KR101965682B1 - Siloxane oligomer having organic metal, process of fabricating siloxane olgomer, hadr coating compostiton containing siloxane oligomer, hard coating flim and display device - Google Patents

Abstract

The present invention relates to a siloxane oligomer obtained by conducting a reaction of three kinds of different siloxane monomers with organic metals, a method for manufacturing the same, a hard coating composition containing the siloxane oligomer, a hard coating film, and a display device which are cured products of the hard coating composition. The hard coat film made of cured products of the siloxane oligomer according to the present invention has excellent physical properties such as scratch resistance and the like. Therefore, 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, thereby realizing the display device having excellent physical properties.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a siloxane oligomer having an organic metal, a method for producing a siloxane oligomer, a hardcoat composition including a siloxane oligomer, a hardcoat film, and a display device using the siloxane oligomer. FLIM AND DISPLAY DEVICE}

The present invention relates to a siloxane oligomer, and more particularly, to a siloxane oligomer containing an organic metal and having improved physical properties, a process for producing the siloxane oligomer, a hardcoat composition, a hardcoat film and a display device.

BACKGROUND ART [0002] Recently, with the development of information communication technology and display technology, a display device for processing and displaying a large amount of information is rapidly developing. Accordingly, a flat panel display device typified by a liquid crystal display device (LCD) or an organic light emitting diode (OLED) display device has been widely used for a TV, a computer monitor, a mobile phone screen, and the like. In recent years, a touch-type display device that allows the user to operate the display screen by touching the panel has become widespread.

The touch-type display device commonly touches the outermost-outer surface of the display device using a user or a touch-pen. Therefore, the outermost surface of the touch-type display device adopts an optical film such as a hard coating film because it needs to control the light incident on the display device and have a certain degree of hardness.

Conventionally, tempered glass is used for a hard coating film applied to a display device. However, since tempered glass has very low elasticity, the tempered glass may be broken even with slight bending. Especially when applied to a flexible or foldable display device, the problem of breaking the hard coating film made of tempered glass becomes more serious. A plastic cover such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI) has 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 are insufficient in impact resistance, and the surface hardness and scratch resistance are lower than those of tempered glass.

Thus, a hard coat film made of a polymer binder instead of tempered glass has been proposed. The polymeric binder may be added with a polymerization initiator in the form of a monomer or an oligomer in the form of a monomer or oligomer, and a polymer is formed by applying heat or irradiating ultraviolet rays to impart hard coatability.

The hard coating film located on the surface of the conventional display device has insufficient physical properties such as impact resistance and surface strength. Various methods have been proposed for solving insufficient physical properties of a hard coating film made of a binder resin. For example, International Publication WO 2013/187699 proposes a high hardness siloxane resin composition comprising an alicyclic epoxy group, a process for producing the same, and an optical film containing the cured product. The optical film according to the international patent has achieved a high hardness of 9H, but with the use of a single monomer and a cationic initiator, there is still a problem that weatherability may be a problem and curling may occur. Therefore, there is a need to develop a hard coating film having improved durability so that it can 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 process for producing the siloxane oligomer, a hard coating composition containing the same, and a hard coating film and a display device produced therefrom.

According to an aspect of the present invention, there is provided 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

Wherein R ¹ is selected from the group consisting of a glycidoxy group, a glycidoxy group-containing functional group, an alicyclic epoxy group and an alicyclic epoxy group-containing functional group, R ² is an unsubstituted or substituted C ₁ to C ₁₀ alkylene group or An unsubstituted or substituted C ₅ -C ₃₀ arylene group wherein the alkylene group and the substituent which may be substituted in the arylene group are C ₁ -C ₃₀ linear or branched alkyl groups, C ₁ -C ₂₀ alkoxy groups, amino groups, acrylic groups A carboxyl group, a vinyl group, a nitro group, a sulfone group, a hydroxyl group, a C ₃ -C ₈ cycloalkyl group, an alkyd group, a urethane group, a carboxyl group, M is aluminum, titanium, zirconium, zinc and mixtures thereof; oxetane group, C ₅ ~ C ₃₀ aryl group, C ₅ ~ C ₃₀ aryl group, C ₅ ~ C ₃₀ aryloxy group and selected from the group consisting of a combination of A metal selected from the group consisting of combinations of Acac is an acetylacetone ligand unsubstituted or substituted with a C ₁ -C ₁₀ linear or branched alkyl group, 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 an exemplary embodiment, 0.32? X? 0.919, 0.04? Y? 0.32, 0.04? Z? 0.32, 0.001? M? 0.04 in the formula 1 and x + y + z + m = 1.

Preferably, 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 in the above formula (1).

Illustratively, in the above formula (1), R ¹ is selected from the group consisting of a gamma-glycidoxin period, a gamma-glycidoxime-containing functional group, a 2- (3,4-epoxycyclohexyl group) Containing group-containing alicyclic epoxy group.

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

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

According to another aspect of the present invention, there is provided a process for preparing a siloxane oligomer represented by the following general formula (1), comprising a first siloxane monomer represented by the following general formula (2), a second siloxane monomer represented by the general formula And reacting a third siloxane monomer represented by the following formula (5) with an organometallic compound represented by the following 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

(2)

R ¹ Si (OR ³ ) _a (R ⁴ ) _b

(3)

Si (OR ⁵⁾ ₄

Formula 4

_{^{(Si (OR 6) 3 -R}} 2 -Si (OR 7) 3) z

Formula 5

(M (acac) _o )

Wherein R ¹ is selected from the group consisting of a glycidoxy group, a glycidoxy group-containing functional group, an alicyclic epoxy group and an alicyclic epoxy group-containing functional group, R ² in the formulas (1) and (4) a C ₁ ~ a C ₁₀ alkyl group or unsubstituted or substituted C ₅ ~ C ₃₀ aryl group, a substituent may be substituted to said arylene wherein the alkylene group is C ₁ ~ C ₃₀ straight or branched alkyl group, C ₁ ~ C ₂₀ alkoxy group, an amino group, an acrylic group, a methacrylic group, a halogen, mercapto group, an allyl group, an ether group, an ester group, a carbonyl group, a carboxyl group, a vinyl group, a nitro group, an alcohol peongi, hydroxyl group, C ₃ ~ C ₈ A cycloalkyl group, an alkyd group, a urethane group, an oxetane group, a C ₅ to C ₃₀ aryl group, a C ₅ to C ₃₀ arylalkyl group, a C ₅ to C ₃₀ aryloxy group, and combinations thereof; And M is at least one element selected from the group consisting of aluminum, titanium, zirconium Acac is an acetylacetone ligand which is unsubstituted or substituted by a C ₁ -C ₁₀ linear or branched alkyl group, o is an integer of 2 to 4, a is an integer from 2 to 3 in the formula (2); at R ^3, and R ^4, R ^5, R ⁶ and R ⁷ are each independently a straight-chain or C ₁ ~ C ₁₀ alkyl group of the side chain in the formula (5) in the formula (3) b is an integer of 0 or 1 and a + b = 3 in the formula 1, 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 hydrolysis condensation reaction under acid catalyst or base catalyst in the reaction step.

In one exemplary embodiment, the first siloxane monomer represented by Formula 2 is at least one selected from the group consisting of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethacrylate (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, and combinations thereof.

The second siloxane monomer represented by the general formula (3) may be at least one selected from the group consisting of tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetrabutyl orthosilicate And a linear or branched C ₁ -C ₄ tetraalkylorthosilicate selected from the group consisting of combinations thereof.

The third siloxane monomer represented by the general formula (4) may be 1,2-bis (triethoxysilyl) ethane, 1,2-bis (trimethoxysilyl) (1,2-bis (trimethoxysilyl) ethane), 1,6-bis (triethoxysilyl) hexane and 1,6-bis (trimethoxysilyl) Bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) octane, 1,8-bis (trimethoxysilyl) bis (trimethoxysilyl) octane, 1,4-bis (triethoxysilyl) benzene, and combinations thereof.

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

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

The crosslinking agent may be selected from the group consisting of a chain type 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 chain type aliphatic epoxy monomer may be 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl Ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of polyether polyol, diglycidyl esters of aliphatic dibasic acid; Monoglycidyl ethers of aliphatic alcohols, glycidyl ethers of fatty acids; Epoxidized soybean oil. Epoxy stearate, octyl stearate, epoxidized linseed oil, epoxidized polybutadiene, and combinations thereof.

The cyclic aliphatic epoxy monomer may be selected from the group consisting of 4-vinylcyclohexene dioxide, cyclohexene vinyl monoxide, (3,4-epoxycyclohexyl) methyl, 3,4-epoxycyclohexylcarboxylate, (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) -1,3-dioxolane and And a combination thereof.

On the other hand, the oxetane group-containing monomer may be at least one selected from the group consisting of 3-methyloxetane, 2-methyloxetane, 3-oxetanole, 2-methylene oxetane, (2, 2-dimethylpropyl) -3-methyl-3-oxetanemethanamine, N- (1,2-dimethylbutyl) (3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyl-3- 3-ethyl [3-ethyloxetane-3-yl] methoxy] methyl] oxetane, and combinations thereof. ≪ / RTI >

Alternatively, the hard-coating composition may comprise a solvent, a polymerization initiator, a photosensitizer, a photosensitizer, a polymerization inhibitor, a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, A silane coupling agent, an inorganic filler, a defoaming agent, and an antifouling agent.

According to another aspect of the present invention, There is provided a hard coat film formed on the substrate and including a hard coat layer comprising a cured product of the hard coat composition described above.

For example, the above-mentioned substrate may be formed of a resin such as a polyester resin, a cellulose resin, a polycarbonate resin, an acrylic resin, a styrene resin, a polyolefin resin, a polyimide resin, a polyether sulfone resin, Or a combination of two or more materials.

According to another aspect of the present invention, there is provided a display panel comprising: a display panel; And a hard coating film disposed on one side of the display panel.

The present invention provides a hard coating composition comprising the siloxane oligomer prepared by reacting three different siloxane monomers with an organometallic compound and the siloxane oligomer, a hard coating film and a display device which is a cured product of the composition.

The organometallic compound is chemically bonded to the silane siloxane, and contains a metal atom in the molecular structure, so that the intermolecular space can be further secured. Thus, the curling phenomenon can be remarkably reduced by minimizing the hardening shrinkage. The hard coat film to which the siloxane oligomer according to the present invention is applied has improved physical properties such as flexibility and scratch resistance, and can be utilized as an optical film of a display device.

1 is a cross-sectional view schematically showing a hard coating film according to an exemplary embodiment of the present invention.
2 is a cross-sectional view schematically showing a display device in which a hard coating film according to an exemplary embodiment of the present invention is applied to a cover window.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings where necessary.

[Siloxane oligomer and production method thereof]

In the hard coating layer made of the binder material, when the hardness of the hard coating layer is improved by increasing the surface hardness of the intermolecular layer, the shrinkability is increased and the flexibility is lowered, and curl phenomenon and hardness, A crack phenomenon occurs in which a part of the coating layer is broken. On the other hand, if the flexibility of the hard coat layer is increased, the curling phenomenon and the cracking phenomenon can be solved, but the surface hardness is lowered. Therefore, the development of a high hardness coating material having excellent flexibility, no curling, and easiness of processing is also an urgent necessity for wider use of the polymer film.

One of the commonly used coating agents for hard coatings is a light or thermosetting coating. The photocurable coating agent can be cured in a short time and can be cured at room temperature, and is used as a surface protective coating for various plastic products. In order for such a coating material to be usefully used for optical purposes, it should have good adhesion to a film along with hardness, and should not have a curling phenomenon or a rainbow phenomenon.

In particular, when a curl phenomenon occurs, it can act as a serious disadvantage in the progress of the mass-production roll-to-roll process, and it is a particularly required property since it may cause problems in future durability even after it is provided as a product. In addition, the display industry is shifting to the flexible display era, which requires hard-coated films with excellent flexibility.

In order to solve these problems, the present invention provides a siloxane oligomer obtained by reacting three different siloxane monomers with an organic metal. Other siloxane oligomers according to one aspect of the present invention may be 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

Wherein R ¹ is selected from the group consisting of a glycidoxy group, a glycidoxy group-containing functional group, an alicyclic epoxy group and an alicyclic epoxy group-containing functional group, R ² is an unsubstituted or substituted C ₁ to C ₁₀ alkylene group or An unsubstituted or substituted C ₅ -C ₃₀ arylene group wherein the alkylene group and the substituent which may be substituted in the arylene group are C ₁ -C ₃₀ linear or branched alkyl groups, C ₁ -C ₂₀ alkoxy groups, amino groups, acrylic groups A carboxyl group, a vinyl group, a nitro group, a sulfone group, a hydroxyl group, a C ₃ -C ₈ cycloalkyl group, an alkyd group, a urethane group, a carboxyl group, M is aluminum, titanium, zirconium, zinc and mixtures thereof; oxetane group, C ₅ ~ C ₃₀ aryl group, C ₅ ~ C ₃₀ aryl group, C ₅ ~ C ₃₀ aryloxy group and selected from the group consisting of a combination of A metal selected from the group consisting of combinations of Acac is an acetylacetone ligand unsubstituted or substituted with a C ₁ -C ₁₀ linear or branched alkyl group, 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 the formula ¹ (R 1 SiO _3/2) a moiety that, sidok glycidyl group, a glycidyl group-containing functional group sidok, an alicyclic epoxy group and / or an alicyclic epoxy group-containing functional group of R ¹ derived from the first siloxane monomer to be described later Have. Since it has an epoxy group such as a glycidoxy group or an alicyclic epoxy group, excellent surface hardness and low curing shrinkage can be achieved, thereby preventing the curling phenomenon.

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

Among the siloxane oligomers represented by the formula (1), x, which is the molar 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, Is 0.43? X? 0.839. When the molar fraction x of the (R ¹ SiO _3/2 ) moiety having an epoxy group satisfies the above-mentioned range, it is possible to obtain a siloxane oligomer having an excellent surface hardness and a low hardening shrinkage ratio.

The (SiO _4/2 ) moiety in formula (1) is derived from the second siloxane monomer described below, and the (SiO _3/2 -R ² -SiO _3/2 ) moiety is derived from the third siloxane monomer described below. The flexibility of the siloxane oligomer represented by the general formula (1) including these components can be improved. For this purpose, the mole fraction y of the (SiO _4/2 ) moiety in the siloxane oligomer represented by the general formula (1) is 0.01? Y? 0.35, preferably 0.04? Y? 0.32, more preferably 0.08? Y? 0.27 , The molar fraction z of the (SiO _3/ ^2- R ² -SiO _3/2 ) moiety in the siloxane oligomer represented by the general formula (1) is 0.01 ≦ z ≦ 0.35, preferably 0.04 ≦ z ≦ 0.32, more preferably 0.08 ≦ z? 0.27.

In one exemplary embodiment, the (C ₁ -C ₁₀₎ alkylene group or the C ₅ -C ₃₀ arylene group constituting R ² of the (SiO _3/ ^2- R ² -SiO _3/2 ) The substituent is a C ₁ to C ₃₀ straight chain or branched alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like; A C ₁ -C ₂₀ alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group; An amino group; Acrylic group; A methacryl group; Halogen such as fluoro, bromo, and chlorine; A mercapto group; Allyl group; Ether group; An ester group; Carbonyl group; A carboxyl group; Vinyl group; A nitro group; Sulphon; A hydroxyl group; A C ₃ -C ₈ cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; An alkyd group; Urethane group, oxetane group; A phenyl group, a biphenyl group, a terphenyl group, a tetraphenyl group, a naphthyl group, an anthracenyl group, an indenyl group, a phenalenyl group, a phenanthrenyl group, an azulenyl group, a pyrenyl group, a fluorenyl group, a tetracenyl group, An aryl group such as a phenyl group, a naphthyl group, an naphthyl group, an naphthyl group, an naphthyl group, an naphthyl group, an naphthyl group, an naphthyl group, , Benzocarbazolyl group, dibenzocarbazolyl group, indolocarbazolyl group, indenocarbazolyl group, benzofuranocarbazolyl group, benzothienocarbazolyl group, quinolinyl group, isoquinolinyl group, phthalazinyl group A quinazolinyl group, a benzoquinolinyl group, a benzoquinazolinyl group, a benzoquinazolinyl group, a benzoquinazolinyl group, a benzoquinazolinyl group, a benzoquinazolinyl group, a quinazolinyl group, An acridinyl group, a phenanthrolinyl group, a furan Thiazolyl group, thiazolyl group, dioxinyl group, benzofuranyl group, dibenzofuranyl group, thiopyranyl group, thiazinyl group, thiophenyl group, or N- A C ₅ -C ₃₀ aryl group such as a non-condensed or condensed heteroaryl group such as a substituted spirobifluorenyl group; C ₅ ~ C ₃₀ aryl group; ₅ ~ C can be selected from the group consisting of C ₃₀ aryloxy group, and combinations thereof.

The siloxane oligomer according to the present invention includes an organometallic moiety defined as (M (acac) _o ). Organometallic can be included to ensure a space between molecular structures, The mole fraction m of the organic metal (M (acac) moiety) is 0.001? M? 0.05, preferably 0.001? M? 0.04, more preferably 0.001 Lt; m < 0.03.

In one exemplary embodiment, the organometallic component (M (acac) _o ) is selected from the group consisting of aluminum acetylacetone, titanium acetylacetone, titanium ethyl acetylacetone, zirconium monoacetylacetone, zirconium tetraacetylacetone, For example, these organic metals may be selected from the group consisting of metal alkylenes (e.g., C ₁ -C ₁₀ alkylene such as ethylene / octylene) glycolates, metal lactic acid ammonium salts, metal Trialkanolamines, trialkanolamines and the like, but the present invention is not limited thereto.

In one exemplary embodiment, the weight average molecular weight of the siloxane oligomer of Formula 1 may range from 1,000 to 100,000, preferably from 1,000 to 50,000, and more preferably from 1,500 to 20,000. When the weight average molecular weight of the siloxane oligomer satisfies the above-mentioned range, it is possible to secure high flexibility, low curing shrinkage, high surface hardness and excellent processing characteristics.

Next, a method for producing the siloxane oligomer represented by the formula (1) will be described. According to another aspect of the present invention, there is provided a process for preparing a siloxane oligomer represented by the following general formula (1), comprising a first siloxane monomer represented by the following general formula (2), a second siloxane monomer represented by the general formula And reacting a third siloxane monomer represented by the following formula (5) with an organometallic compound represented by the following 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

(2)

R ¹ Si (OR ³ ) _a (R ⁴ ) _b

(3)

Si (OR ⁵⁾ ₄

Formula 4

_{^{(Si (OR 6) 3 -R}} 2 -Si (OR 7) 3) z

Formula 5

(M (acac) _o )

Wherein R ¹ is selected from the group consisting of a glycidoxy group, a glycidoxy group-containing functional group, an alicyclic epoxy group and an alicyclic epoxy group-containing functional group, R ² in the formulas (1) and (4) a C ₁ ~ a C ₁₀ alkyl group or unsubstituted or substituted C ₅ ~ C ₃₀ aryl group, a substituent may be substituted to said arylene wherein the alkylene group is C ₁ ~ C ₃₀ straight or branched alkyl group, C ₁ ~ C ₂₀ alkoxy group, an amino group, an acrylic group, a methacrylic group, a halogen, mercapto group, an allyl group, an ether group, an ester group, a carbonyl group, a carboxyl group, a vinyl group, a nitro group, an alcohol peongi, hydroxyl group, C ₃ ~ C ₈ A cycloalkyl group, an alkyd group, a urethane group, an oxetane group, a C ₅ to C ₃₀ aryl group, a C ₅ to C ₃₀ arylalkyl group, a C ₅ to C ₃₀ aryloxy group, and combinations thereof; And M is at least one element selected from the group consisting of aluminum, titanium, zirconium Acac is an acetylacetone ligand which is unsubstituted or substituted by a C ₁ -C ₁₀ linear or branched alkyl group, o is an integer of 2 to 4, a is an integer from 2 to 3 in the formula (2); at R ^3, and R ^4, R ^5, R ⁶ and R ⁷ are each independently a straight-chain or C ₁ ~ C ₁₀ alkyl group of the side chain in the formula (5) in the formula (3) b is an integer of 0 or 1 and a + b = 3 in the formula 1, 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 represented by the formula (2), which is a siloxane monomer having an epoxy group, an excellent surface hardness and a low curing shrinkage ratio of the siloxane oligomer represented by the formula (1) can be secured. On the other hand, 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). Further, by using the organometallic compound represented by the formula (5), the intermolecular spacing of the siloxane oligomer represented by the formula (1) can be further secured to improve flexibility and processing characteristics.

In one exemplary embodiment, the first siloxane monomer represented by Formula 2 is selected from the group consisting of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- , 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 general formula (3) includes straight or branched C ₁ -C ₄ tetraalkyl orthosilicates. Such tetraalkyl orthosilicates may be selected from the group consisting of tetramethyl orthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetrabutyl orthosilicate, and combinations thereof Group, but the present invention is not limited thereto.

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

In order to prepare the siloxane oligomer represented by the general formula (1), the three different siloxane monomers represented by the general formulas (2) to (4), the acidic catalyst or the basic catalyst capable of promoting the hydrolysis and condensation reaction of the organometal represented by the general formula Can be used. In order to accelerate the reaction, stirring may be carried out at 50 to 120 ° C for 1 to 120 hours.

Specific catalysts capable of accelerating the hydrolysis and condensation reaction of the three different siloxane monomers and the organic metal include acid catalysts such as hydrochloric acid, acetic acid, hydrogen fluoride, nitric acid, and sulfuric acid iodic acid, ammonia, potassium hydroxide, sodium hydroxide, , Imidazole and the like, and an ion exchange resin such as Amberite. These catalysts may be used alone or in combination. The amount of the catalyst is not particularly limited, but about 0.0001 to about 10 parts by weight may be added based on 100 parts by weight of the total components of the siloxane monomer and the organic metal represented by the above-mentioned formulas (2) to (5).

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

The present invention also provides a hard coating composition comprising a siloxane oligomer represented by the above-mentioned formula (1), a hard coating film containing a cured product of the hard coating composition, and a display device wherein the hard coating film is applied as an optical film.

The hard coating film contains a siloxane oligomer represented by the general formula (1) as an essential component and, if necessary, a crosslinking agent, a polymerization initiator, a solvent, a surfactant, a leveling agent, an antioxidant and the like.

The cross-linker for promoting crosslinking of the siloxane oligomer includes, but is not limited to, at least one of a chain aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated aromatic hydrocarbon epoxy monomer, and an oxetane monomer And these may be included singly or in combination.

Chain aliphatic epoxy monomers include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol But are not limited to, neopentylglycoldiglycidyl ether, trimethylolpropane triglycidyl ether, polyethyleneglycol diglycidylether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ether, Polypropyleneglycol diglycidyl ether; Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Diglycidyl esters of aliphatic long chain (C ₅ -C ₂₀ ) dibasic acids; Monoglycidyl ethers of aliphatic higher alcohols (C ₅ -C ₃₀ ); Glycidyl ethers of higher fatty acids (C ₅ -C ₃₀ ); Epoxidized soybean oil; Butyl stearate; Octyl stearate; Epoxidized linseed oil; Epoxidized polybutadiene, and the like, but the present invention is not limited thereto.

The cyclic aliphatic epoxy monomer is a compound having at least one epoxy group in the alicyclic group, and may specifically include an alicyclic epoxy carboxylate, an alicyclic epoxy (meth) acrylate, and the like.

More specifically, the cyclic aliphatic epoxy monomer is (3,4-epoxycyclohexyl) methyl-3 ', 4'-epoxycyclohexyl methyl-3', 4'-epoxycyclohexanecarboxylate, , Diglycidyl 1,2-cyclohexanedicarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metha-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate 4-epoxycyclohexylmethyl adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclo 4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (? -Caprolact epoxycyclohexylmethyl-3 ', 4'-epoxy-cyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate -3 ', 4'-epoxy-cyclohexanecarboxylate), β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate (β- valerolactonemodified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate) ), Ethylene (3,4-epoxycyclohexylmethyl) ether, and ethylene bis (3,4-epoxycyclohexanecarboxylate) (ethylenebis (3, 4-epoxycyclohexanecarboxylate), 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) ate, bis (3,4-epoxycyclohexylmethyl) adipate, 4-vinylcyclohexene dioxide, vinylcyclohexene monoxide vinylcyclohexen monoxide), and the like, but the present invention is not limited thereto.

The hydrogenated aromatic hydrocarbon epoxy monomer means a compound obtained by selectively hydrogenating an aromatic epoxy monomer under a pressure in the presence of a catalyst. Aromatic epoxy monomers include, for example, bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S and the like; Novolak type epoxy resins such as phenol novolak epoxy resin, cresol novolak epoxy resin, and hydroxybenzaldehyde phenol novolak epoxy resin; And polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxylated polyvinyl phenol. However, the present invention is not limited thereto. It does not.

On the other hand, the oxetane group-containing monomers include 3-methyloxetane, 2-methyloxetane, 3-oxethanol, 2-methylene oxetane, (2,2-dimethylpropyl) -3-methyl-3-oxetanemethanamine, N- (1,2-dimethylbutyl) -3-methyl- (3-ethyloxetan-3-yl) methyl methacrylate, and 4 - [(3-ethyloxetan-3- yl) methoxy] butan- Ethyloxycarbonyloxyethyl, xylylene bisoxetane, 3-ethyl-3 [[[3-ethyloxetan-3-yl] methoxy] methyl] oxetane, and combinations thereof Group, but the present invention is not limited thereto.

The crosslinking agent may be contained in an amount of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the siloxane oligomer represented by the formula (1) which is cured with a siloxane resin. When the content of the cross-linking agent satisfies the above-described range, physical properties such as hardness, flexibility and scratch resistance of the hard coat film to be produced can be improved.

On the other hand, the hard coating composition may further comprise 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 comprises a suitable solvent capable of dispersing the solid components, such as the siloxane oligomers described above. As the solvent, an organic solvent may be suitable. The organic solvent is preferably a polar, non-polar and / or aprotic solvent. In one example, the organic solvent is selected from the group consisting of C ₁ -C ₆ aliphatic alcohols, especially lower alcohols such as methanol, ethanol and 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 butane; Esters such as ethyl acetate; Ethers such as diethyl ether, tetrahydrofuran and tetrahydropyran; Amides such as dimethylacetamide and dimethylformamide; Sulfoxides and sulfones such as sulfolane and dimethyl sulfoxide; Aliphatic (even 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. For example, the solvent preferably has a boiling point of 200 占 폚 or lower, particularly 150 占 폚 or lower. The exemplified solvents may be included in the hard coating composition in a ratio of 50 to 95 parts by weight. When the content of the solvent is less than 50 parts by weight, the viscosity is high and the coating of the thin film is difficult. When the amount of the solvent is more than 95 parts by weight, the curing process takes a long time.

The hard coating composition may comprise a polymerization initiator. As the polymerization initiator, a photo radical polymerization initiator, a photo polymerization initiator, a thermal polymerization initiator and the like may be used, and these may be used singly or in combination of two or more. It is preferably a photopolymerization initiator.

Examples of the photoradical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2'-dimethoxy-2-phenylacetophenone, xanthone, fluorene, fluorenone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methyl acetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, mihira ketone, benzoyl propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1 2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl 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) -Hydroxy-2-methylpropan-1-one, and the like. Products currently on the market 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.

As the photopolymerization initiator, a photopolymerization initiator may be used. As the initiator of the cationic ion polymerization, for example, an onium salt and / or an organic metal salt may be used, but the present invention is not limited thereto. For example, a diaryl iodonium salt, a triarylsulfonium salt, an aryldiazonium salt, an iron-arene complex, and the like can be used as a photopolymerization initiator.

As a more specific example, the photocationic polymerization initiator may be an arylsulfonium hexafluoroantimonium salt, an arylsulfonium hexafluorophosphate salt, a diphenyliodonium hexafluoroantimonium salt, a diphenyliodonium salt, (4-hydroxyethoxyphenyl) cyan sulium hexafluorophosphate salt, and the like, and the antimony salt may contain at least one compound selected from the group consisting of Since there is a contamination problem, hexafluorophosphate salt-based initiators are more preferred. These may be used alone or in combination of two or more.

Examples of the thermal polymerization initiator include 3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate salt, ytterbium triplomethanesulfonate salt, samarium triflumromethanesulfonate salt, erbium triflate Tetrabutylphosphonium methanesulfonate salts, ethyltriphenylphosphonium bromide salts, benzyldimethylamine salts, benzyldimethylamine salts, benzyldimethylamine salts, benzyldimethylamine salts, Dimethylaminomethylphenol, triethanolamine, N-butylimidazole, 2-ethyl-4-methylimidazole and the like can be used. These may be used alone or in combination of two or more.

In one exemplary embodiment, the cationic polymerization initiator may be any of those known in the art as acids or bases of Bronsted-Lowry or acids capable of generating acids according to the Lewis acid / base definitions, without limitation have. For example, the cationic polymerization initiator may be selected from the group consisting of 3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate salt, ytterbium (III) triplomethanesulfonate salt, samarium (III) Tetrabutylammonium salts, triarylsulfonium hexafluorophosphate salts, lanthanum (III) trifluoromethanesulfonate salts, tetrabutylammonium salts, tetrabutylammonium salts, tetrabutylammonium salts, Phosphonium methanesulfonate salts, ethyltriphenylphosphonium bromide salts, diphenyliodonium hexafluoroantimonate salts, diphenyliodonium hexafluorophosphate salts, ditolyl iodonium hexafluorophosphate (3-methylbut-2-enyl) tetrahydro-1H-thiophenium hexafluoroantimonate (hereinafter referred to as " Made of salt May include one or more selected from, but are not limited to,

The anionic polymerization initiator may include, but is not limited to, a tertiary amine or imidazole. For example, the anionic polymerization initiator may be selected from the group consisting of ο- (dimethylaminomethyl) phenol, tris- (dimethylaminomethyl) phenol, benzyldimethylamine, α-methylbenzyldimethylamine, But are not limited to, at least one selected from the group consisting of amino acids,

The content of the polymerization initiator in the hard coating composition according to the present invention is not particularly limited and is, for example, 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the siloxane oligomer represented by the formula (1) By weight. When the content of the polymerization initiator is within the above range, the curing efficiency of the hard coating composition can be kept excellent, and deterioration of the physical properties of the hard coating film due to the remaining components after curing can be prevented.

In addition, the hard coating composition according to the present invention may further contain at least one of a photosensitizer, a photosensitizer, a polymerization inhibitor, a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, And at least one functional additive selected from the group consisting of antioxidants.

For example, the leveling agent may be selected from the group consisting of an acrylic leveling agent, a silicon leveling agent, a fluorine leveling agent, a silicon-acrylate copolymer leveling agent, a fluorine-modified acrylic leveling agent, a fluorine-modified silicone leveling agent, A leveling agent into which a group such as a methoxy group or an ethoxy group, an acyloxy group, a halogen group, an amino group, a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group or an isocyanate group is introduced and a combination thereof Can be selected.

The content of these functional additives is not particularly limited as long as the properties of the hard coating film of the present invention can be controlled within a range that does not impair the physical properties. For example, 100 parts by weight of a siloxane oligomer represented by the formula (1) , Preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the total composition.

Next, a hard coating film and a display device manufactured using the composition for hard coating according to the present invention will be described. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view of a hard coat film made from a composition for hard coating according to an exemplary embodiment of the present invention. Fig. 1, the hard coating film 100 includes a substrate 110, and a hard coating layer 120 stacked on top of the substrate 110. The hard coating layer 120 may include a hard coat layer 120,

The substrate 110 is preferably excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, and the like. For example, the substrate 100 may be a polyester resin such as polyethylene terephthalate, polyethylene isophthalate, or polybutylene terephthalate; Cellulose-based resins such as diacetylcellulose and triacetylcellulose; Polycarbonate resin; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene-based resins such as polystyrene acrylonitrile-styrene copolymer; Polyolefin resins such as polyolefin resins having polyethylene, polypropylene, cyclo or norbornene structure, and ethylene propylene copolymers; Polyimide resin; Polyether sulfone type resin; Sulfone based resin; And copolymers thereof, and the like. The thickness of the substrate 110 is not particularly limited, and may be, for example, 10 to 3000 占 퐉.

The hard coat layer 120 includes the siloxane oligomer represented by the formula (1), and can be obtained from the above-mentioned hard coat composition including a cross-linking agent, a solvent, a polymerization initiator, a functional additive, and the like if necessary. For example, the hard coat layer 120 may be formed by coating a suitable hard coat composition containing a siloxane oligomer represented by the formula (1) on an appropriate substrate 110, followed by drying, polymerization, and the like.

When the composition for hard coating described above is coated on the substrate 110, the coating method is not particularly limited. For example, it is possible to coat the composition for hard coating by an appropriate method such as die coater, air knife, reverse roll, spray, blade, casting, gravure, microgravure or spin coating.

For example, the above-mentioned hard coating composition may be coated on the substrate 110 and then dried at a temperature of 30 to 150 ° C, for example, 30 to 100 ° C for 10 seconds to 1 hour, more preferably 30 seconds to 30 minutes The volatiles are evaporated to dryness (soft baking). And then cured by irradiating UV light. The irradiation amount of the UV light may be 0.01 to 10 J / cm 2, preferably 0.1 to 2 J / cm 2. If necessary, it can be cured or aged (hard baking) for 30 minutes to 48 hours at a temperature of 30 to 150 ° C, for example 40 to 120 ° C, after UV irradiation. The hard coating layer 120 may be formed on the substrate 110 through such a process. The thickness of the hard coat layer 120 is not particularly limited, and may be, for example, 0.05 to 100 占 퐉, preferably 0.5 to 50 占 퐉. Since the hard coating layer 120 has a siloxane resin which is a cured product of the siloxane oligomer represented by the general formula (1), the flexibility, surface hardness and scratch resistance of the hard coating film 100 are improved, and the curling phenomenon And the like can be prevented.

As described above, the hard coating film 100 according to the present invention is excellent in hardness, scratch resistance, abrasion resistance and chemical resistance. Therefore, the hard coating film 100 of the present invention can be applied to an optical film, for example, a window film such as a cover window, for which a hardness characteristic and the like are required in a display device. 2 is a cross-sectional view schematically showing a display device 200 to which a cover window 100 made of a hard coating 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 side of the display panel 210 displaying an image, and protects the display panel 210. For example, the cover window 100 made of a hard coating film according to the present invention can prevent damage due to an external impact and damage caused by scratches, thereby preventing the display device 200 having a flexible or foldable property, .

The display device 200 includes a display panel 210, a back cover 230 in which the display panel 210 is housed, a cover window 230 coupled with the back cover 230 from the front surface of the display panel 210, 100). The display panel 210 may be a liquid crystal display panel, an organic light emitting diode (OLED) device, or 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) located below the liquid crystal panel, A bottom frame connected to the main frame from the rear surface of the backlight unit, and a top frame covering the front edge of the liquid crystal panel. The back cover 230 covers the back surface of the display panel 210 and includes a space in which the display panel 210 is housed.

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 an external contact is made. An adhesive layer 220 such as an optically clear adhesive (OCA) may be interposed between the cover window 100 and the display panel 210 so that the cover window 100 and the display panel 210 can be adhered to each other. have. The cover window 100 is formed of the hard coating film according to the present invention and is excellent in physical properties such as flexibility, impact resistance, surface hardness and scratch resistance. Therefore, the damage or breakage of the cover window 100 can be minimized by the user's contact or external pressure.

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

Example 1: Preparation of an epoxy siloxane oligomer

155.22 g of glycidoxypropyltrimethoxysilane, 2.13 g of tetraethoxysilane and 3.6 g of 1,2-bis (triethoxysilyl) ethane were mixed and placed in a 300-mL three-necked flask. After 160.2 g of methanol was added, 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, and then 41.9 g of water was slowly added dropwise over 30 minutes, followed by reaction at 60 ° C for 12 hours. The reaction product was distilled under reduced pressure to remove methanol to prepare a siloxane oligomer.

Examples 2 to 23: Preparation of oligosaccharide epoxysiloxane oligomer

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

Examples 24 to 26: Preparation of siloxane oligomer mixed with glycidoxy epoxy and alicyclic epoxy

Starting materials such as glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane are shown in the following table 1, the procedure of Example 1 was followed to prepare a siloxane oligomer.

Example 27: 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 1 below, The procedure of Example 1 was followed to prepare a siloxane oligomer.

Comparative Example 1: Preparation of oligosaccharide epoxysiloxane oligomer

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

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

Starting materials such as glycidoxypropyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane were introduced in the amounts shown in Table 2 below, and the same procedures as in Comparative Example 1 were carried out 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 glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane are shown in the following table The siloxane oligomer was prepared in the same manner as in Comparative Example 1, except that the amount of the siloxane oligomer was changed.

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 amounts as shown in Table 2 below The procedure of Comparative Example 1 was followed to prepare a siloxane oligomer.

Comparative Examples 15 to 16: Preparation of oligosaccharide epoxysiloxane oligomer

And the starting materials such as glycidoxypropyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane are added as shown in Table 2 below And the same procedure as in Comparative Example 1 was carried out to prepare a siloxane oligomer.

Comparative Examples 17 to 19: Preparation of epoxy siloxane oligomer at glycidoxine

And the starting materials such as glycidoxypropyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane are introduced into the reactor as shown in Table 2 below The siloxane oligomer was prepared in the same manner as in Comparative Example 1, and a siloxane oligomer was prepared.

Comparative Examples 20 to 21: Preparation of glycidoxy epoxysiloxane oligomer

And adding tetraisopropyl titanate,

Starting materials such as glycidoxypropyltrimethoxysilane, tetraethoxysilane and 1,2-bis (triethoxysilyl) ethane were introduced in the amounts shown in Table 2 below, and the same procedures as in Comparative Example 1 were carried out 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 (R ¹ SiO _3/2 ) (SiO4 / ₂ ) (SiO _3/ ^2- R ² -SiO _3/2 (M (acac) _o ) A (mole fraction) B (mole fraction) C (molar 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) 66.072g
(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) 185.7g
(0.320) 316.1 g
(0.320) 0.920g
(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) 33.8g
(0.080) 0.393 g
(0.001) Example 10 152.22 g
(0.810) 20.58g
(0.080) 35.0 g
(0.080) 12.236 g
(0.030) Example 11 152.22 g
(0.459) 122.55 g
(0.270) 208.6g
(0.270) 0.720g
(0.001) Example 12 152.22 g
(0.430) 130.81 g
(0.270) 222.6 g
(0.270) 23.048g
(0.03) Example 13 152.22 g
(0.828) 20.63 g
(0.082) 34.3g
(0.080) 3.999 g
(0.01) Example 14 152.22 g
(0.758) 41.78 g
(0.152) 37.4g
(0.080) 4.358g
(0.01) Example 15 152.22 g
(0.690) 66.420g
(0.22) 41.1 g
(0.08) 4.788g
(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) 47.1g
(0.08) 5.488g
(0.01) Example 18 152.22 g
(0.690) 24.15 g
(0.080) 113.1 g
(0.220) 4.788g
(0.01) Example 19 152.22 g
(0.645) 25.84 g
(0.080) 145.7g
(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) 64.06g
(0.214) 40.8g
(0.080) 4.747 g
(0.01) Example 23 152.22 g
(0.686) 64.99g
(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) 197.10g
(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: glycidoxypropyltrimethoxysilane
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 (R ¹ SiO _3/2 ) (SiO4 / ₂ ) (SiO _3/ ^2- R ² -SiO _3/2 (M (acac) _o ) A (mole fraction) B (mole fraction) C (molar 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) 65.48g
(0.220) 40.5g
(0.080) Comparative Example 4 152.22 g
(0.655) 84.29 g
(0.265) 43.3g
(0.080) Comparative Example 5 152.22 g
(0.612) 104.85 g
(0.308) 46.4g
(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) 143.5g
(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) 118.2g
(0.200) Comparative Example 12 30.44 g
(0.118) 197.10g
(0.472) 72.39 g
(0.205) 123.2g
(0.205) Comparative Example 13 121.78 g
(0.472) 49.28 g
(0.118) 72.39 g
(0.205) 123.2g
(0.205) Comparative Example 14 246.38 g
(0.600) 69.44 g
(0.200) 118.2g
(0.200) Comparative Example 15 152.2 g
(0.612) 104.85 g
(0.308) 46.4g
(0.08) 4.308 g
(0.003) Comparative Example 16 152.2 g
(0.612) 104.85 g
(0.308) 46.4g
(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) 43.2g
(0.08) 18.74 g
(0.05) Comparative Example 19 152.2 g
(0.607) 73.1 g
(0.213) 46.7g
(0.08) 40.582g
(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) 43.2g
(0.08) 21.63 g
(0.05) * Siloxane oligomer was gelled at the time of preparation in Comparative Example 10, Comparative Example 19 and Comparative Example 21
A: glycidoxypropyltrimethoxysilane
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: Hard Coating Film Production

100 parts by weight of the siloxane oligomer prepared in each of 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) 3 parts by weight of methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate (Irgacure-250, BASF) and a solvent methyl ethyl ketone were mixed to prepare a composition for forming a window coating layer Weight%). The composition for forming a window coating layer was coated on one side of a transparent polyimide film (CPI (Colorless POlymidie, thickness: 100 μm) as a base layer with Meyer bar # 34, dried at 100 ° C. for 5 minutes , 1000 mJ / cm ² of UV light, and aging at 50 캜 for 24 hours to prepare a window film having a window coating layer (thickness: 20 탆) formed on one side of the transparent polyimide film.

Experimental Example 2: Property evaluation of window film

[Property evaluation method]

(1) Pencil Hardness

The coating layer of the film was measured by a JIS K5400 method using a pencil hardness meter (Heidon). When measuring the pencil hardness, the pencil was a pencil of 6B to 9H from Mitsubishi. The load of the pencil on the coating layer was 0.75 kg, the angle of the pencil was 45 °, and the pencil was drawn at a rate of 60 mm / min. The results are shown in Tables 3 and 4. The results are shown in Tables 3 and 4. The results are shown in Tables 3 and 4, and the results are shown in Tables 3 and 4, respectively.

(2) Curling

The maximum height (H) from the bottom surface to the edge of the cutting film was measured when the coated film was cut to a width x length (10 cm x 10 cm) and left on the floor at 25 ° C and 40% relative humidity, Are shown in Tables 3 and 4.

(3) Curvature radius

A CPI (Colorless Polyimide) window film (width x length x thickness, 3 cm x 15 cm x 100 m) was wound around a curvature radius test JIG (CFT-200R, COVOTECH) The film was visually evaluated for cracking when it was loosened. The radius of curvature is measured by bringing the window coating layer into contact with the JIG. The radius of curvature was measured by gradually decreasing the diameter of the JIG starting from when the radius of the JIG was the maximum. The minimum radius of the JIG without cracking is shown in Table 3 and Table 4 as the radius of curvature.

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

(5) wear resistance test

In order to evaluate the scratch resistance of the transparent flexible hard coating film prepared according to Examples and Comparative Examples, a scratch resistance of the hard coating film was measured at a load of 1.5 N / cm < ² > The surface was reciprocated ten times, and the presence or absence of scratches was confirmed. The results are shown in Tables 3 and 4 as O (no scratch occurrence) and X (scratch occurrence).

(6) Chemical resistance

The film cut into 1 cm x 1 cm on the slide glass was fixed with an adhesive tape (3M) so that its coated surface was on top, and then immersed in an aqueous solution of acetone, NMP and 0.05% KOH for 12 hours to measure whether or not the peeling of the coating layer occurred It was judged to be defective when peeling occurred and good when peeling did not occur. The evaluation results of physical properties of the window film, which is a cured product of the siloxane oligomers of Examples 1 to 27, are shown in the following Table 3, and the evaluation results of physical properties of the window film, which is a cured product of the siloxane oligomer of Comparative Examples 1 to 21, 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, are greatly improved.

The hardcoat film properties of the siloxane oligomer cures according to the Examples Pencil Hardness (H) Curling (mm) Radius of curvature ΔYI Abrasion 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

The hard coat film properties of the siloxane oligomer cured product according to the comparative example Pencil Hardness (H) Curling (mm) Radius of curvature ΔYI Abrasion 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 - - - - - - ** Siloxane oligomer was not gellated and measured in the preparation in Comparative Example 10, Comparative Example 19 and Comparative Example 21. [

Although the present invention has been described based on the exemplary embodiments and examples of the present invention, the present invention is not limited to the technical ideas described in the above embodiments and examples. Those skilled in the art will appreciate that various modifications and changes may be made without departing from the spirit and scope of the present invention as defined by the appended claims. It is apparent, however, that the appended claims are intended to cover all such modifications and changes as fall within the true scope of the invention.

100: Hard coating film (optical film, cover window)
110: Base material 120: Hard coating layer
200: display device 210: display panel

Claims (21)

A siloxane oligomer represented by the following formula (1) for forming a hard coating 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
Wherein R ¹ is selected from the group consisting of a glycidoxy group, a glycidoxypropyl group, an alicyclic epoxy group, an epoxycyclohexylethyl group, and an epoxycyclohexylmethyl group, R ² is an unsubstituted or substituted C ₁ -C as ₁₀ alkyl group or unsubstituted or substituted C ₅ ~ C ₃₀ aryl group, a substituent may be substituted to said alkylene group and the arylene group is a C ₁ ~ C ₃₀ straight or branched alkyl group, C ₁ ~ C ₂₀ alkoxy group, A carboxyl group, a vinyl group, a nitro group, a sulfone group, a hydroxyl group, a C ₃ - C ₈ cycloalkyl group, an alkyd group, an alkoxy group, an amino group, an acrylic group, a methacrylic group, a halogen, a mercapto group, , a urethane group, an oxetane group, a C ₅ ~ C ₃₀ aryl group, C ₅ ~ C ₃₀ aryl group, C ₅ ~ C ₃₀ aryloxy group and selected from the group consisting of a combination thereof; M is aluminum, titanium, zirconium , Zinc and combinations thereof And the metal atom is selected from, acac is unsubstituted or substituted with C ₁ ~ C ₁₀ straight-chain or being an acetylacetone ligand substituted by a branched alkyl group, o is an integer from 2 to 4; 0.25 ≤ x ≤ 0.979, 0.01 ≤ y ≤ 0.35, 0.01 0.001? M? 0.05; x + y + z + m = 1)
The siloxane oligomer according to claim 1, wherein in the above 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 =
The siloxane oligomer according to claim 1, wherein 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 =
The method of claim 1, wherein in Formula 1 R ¹ is gamma-glycidyl sidok group, gamma-glycidoxypropyl group, a 2- (3,4-epoxy cyclohexyl) and 2- (3,4-epoxycyclohexyl ) Ethyl group. ≪ / RTI >
2. The process according to claim 1, wherein M (acac) _o of formula 1 is selected from the group consisting of aluminum acetylacetone, titanium acetylacetone, titanium ethyl acetylacetone, zirconium monoacetylacetone, zirconium tetraacetylacetone, zinc acetylacetone, ≪ / RTI >
The siloxane oligomer of claim 1, wherein the siloxane oligomer has a weight average molecular weight of from 1,000 to 100,000.
A process for preparing a siloxane oligomer represented by the following formula (1) for forming a hard coating film of a display device,
Reacting a first siloxane monomer represented by the following formula (2), a second siloxane monomer represented by the following formula (3), a third siloxane monomer represented by the following formula (4), and an organometallic compound represented by the following 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
(2)
R ¹ Si (OR ³ ) _a (R ⁴ ) _b
(3)
Si (OR ⁵⁾ ₄
Formula 4
_{^{(Si (OR 6) 3 -R}} 2 -Si (OR 7) 3) z
Formula 5
(M (acac) _o )
Wherein R ¹ is selected from the group consisting of a glycidoxy group, a glycidoxypropyl group, an alicyclic epoxy group, an epoxycyclohexylethyl group, and an epoxycyclohexylmethyl group, and R ² in the general formulas (1) and (4) An unsubstituted or substituted C ₁ to C ₁₀ alkylene group or an unsubstituted or substituted C ₅ to C ₃₀ arylene group in which the alkylene group and the substituent which may be substituted in the arylene group are C ₁ to C ₃₀ linear or branched alkyl groups , A C ₁ -C ₂₀ alkoxy group, an amino group, an acryl group, a methacryl group, a halogen, a mercapto group, an allyl group, an ether group, an ester group, a carbonyl group, a carboxyl group, a vinyl group, a nitro group, _A group consisting of a C ₃ to C ₈ cycloalkyl group, an alkyd group, a urethane group, an oxetane group, a C ₅ to C ₃₀ aryl group, a C ₅ to C ₃₀ arylalkyl group, a C ₅ to C ₃₀ aryloxy group, In the formulas (1) and (5), M represents an al Minyum, titanium, zirconium, and zinc, and a metal atom selected from the group consisting of a combination thereof, acac is being an acetylacetone ligand substituted with unsubstituted C ₁ ~ C ₁₀ straight or branched alkyl group, o is 2 to 4 Wherein R ³ and R ⁴ in formula (2), R ⁵ in formula (3), R ⁶ and R ⁷ in formula (5) are each independently a linear or branched C ₁ -C ₁₀ alkyl group, a is 2 or 3 B is an integer of 0 or 1 and a + b = 3 in the formula 1, 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. The method of claim 7, wherein the siloxane oligomer is synthesized by hydrolysis condensation reaction in the presence of an acid catalyst or a base catalyst.
The method of claim 7, wherein the first siloxane monomer represented by Formula 2 is at least one selected from the group consisting of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- , 4-epoxycyclohexyl) ethyltripropoxysilane, and combinations thereof.
[8] The method of claim 7, wherein the second siloxane monomer represented by Formula 3 is at least one selected from the group consisting of tetramethyl orthosilicate (TMOS), tetraethyl ortho silicate (TEOS), tetrapropyl orthosilicate, tetraisopropyl ortho silicate, butyl ortho silicate, and a linear or branched chain selected from the group consisting of a combination of C ₁ ~ C ₄ comprising the tetraalkyl ortho silicate.
The method of claim 7, wherein the third siloxane monomer represented by Formula 4 is selected from the group consisting of 1,2-bis (triethoxysilyl) ethane, 1,2-bis Bis (trimethoxysilyl) ethane, 1,6-bis (triethoxysilyl) hexane, 1,6-bis (trimethoxysilyl) Bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) octane, 1,8-bis (trimethoxysilyl) (1, 8-bis (trimethoxysilyl) octane), 1,4-bis (triethoxysilyl) benzene and combinations thereof.
A hardcoat composition comprising the siloxane oligomer of claim 1 for forming a hardcoat 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 cross-linking 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 combinations thereof.
15. The method of claim 14, wherein the chain type aliphatic epoxy monomer is 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglyceride Polyglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of polyether polyol, diglycidyl esters of aliphatic dibasic acid; Monoglycidyl ethers of aliphatic alcohols, glycidyl ethers of fatty acids; Epoxidized soybean oil. Butyl stearate, butyl stearate, butyl stearate, butyl stearate, octyl stearate, epoxidized linseed oil, epoxidized polybutadiene, and combinations thereof.
The method of claim 14, wherein the cyclic aliphatic epoxy monomer is selected from the group consisting of 4-vinylcyclohexene dioxide, cyclohexene vinyl monoxide, (3,4-epoxycyclohexyl) methyl, 3,4-epoxycyclohexylcarboxylate, 3 Epoxycyclohexylmethyl methacrylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) 3-dioxolane, and combinations thereof.
The method of claim 14, wherein the oxetane group-containing monomer is at least one selected from the group consisting of 3-methyloxetane, 2-methyloxetane, 3-oxetanole, 2-methylene oxetane, (2,2-dimethylpropyl) -3-methyl-3-oxetanemethanamine, N- (1,2-dimethylbutyl) -3-methyl (3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3- Ethyl-3 - [[3-ethyloxetane-3-yl] methoxy] methyl] oxetane, ≪ / RTI > or a combination thereof.
14. The composition of claim 13, wherein the hard coat composition is selected from the group consisting of a solvent, a polymerization initiator, a photosensitizer, a photosensitizer, a polymerization inhibitor, a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, Wherein the hard coat composition further comprises at least one component selected from the group consisting of an antioxidant, a lubricant, an inorganic filler, a defoaming agent, and an antifouling agent.
materials;
A hard coat layer formed on the substrate and made of a cured product of the hard coat composition according to any one of claims 12 to 18
≪ / RTI >
20. The method according to claim 19, wherein the substrate is selected from the group consisting of a polyester resin, a cellulose resin, a polycarbonate resin, an acrylic resin, a styrene resin, a polyolefin resin, a polyimide resin, a polyether sulfone resin, Wherein the hard coating film comprises a material selected from the group consisting of polyvinyl chloride and polyvinyl alcohol.
Display panel; And
And a hard coating film according to claim 19, which is located on one side of the display panel.

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