamination problem, hexafluorophosphate salt-based initiators are more preferred. These can be used individually or in mixture of 2 or more types.

As a thermal polymerization initiator, for example, 3-methyl-2 butenyl tetramethylenesulfonium hexafluorolomonmonate salt, ytterbium trilomethenesulfonate salt, samarium trifluoromethenesulfonate salt, erbium trifluoro Lomethenesulfonate salt, dysprosium trifluoromethenesulfonate salt, lanthanum trifluoromethenesulfonate salt, tetrabutylphosphonium methenesulfonate salt, ethyltriphenylphosphonium bromide salt, benzyldimethylamine, Dimethylaminomethylphenol, triethanolamine, Nn-butylimidazole, 2-ethyl-4-methylimidazole, etc. can be used. These can be used individually or in mixture of 2 or more types.

In one exemplary embodiment, as the cationic polymerization initiator, those known in the art can be used without limitation as materials capable of generating acids according to Bronsted-Lowry's acid-base definition or Lewis acid-base definition. have. For example, the cationic polymerization initiator is 3-methyl-2butenyltetramethylenesulfonium hexafluoroantimonate salt, ytterbium (III) trifluoromethenesulfonate salt, samarium (III) trifluoromethenesulfo Nate salt, erbium trifluoromethenesulfonate salt, triaryl sulfonium hexafluoroantimonate salt, triaryl sulfonium hexafluorophosphate salt, lanthanum (III) trifluoromethenesulfonate salt, tetrabutyl Phosphonium methenesulfonate salt, ethyltriphenylphosphonium bromide salt, diphenyliodonium hexafluoroantimonate salt, diphenyliodonium hexaflourophosphate salt, ditoryliodonium hexafluorophosphate Salts, 9- (4-hydroxyethoxyphenyl) cyanthrenium hexafluorophosphate salts, and 1- (3-methylbut-2-enyl) tetrahydro-1H-thiophenium hexafluoroantimonate A group of salts It may include one or more selected from, but are not limited to,

The anionic polymerization initiator may be, but not limited to, tertiary amine or imidazole. For example, the anionic polymerization initiators include ο- (dimethylaminomethyl) phenol, tris- (dimethylaminomethyl) phenol, benzyldimethylamine, α-methylbenzyldimethylamine, and 2-ethyl-4methyl. It may include one or more selected from the group consisting of midazoles, but is not limited thereto.

The content of the polymerization initiator in the hard coating composition according to the present invention is not particularly limited, for example, 0.1 to 20 parts by weight, preferably 0.5 to 10, based on 100 parts by weight of the siloxane oligomer represented by Formula 1 cured with a silicone resin. It may be included in parts by weight. When the content of the polymerization initiator is in the above range, it is possible to maintain the curing efficiency of the hard coating composition excellent, and to prevent the reduction of physical properties of the hard coating film due to the remaining components after curing.

In addition, the hard coating composition according to the present invention is a photosensitizer, a photosensitizer, a polymerization inhibitor, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, a UV absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler, an antifoaming agent. And at least one functional additive from the group consisting of antifouling agents.

For example, the leveling agent may be an acrylic leveling agent, a silicone leveling agent, a fluorine leveling agent, a silicone-acrylate copolymer leveling agent, a fluorine-modified acrylic leveling agent, a fluorine-modified silicone leveling agent, and a functional group (eg, alkoxy). Groups such as methoxy or ethoxy groups, acyloxy groups, halogen groups, amino groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, or isocyanate groups), and in the group consisting of combinations thereof Can be selected.

Since the content of these functional additives can be variously adjusted within the range of not lowering the physical properties of the hard coat film of the present invention, it is not particularly limited, for example, 100 parts by weight of the siloxane oligomer represented by the formula (1) cured with a siloxane resin 0.01 to 20 parts by weight, preferably 0.01 to 10 parts by weight.

Next, the hard coat film and the display apparatus manufactured using the composition for hard coating which concerns on this invention are demonstrated. 1 is a cross-sectional view schematically showing a hard coating film prepared from a composition for hard coating according to an exemplary embodiment of the present invention. As shown in FIG. 1, the hard coating film 100 includes a substrate 110 and a hard coating layer 120 stacked on the substrate 110.

Substrate 110 is preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding, isotropy. For example, the base material 100 may include polyester resins such as polyethylene terephthalate, polyethylene isophthalate, and polybutylene terephthalate; Cellulose resins such as diacetyl cellulose and triacetyl cellulose; Polycarbonate resins; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene resins such as polystyrene acrylonitrile-styrene copolymer; Polyolefin resins such as polyethylene, polypropylene, cycloolefin or polyolefin resin having a norbornene structure, and ethylene propylene copolymer; Polyimide resin; Polyether sulfone resin; Sulfone resins; And it may be a substrate made of a copolymer thereof. The thickness of the substrate 110 is not particularly limited, and may be, for example, 10 to 3000 μm.

The hard coating layer 120 may include a siloxane oligomer represented by Formula 1, and may be obtained from the above-described hard coating composition including a crosslinking agent, a solvent, a polymerization initiator, a functional additive, and the like, as necessary. For example, the hard coating composition including the siloxane oligomer represented by Chemical Formula 1 may be coated on an appropriate substrate 110, and may be dried, polymerized, or the like to form a hard coating layer 120.

When the hard coating composition described in detail above is coated on the substrate 110, the coating method is not particularly limited. For example, a coating process may be performed in a suitable manner such as a die coater, air knife, reverse roll, spray, blade, casting, gravure, micro gravure, or spin coating to coat the composition for hard coating.

In one example, after coating the above-described hard coating composition on the substrate 110, for 10 seconds to 1 hour, more preferably for 30 seconds to 30 minutes at a temperature of 30 to 150 ℃, for example 30 to 100 ℃ The volatiles are evaporated to dryness (soft baking). After curing by irradiation with UV light. The irradiation amount of the UV light may be 0.01 to 10 J / ㎠, preferably 0.1 to 2 J / ㎠. If necessary, after UV irradiation, it may be cured or aged for 30 minutes to 48 hours at a temperature of 30 to 150 ℃, for example 40 to 120 ℃ (hard baking). Through such a process, the hard coating layer 120 may be formed on the substrate 110. The thickness of the hard coating layer 120 is not particularly limited, and may be, for example, 0.05 to 100 μm, preferably 0.5 to 50 μm. Since the hard coating layer 120 has a siloxane resin which is a cured product of the siloxane oligomer represented by Chemical Formula 1, the hard coating film 100 may improve the flexibility, surface hardness and scratch resistance of the hard coating film 100, and may cause curling due to a decrease in curing shrinkage. Etc. can be prevented.

As such, the hard coat film 100 according to the present invention is excellent in hardness, scratch resistance, wear resistance, chemical resistance, and the like. Therefore, the hard coat film 100 of the present invention may be applied to an optical film, for example, a window film such as a cover window, for which hardness characteristics are required in the display device. 2 is a schematic cross-sectional view of a display apparatus 200 to which a cover window 100 made of a hard coat film according to the present invention is applied.

 As shown in FIG. 2, the cover window 100 made of a hard coating film covers one surface of the display panel 210 displaying an image and protects the display panel 210. In one example, the cover window 100 made of a hard coating film according to the present invention is a display device 200 having a flexible or foldable characteristics by preventing damage caused by external impact and damage caused by scratch Applicable to

The display apparatus 200 includes a display panel 210, a back cover 230 in which the display panel 210 is accommodated, and a cover window coupled to the back cover 230 at the front of the display panel 210. 100). The display panel 210 may be a liquid crystal display panel, an organic light emitting diode (OLED) device, and a quantum dot light emitting diode (QLED) device.

For example, when the display panel 210 is a liquid crystal display panel, the display panel 210 includes a liquid crystal panel for displaying an image, a backlight unit (not shown) disposed under the liquid crystal panel, a liquid crystal panel and a backlight. It may include a main frame surrounding the side of the unit, a bottom frame connected to the main frame from the back of the backlight unit, and a top frame covering the front edge of the liquid crystal panel. The back cover 230 covers a rear surface of the display panel 210 and includes a space in which the display panel 210 is accommodated.

The cover window 100 covers the front surface of the display panel 210 to protect the display panel 210 and is a surface on which a user or external contact is made. In order to bond the cover window 100 to the display panel 210, an adhesive layer 220 such as an optically clear adhesive (OCA) may be interposed between the cover window 100 and the display panel 210. have. Cover window 100 is composed of a hard coating film according to the present invention, excellent physical properties such as flexibility, impact resistance, surface hardness, scratch resistance. Therefore, damage or breakage of the cover window 100 may be minimized due to user contact or external pressure.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the technical spirit described in the following examples.

Example 1: Preparation of epoxy siloxane oligomer

155.22 g of glycidoxypropyl trimethoxysilane, 2.13 g of tetraethoxysilane, and 3.6 g of 1,2-bis (triethoxysilyl) ethane were mixed and mixed in a 300 mL three neck flask. After adding 160.2 g of methanol, 0.337 g of aluminum acetylacetonate was added and stirred for 30 minutes. Thereafter, 0.5 g of 0.1 N nitric acid catalyst was added thereto, and then 41.9 g of water was slowly added dropwise for 30 minutes, and reacted at 60 ° C. for 12 hours. The reaction was distilled under reduced pressure to remove methanol to prepare a siloxane oligomer.

Examples 2 to 23 Preparation of Glycidoxy Epoxy Silica Oligomers

Starting materials such as glycidoxypropyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane were added in the same amounts as shown in Table 1, and the procedure was carried out in the same manner as in Example 1. Proceeding to prepare a siloxane oligomer.

Examples 24-26 Preparation of siloxane oligomers in which glycidoxy epoxy and alicyclic epoxy are mixed

Starting materials such as glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane are shown in the following table. A siloxane oligomer was prepared in the same manner as in Example 1 by adding the same amount as indicated in Example 1.

Example 27 Preparation of Siloxane Oligomers Mixed with Alicyclic Epoxy

Starting materials such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane were added in the same amounts as shown in Table 1 below. The procedure was carried out as in Example 1 to prepare a siloxane oligomer.

Comparative Example 1: Preparation of glycidoxy epoxy siloxane oligomer

155.22 g of glycidoxypropyl trimethoxysilane, 20.39 g of tetraethoxysilane, and 33.9 g of 1,2-bis (triethoxysilyl) ethane were mixed and mixed in a 2 L three neck flask. After adding 160.2 g of methanol, 0.5 g of 0.1N nitric acid catalyst was added thereto, and then 41.9 g of water was slowly added dropwise for 30 minutes, followed by reaction at 60 degrees for 12 hours. The reaction was distilled under reduced pressure to remove methanol to prepare a siloxane oligomer.

Comparative Examples 2 to 10: Preparation of glycidoxy epoxy siloxane oligomer

Starting materials such as glycidoxypropyl trimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane were added in the same amounts as shown in Table 2, and the procedure was the same as in Comparative Example 1. To proceed to prepare a siloxane oligomer.

Comparative Examples 11 to 13: Preparation of siloxane oligomer mixed with glycidoxy epoxy and alicyclic epoxy

Starting materials such as glycidoxypropyl trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane are shown in the following table. A siloxane oligomer was prepared in the same manner as in Comparative Example 1 by adding the same amount as indicated in 2.

Comparative Example 14 Preparation of Siloxane Oligomer Mixed with Alicyclic Epoxy

Starting materials such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane were added in the amounts shown in Table 2 below. The procedure was performed in the same manner as in Comparative Example 1 to prepare a siloxane oligomer.

Comparative Examples 15 to 16: Preparation of glycidoxy epoxy siloxane oligomer

It is prepared by adding aluminum acetylacetonate, and starting materials such as glycidoxypropyl trimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane are shown in Table 2 below. The same amount was added to the procedure in the same manner as in Comparative Example 1 to prepare a siloxane oligomer.

Comparative Examples 17 to 19: Preparation of Glycidoxy Epoxy Silica Oligomers

It is prepared by adding aluminum butoxide, and starting materials such as glycidoxypropyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane are shown in Table 2 below. A siloxane oligomer was prepared in the same manner as in Comparative Example 1 by adding an amount.

Comparative Examples 20 to 21: Preparation of Glycidoxy Epoxy Silica Oligomers

It is prepared by adding tetraisopropyl titanate,

Starting materials such as glycidoxypropyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane were added in the same amounts as shown in Table 2, and the procedure was the same as in Comparative Example 1. To proceed to prepare a siloxane oligomer.

(R ¹ SiO _3/2 ) _x (SiO _4/2 ) _y (SiO _3/2 -R ² -SiO _3/2 ) _z (M (acac) _o ) _m

Sample	(R 1 SiO 3/2 )		(SiO 4/2 )	(SiO 3/2 -R 2 -SiO 3/2	(M (acac) o )
	A (mole fraction)	B (mole fraction)	C (mole fraction)	D (mole fraction)	E (mole fraction)
Example 1	152.22 g (0.979)		2.13 g (0.010)	3.6 g (0.010)	0.337 g (0.001)
Example 2	152.22 g (0.930)		2.24 g (0.01)	3.8 g (0.01)	17.761 g (0.05)
Example 3	152.22 g (0.299)		243.86 g (0.350)	415.1 g (0.350)	1.105 g (0.001)
Example 4	152.22 g (0.250)		291.66 g (0.350)	496.4 g (0.350)	66.072 g (0.05)
Example 5	152.22 g (0.919)		9.07 g (0.040)	15.4 g (0.040)	0.359 g (0.001)
Example 6	152.22 g (0.880)		9.47 g (0.040)	16.1 g (0.040)	15.016 g (0.040)
Example 7	152.22 g (0.359)		185.7 g (0.320)	316.1 g (0.320)	0.920 g (0.04)
Example 8	152.22 g (0.320)		208.33 g (0.320)	354.6 g (0.320)	41.295 g (0.001)
Example 9	152.22 g (0.839)		19.86 g (0.080)	33.8 g (0.080)	0.393 g (0.001)
Example 10	152.22 g (0.810)		20.58 g (0.080)	35.0 g (0.080)	12.236 g (0.030)
Example 11	152.22 g (0.459)		122.55 g (0.270)	208.6 g (0.270)	0.720 g (0.001)
Example 12	152.22 g (0.430)		130.81 g (0.270)	222.6 g (0.270)	23.048 g (0.03)
Example 13	152.22 g (0.828)		20.63 g (0.082)	34.3 g (0.080)	3.999 g (0.01)
Example 14	152.22 g (0.758)		41.78 g (0.152)	37.4 g (0.080)	4.358 g (0.01)
Example 15	152.22 g (0.690)		66.420 g (0.22)	41.1 g (0.08)	4.788 g (0.01)
Example 16	152.22 g (0.645)		85.59 g (0.265)	44.0 g (0.080)	5.122 g (0.01)
Example 17	152.22 g (0.602)		106.59 g (0.308)	47.1 g (0.08)	5.488 g (0.01)
Example 18	152.22 g (0.690)		24.15 g (0.080)	113.1 g (0.220)	4.788 g (0.01)
Example 19	152.22 g (0.645)		25.84 g (0.080)	145.7 g (0.265)	5.122 g (0.01)
Example 20	152.22 g (0.790)		26.37 g (0.1)	44.9 (0.1)	4.182 (0.01)
Example 21	152.22 g (0.590)		70.62 g (0.2)	120.2 g (0.2)	5.599 g (0.01)
Example 22	152.22 g (0.696)		64.06 g (0.214)	40.8 g (0.080)	4.747 g (0.01)
Example 23	152.22 g (0.686)		64.99 g (0.214)	41.4 g (0.080)	9.631 g (0.02)
Example 24	76.11 g (0.295)	123.19 g (0.295)	70.62 g (0.20)	120.2 g (0.20)	5.599 g (0.01)
Example 25	30.44 g (0.118)	197.10 g (0.472)	70.62 g (0.20)	120.2 g (0.20)	5.599 g (0.01)
Example 26	121.79 g (0.472)	49.28 g (0.118)	70.62 g (0.20)	120.2 g (0.20)	5.599 g (0.01)
Example 27		246.38 g (0.590)	70.62 g (0.20)	120.2 g (0.20)	5.599 g (0.01)
A: glycidoxypropyl trimethoxysilane B: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane C: tetraethoxysilane D: 1,2-bis (triethoxysilyl) ethane E: Aluminum acetylacetonate

(R ¹ SiO _3/2 ) _x (SiO _4/2 ) _y (SiO _3/2 -R ² -SiO _3/2 ) _z (M (acac) _o ) _m

Sample	(R 1 SiO 3/2 )		(SiO 4/2 )	(SiO 3/2 -R 2 -SiO 3/2	(M (acac) o )
	A (mole fraction)	B (mole fraction)	C (mole fraction)	D (mole fraction)	E	F	G
Comparative Example 1	152.22 g (0.838)		20.39 g (0.082)	33.9 g (0.080)
Comparative Example 2	152.22 g (0.768)		41.23 g (0.152)	36.9 g (0.080)
Comparative Example 3	152.22 g (0.700)		65.48 g (0.220)	40.5 g (0.080)
Comparative Example 4	152.22 g (0.655)		84.29 g (0.265)	43.3 g (0.080)
Comparative Example 5	152.22 g (0.612)		104.85 g (0.308)	46.4 g (0.080)
Comparative Example 6	152.22 g (0.700)		23.81 g (0.080)	114.4 g (0.220)
Comparative Example 7	152.22 g (0.655)		25.44 g (0.080)	143.5 g (0.265)
Comparative Example 8	152.22 g (0.300)		451.38 g (0.650)	59.1 g (0.050)
Comparative Example 9	152.22 g (0.612)		27.23 g (0.080)	178.5 g (0.308)
Comparative Example 10	152.22 g (0.20)		781.24 g (0.750)	88.6 g (0.050)
Comparative Example 11	76.11 g (0.30)	123.19 g (0.30)	69.44 g (0.200)	118.2 g (0.200)
Comparative Example 12	30.44 g (0.118)	197.10 g (0.472)	72.39 g (0.205)	123.2 g (0.205)
Comparative Example 13	121.78 g (0.472)	49.28 g (0.118)	72.39 g (0.205)	123.2 g (0.205)
Comparative Example 14		246.38 g (0.600)	69.44 g (0.200)	118.2 g (0.200)
Comparative Example 15	152.2 g (0.612)		104.85 g (0.308)	46.4 g (0.08)	4.308 g (0.003)
Comparative Example 16	152.2 g (0.612)		104.85 g (0.308)	46.4 g (0.08)		32.388 (0.008)
Comparative Example 17	152.2 g (0.706)		62.85 g (0.213)	40.2 g (0.08)		0.513 g (0.001)
Comparative Example 18	152.22 g (0.657)		67.54 g (0.213)	43.2 g (0.08)		18.74 g (0.05)
Comparative Example 19	152.2 g (0.607)		73.1 g (0.213)	46.7 g (0.08)		40.582 g (0.1)
Comparative Example 20	152.22 g (0.706)		62.85 g (0.213)	40.2 g (0.08)			0.349 g (0.001)
Comparative Example 21	152.22 g (0.657)		67.54 g (0.213)	43.2 g (0.08)			21.63 g (0.05)
When prepared in Comparative Example 10, Comparative Example 19 and Comparative Example 21, the siloxane oligomer is Gelated A: Glycidoxypropyl trimethoxysilane B: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane C : Tetraethoxysilane D: 1,2-bis (triethoxysilyl) ethane E: Aluminum acetylacetonate F: Aluminum butoxide G: tetraisopropyl titanate

Experimental Example 1 Preparation of Hard Coating Film

100 parts by weight of the siloxane oligomers prepared in Examples 1 to 27 and Comparative Examples 1 to 21, 20 parts by weight of a crosslinking agent (3-ethyl-3-hydroxymethyloxetane, OXT 101, Toagosei), and a photopolymerization initiator (4- Methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate (Irgacure-250, BASF Co.) 3 parts by weight, solvent methyl ethyl ketone by mixing the composition for forming a window coating layer (all components except solvent: 50 Weight percent)). The prepared composition for forming a window coating layer was coated on one surface of a transparent polyimide film (CPI (Colorless POlymidie, thickness: 100 μm)) as a base layer with Mey bar # 34, and dried at 100 ° C. for 5 minutes. , 1000 mJ / cm ² was irradiated with UV, Aging at 50 ℃ for 24 hours to prepare a window film having a window coating layer (thickness: 20㎛) formed on one surface of the transparent polyimide film.

Experimental Example 2: Evaluation of Physical Properties of Window Film

[Property evaluation method]

(1) pencil hardness

The coating layer of the film was measured by the JIS K5400 method using a pencil hardness tester (Heidon). When measuring pencil hardness, the pencil used the pencil of 6B-9H by Mitsubishi. The load of the pencil on the coating layer was 0.75 kg, the angle at which the pencil was drawn was 45 °, and the speed at which the pencil was drawn was 60 mm / min. When the scratch occurs more than one time to evaluate five times, the pencil hardness was measured using the pencil of the step below, and the maximum pencil hardness value when there is no scratch in all five evaluations are shown in Table 3 and Table 4.

(2) curling

When the coated film was cut horizontally x vertically (10 cm x 10 cm), placed on the floor and left at 25 ° C. and 40% relative humidity, the highest height (H) from the bottom to the edge of the cutting film was measured and averaged. Are shown in Table 3 and Table 4.

(3) radius of curvature

CPI (Colorless Polyimide) window film (width x length x thickness, 3 cm x 15 cm x 100 μm) was wound on JIG (CFT-200R, COVOTECH Co., Ltd.) for curvature radius test, and the wound state was kept for 5 seconds or more. It was visually evaluated whether cracks occurred in the film when solved at. The radius of curvature is measured by making the window coating layer contact JIG. The radius of curvature was measured by gradually decreasing the diameter of the JIG starting from the maximum radius of the JIG, and the minimum radius of the JIG without cracking is shown in Table 3 and Table 4 as the radius of curvature.

(4) ΔY.I. measured the yellow index (Y1) using a color difference meter (CM3600D, Konica Minolta) at a D65 light source 2 ° (angle of the window film and the light source) for the window film. Then, the window film was irradiated with light having a peak wavelength of 306 nm for 72 hours using an optical device (CT-UVT, Core Tech), and the yellow index (Y2) was evaluated in the same manner. Light reliability was shown in Table 3 and Table 4 using the difference between the yellow index before light irradiation and after light irradiation (Y2-Y1, ΔY.I.).

(5) wear resistance test

In order to evaluate the scratch resistance of the transparent flexible hard coating film prepared according to the Examples and Comparative Examples, using a steel wool of # 0000 using the scratch resistance measuring equipment of the hard coating film at a load of 1.5 N / cm ² The surface was reciprocated ten times, and the presence or absence of the scratch was confirmed according to the result. The results are shown in Tables 3 and 4 as ○ (no scratch) and X (no scratch).

(6) chemical resistance

After fixing the film cut to 1cm X 1cm in slide glass with the adhesive tape (3M) facing upwards, soak it in acetone, NMP, KOH 0.05% aqueous solution for 12 hours, and then measure whether peeling of the coating layer occurred. When peeling occurred, it was judged to be defective, and when not occurring, good. The physical property evaluation result of the window film which is the hardened | cured material of the siloxane oligomer of Examples 1-27 is shown in Table 3 below, and the physical property evaluation result of the window film which is the hardened | cured material of the siloxane oligomer of Comparative Examples 1-21 is shown in following Table 4, respectively. It was confirmed that the physical properties of the window film, which is a cured product of the siloxane oligomer prepared according to the present invention, were greatly improved.

Hard coating film properties of the siloxane oligomer cured product according to the embodiment

Sample	Pencil hardness (H)	Curling (mm)	Radius of curvature	ΔYI	Wear resistance	Chemical resistance
Example 1	6	6	1.5	2.2	pass	pass
Example 2	7	5	1.5	2.1	pass	pass
Example 3	9	5	1.8	2.0	pass	pass
Example 4	9	6	1.8	2.0	pass	pass
Example 5	7	5	1.5	1.95	pass	pass
Example 6	7	5	1.5	1.90	pass	pass
Example 7	9	3	1.9	1.85	pass	pass
Example 8	9	3	1.9	1.55	pass	pass
Example 9	7	3	1.6	1.56	pass	pass
Example 10	7	3	1.5	1.95	pass	pass
Example 11	9	2	1.7	1.78	pass	pass
Example 12	9	2	1.9	1.64	pass	pass
Example 13	7	2	1.5	1.5	pass	pass
Example 14	8	3	1.6	1.8	pass	pass
Example 15	8	3	1.5	1.9	pass	pass
Example 16	9	2	1.6	1.78	pass	pass
Example 17	8	0	1.7	1.78	pass	pass
Example 18	9	2	1.8	1.80	pass	pass
Example 19	8	0	1.7	2.10	pass	pass
Example 20	9	4	1.5	1.98	pass	pass
Example 21	9	3	1.6	2.00	pass	pass
Example 22	9	3	1.7	1.92	pass	pass
Example 23	9	3	1.8	2.01	pass	pass
Example 24	9	5	1.6	1.70	pass	pass
Example 25	9	6	1.9	2.15	pass	pass
Example 26	9	6	1.8	1.95	pass	pass
Example 27	9	8	2.2	1.92	pass	pass

Hard Coating Film Properties of Cured Siloxane Oligomers According to Comparative Example

Sample	Pencil hardness (H)	Curling (mm)	Radius of curvature	ΔYI	Wear resistance	Chemical resistance
Comparative Example 1	4	20	4.2	6.87	Fail	Fail
Comparative Example 2	5	18	5.2	6.99	Fail	Fail
Comparative Example 3	5	17	5.5	5.66	Fail	Fail
Comparative Example 4	5	15	6	5.42	Fail	Fail
Comparative Example 5	6	15	5.5	4.36	Fail	Fail
Comparative Example 6	5	14	6.5	4.87	Fail	Fail
Comparative Example 7	5	10	6	5.84	Fail	Fail
Comparative Example 8	7	20	7	6.25	Fail	Fail
Comparative Example 9	6	25	21	5.77	Fail	Fail
Comparative Example 10	-	-	-	-	-	-
Comparative Example 11	5	30	17	5.66	Fail	Fail
Comparative Example 12	6	15	18	5.87	Fail	Fail
Comparative Example 13	6	10	5.5	5.15	Fail	pass
Comparative Example 14	7	10	6.5	4.66	Fail	pass
Comparative Example 15	6	10	5.4	5.66	Fail	pass
Comparative Example 16	7	15	3.8	5.55	Fail	Fail
Comparative Example 17	5	20	7	5.97	Fail	Fail
Comparative Example 18	6	25	21.5	6.52	Fail	Fail
Comparative Example 19	-	-	-	-	-	-
Comparative Example 20	4	30	17	7.25	Fail	Fail
Comparative Example 21	-	-	-	-	-	-
** When prepared in Comparative Example 10, Comparative Example 19, Comparative Example 21, the siloxane oligomer was not measured by Gellation.

The present invention has been described above based on exemplary embodiments and examples of the present invention, but the present invention is not limited to the technical idea described in the above embodiments and examples. Rather, those skilled in the art can easily make various modifications and changes based on the above-described embodiments and examples. However, it is apparent in the appended claims that all such modifications and variations fall within the scope of the present invention.

Claims (21)

1. A siloxane oligomer represented by the following formula (1) for forming a hard coat film of a display device.

   Formula 1

   (R ¹ SiO _3/2 ) _x (SiO _4/2 ) _y (SiO _3/2 -R ² -SiO _3/2 ) _z (M (acac) _o ) _m

   (Formula 1, R ¹ is directly connected to a silicon atom or silicon via a C ₁ to C ₁₀ aliphatic linking group, C ₃ to C ₁₀ cycloaliphatic linking group, C ₆ to C ₂₀ aromatic linking group or C ₆ to C ₂₀ heteroaromatic linking group Silicon directly connected to a glycidoxy group or silicon atom linked to an atom, or via a C ₁ to C ₁₀ aliphatic linking group, a C ₃ to C ₁₀ cycloaliphatic linking group, a C ₆ to C ₂₀ aromatic linking group or a C ₆ to C ₂₀ heteroaromatic linking group An alicyclic epoxy group connected to an atom; R ² is an unsubstituted or substituted C ₁ to C ₁₀ alkylene group or an unsubstituted or substituted C ₅ to C ₃₀ arylene group, which may be substituted with the alkylene group and the arylene group Substituents include C ₁ to C ₃₀ straight or branched chain alkyl groups, C ₁ to C ₂₀ alkoxy groups, amino groups, acrylic groups, methacryl groups, halogens, mercapto groups, allyl groups, ether groups, ester groups, carbonyl groups, carboxyl groups, vinyl groups , Nitro , Sulfen group, hydroxy group, C ₃ to C ₈ cycloalkyl group, alkyd group, urethane group, oxetane group, C ₅ to C ₃₀ aryl group, C ₅ to C ₃₀ arylalkyl group, C ₅ to C ₃₀ aryloxy group And combinations thereof; M is a metal atom selected from the group consisting of aluminum, titanium, zirconium, zinc, and combinations thereof, and acac is unsubstituted or a C ₁ to C ₁₀ straight or branched chain alkyl group. Substituted acetylacetone ligand, o is an integer from 2 to 4; 0.25 ≦ x ≦ 0.979, 0.01 ≦ y ≦ 0.35, 0.01 ≦ z ≦ 0.35; 0.001 ≦ m ≦ 0.05, x + y + z + m = 1)
2. The siloxane oligomer of claim 1, wherein in Formula 1, 0.32 ≦ x ≦ 0.919, 0.04 ≦ y ≦ 0.32, 0.04 ≦ z ≦ 0.32, 0.001 ≦ m ≦ 0.04, and x + y + z + m = 1.
3. The siloxane oligomer of claim 1, wherein in Formula 1, 0.43 ≦ x ≦ 0.839, 0.08 ≦ y ≦ 0.27, 0.08 ≦ z ≦ 0.27, 0.001 ≦ m ≦ 0.03, and x + y + z + m = 1.
4. The method according to claim 1, wherein in Formula 1, R ¹ is a gamma-glycidoxy group, a gamma-glycidoxypropyl group, and 2- (3,4-epoxycyclohexyl group) and 2- (3,4-epoxycyclohexyl). Siloxane oligomers selected from the group consisting of ethyl groups.
5. According to claim 1, M (acac) _o of Formula 1 is a group consisting of aluminum acetyl acetone, titanium acetyl acetone, titanium ethyl acetyl acetone, zirconium monoacetyl acetone, zirconium tetraacetyl acetone, zinc acetyl acetone and combinations thereof Siloxane oligomers selected from.
6. The siloxane oligomer of claim 1, wherein the weight average molecular weight of the siloxane oligomer is 1,000 to 100,000.
7. As a method of manufacturing a siloxane oligomer represented by the formula (1) for forming a hard coat film of the display device,

   A method comprising reacting a first siloxane monomer represented by Formula 2, a second siloxane monomer represented by Formula 3, a third siloxane monomer represented by Formula 4, and an organic metal represented by Formula 5.

   Formula 1

   (R ¹ SiO _3/2 ) _x (SiO _4/2 ) _y (SiO _3/2 -R ² -SiO _3/2 ) _z (M (acac) _o ) _m

   Formula 2

   R ¹ Si (OR ³ ) _a (R ⁴ ) _b

   Formula 3

   Si (OR ⁵ ) ₄

   Formula 4

   (Si (OR ⁶ ) ₃ -R ² -Si (OR ⁷ ) ₃ ) _z

   Formula 5

   (M (acac) _o )

   In Formula 1 and Formula 2, R ¹ is directly connected to a silicon atom or is C ₁ ~ C ₁₀ aliphatic linking group, C ₃ ~ C ₁₀ cycloaliphatic linking group, C ₆ ~ C ₂₀ aromatic linking group or C ₆ ~ C ₂₀ heteroaromatic linking group Glycidoxy or C ₁ to C ₁₀ aliphatic linking group, C ₃ to C ₁₀ cycloaliphatic linking group, C ₆ to C ₂₀ aromatic linking group or C ₆ to C ₂₀ heteroaromatic linking group directly connected to silicon atom or silicon atom via an alicyclic that is connected to a silicon atom through an epoxy group being; formula (I) and the formula from 4 R ² is unsubstituted or substituted C ₁ ~ C ₁₀ alkyl group or unsubstituted or substituted C ₅ ~ C as ₃₀ aryl group, said alkyl Substituents which may be substituted with the ethylene group and the arylene group may be C ₁ to C ₃₀ straight or branched alkyl group, C ₁ to C ₂₀ alkoxy group, amino group, acryl group, methacryl group, halogen, mercapto group, allyl group, ether group, Ester group, Carr Group, a carboxyl group, a vinyl group, a nitro group, an alcohol peongi, hydroxyl group, C ₃ ~ C ₈ cycloalkyl group, an alkyd group, a urethane group, an oxetane group, a C ₅ ~ C ₃₀ aryl group, C ₅ ~ C ₃₀ aryl group Selected from the group consisting of C ₅ to C ₃₀ aryloxy groups and combinations thereof; in Formulas 1 and 5, M is a metal atom selected from the group consisting of aluminum, titanium, zirconium, zinc and combinations thereof, acac is an acetylacetone ligand which is unsubstituted or substituted with a C ₁ to C ₁₀ straight or branched alkyl group, o is an integer from 2 to 4; R ³ in Formula 2 and R ⁴ , R ⁵ in Formula 3, R in Formula 5 ⁶ and R ⁷ are each independently a straight or branched C ₁ to C ₁₀ alkyl group; in Formula 2, a is an integer of 2 or 3, b is an integer of 0 or 1, and a + b = 3; At 0.25 ≤ x ≤ 0.979, 0.01 ≤ y ≤ 0.35, 0.01 ≤ z ≤ 0.35; 0.001 ≤ m ≤ 0.05; x + y + z + m = 1)
8. 8. The method according to claim 7, wherein the siloxane oligomer is synthesized by a hydrocondensation reaction under an acid catalyst or a base catalyst in the reacting step.
9. The method of claim 7, wherein the first siloxane monomer represented by the formula (2) is gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl methyldimethoxysilane , Gamma-glycidoxypropyl methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltripropoxysilane and combinations thereof.
10. The method of claim 7, wherein the second siloxane monomer represented by Formula 3 is tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylorthosilicate, tetraisopropylorthosilicate or tetra A method comprising a straight or branched C ₁ to C ₄ tetraalkyl orthosilicate selected from the group consisting of butyl orthosilicate and combinations thereof.
11. The method of claim 7, wherein the third siloxane monomer represented by the formula (4), 1,2-bis (triethoxysilyl) ethane (1,2-bis (triethoxysilyl) ethane), 1,2-bis (trimeth Methoxysilyl) ethane (1,2-bis (trimethoxysilyl) ethane), 1,6-bis (triethoxysilyl) hexane (1,6-bis (triethoxysilyl) hexane), 1,6-bis (trimethoxysilyl ) Hexane (1,6-bis (trimethoxysilyl) hexane), 1,8-bis (triethoxysilyl) octane (1,8-bis (triethoxysilyl) octane), 1,8-bis (trimethoxysilyl) octane (1,8-bis (trimethoxysilyl) octane), 1,4-bis (triethoxysilyl) benzene (1,4-bis (triethoxysilyl) benzene) and a combination thereof.
12. A hard coat composition comprising the siloxane oligomer of claim 1 for forming a hard coat film of a display device.
13. The hard coating composition of claim 12, wherein the hard coating composition further comprises a crosslinking agent.
14. The hard coating composition of claim 13, wherein the crosslinking agent is selected from the group consisting of a chain aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated hydrocarbon epoxy monomer, a monomer having an oxetane group, and a combination thereof.
15. The said chain aliphatic epoxy monomer is a 1, 4- butanediol diglycidyl ether, 1, 6- hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and a trimethylol propane triglycol. Cydyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of polyether polyols, and diglycidyl esters of aliphatic dibasic acids; Monoglycidyl ethers of aliphatic alcohols and glycidyl ethers of fatty acids; Epoxidized soybean oil. Hard coating composition selected from the group consisting of butyl epoxy stearate, octyl epoxy stearate, epoxidized amine oil, epoxidized polybutadiene and combinations thereof.
16. 15. The method of claim 14, wherein the cyclic aliphatic epoxy monomer is 4-vinylcyclohexene dioxide, cyclohexene vinyl monooxide, (3,4-epoxycyclohexyl) methyl, 3,4-epoxycyclohexylcarboxylate, , 4-epoxycyclohexylmethyl methacrylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) -1, Hard coating composition selected from the group consisting of 3-dioxolane and combinations thereof.
17. The monomer according to claim 14, wherein the monomer having an oxetane group is 3-methyloxetane, 2-methyloxetane, 3-oxetanol, 2-methyleneoxetane, 3,3-oxetane dimethane thiol, 4- (3-methyloxetan-3-yl) benzonitrile,-(2,2-dimethylpropyl) -3-methyl-3-oxetanemethaneamine, N- (1,2-dimethylbutyl) -3-methyl -3-oxetanemethaneamine, (3-ethyloxetan-3-yl) methylmethacrylate, and 4-[(3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3- Ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, xylylene bis oxetane, 3-ethyl-3 [[[3-ethyloxetan-3-yl] methoxy] methyl] oxetane and these Hard coating composition selected from the group consisting of.
18. The method of claim 13, wherein the hard coating composition is a solvent, a polymerization initiator, a photosensitizer, a photosensitizer, a polymerization inhibitor, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, a ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupler. A hard coating composition further comprising at least one component selected from the group consisting of a ring agent, an inorganic filler, an antifoaming agent, and an antifouling agent.
19. materials;

    The hard coating layer formed on the said base material and consisting of hardened | cured material of the hard coat composition of any one of Claims 12-18.

    Hard coating film for a display device comprising a.
20. 20. The method of claim 19, wherein the substrate is polyester resin, cellulose resin, polycarbonate resin, acrylic resin, styrene resin, polyolefin resin, polyimide resin, polyether sulfone resin, sulfone resin and these Hard coating film made of a material selected from the group consisting of a copolymer of.
21. Display panel; And

    A display device, located on one surface of the display panel, comprising the hard coating film of claim 19.

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