KR102068255B1 - Hard coating film alternative to tempered glass - Google Patents

Abstract

The present invention relates to a hard coating film for tempered glass replacement, more specifically, a polysilsesquioxane compound, a fluorine (meth) acrylate oligomer, and a (meth) acrylate monomer, and has a thickness of 10 to 80 µm. Phosphorus hard coating layer has excellent transparency and has the same surface hardness as glass (pencil hardness of 7H or more), and has antifouling properties such as water contact angle, oil contact angle and fingerprint wiping property. It is about.

Description

Hard Coating Film for Tempered Glass Replacement {HARD COATING FILM ALTERNATIVE TO TEMPERED GLASS}

The present invention relates to a hard coating film for tempered glass having excellent surface hardness and stain resistance.

Recently, due to the slimming trend of mobile, designs have been tried in which the outermost layer of plastic plates is removed and the outermost hard coating film of the polarizing film attached directly under the panel is exposed to the outside. However, since the hard coating film is still weak compared to the plastic plate has not been put to practical use.

At the time of manufacturing the polarizing film, a lot of defects of the polarizing film is generated by the scratch of the roll, the hard coating film is used to prevent this because the failure rate of the panel increases. However, in spite of the use of the hard coating film, defects due to scratching still occur. As described above, the hard coating film is also applied to the lower polarizing film to prevent scratches of the lower polarizing film during the panel process as well as the outermost layer of the polarizing film.

Conventional hard coating film has a pencil hardness of about 3H is commercialized. When the same hard coating composition is applied to glass, pencil hardness of about 7H to 9H is obtained. However, when the conventional hard coating composition is applied to the plastic substrate, since the plastic substrate having a weak hardness is easily deformed by external pressure, the hard coating layer formed on the plastic substrate is also deformed accordingly, so that the hard coating film has a pencil strength of about 3H. There is a problem that is not obtained.

In order to increase the hardness of the pencil in the plastic film, a conventional method of forming a hard coating layer having a thickness of 20 μm or more has been attempted. However, the hard coating film obtained by this method has a problem that the hardness is improved, but the impact resistance is weak, so that cracking or breaking occurs even in a small impact, and curling occurs a lot during the process.

As a method for improving this, a hard coating optical film (Korean Patent Publication No. 2008-55698) provided with a rigid layer between a substrate and a hard coating layer has been proposed. However, the method is excellent in impact resistance and hardness, but has a disadvantage in that a separate layer is introduced between the substrate and the hard coating layer, such as workability, handleability and the like.

The present invention is excellent in impact resistance and hardness, and there is no introduction of a separate functional layer to provide a hard coating film for tempered glass replacement excellent in workability and handleability.

In addition, an object of the present invention is to provide a hard coating film for tempered glass, which is useful when applied to the outermost layer of the display device due to its high hardness and antifouling properties.

In order to achieve the above object, the present invention comprises a polysilsesquioxane compound, a fluoro (meth) acrylate oligomer, and a (meth) acrylate monomer, the tempered glass with a hard coating layer having a thickness of 10 to 80㎛ It provides an alternative hard coating film.

Preferably, the hard coating layer may have a thickness of 10 to 50㎛.

The polysilsesquioxane compound may be represented by Formula 1 or Formula 2.

(In Formula 1 or Formula 2, R is an aliphatic or aromatic hydrocarbon having 2 to 80 carbon atoms containing 2 to 20 (meth) acrylate groups may or may not include a hetero atom.)

The fluorine (meth) acrylate oligomer may be a polymerized compound having three or more isocyanate groups in a molecule, a fluoro alcohol of Formula 3 below, and 2-hydroxyethyl (meth) acrylate.

(In Formula 3, Y is H or F, and n and m are each an integer of 0 to 200).

The hard coating layer is 0.1 to 50 parts by weight of a polysilsesquioxane compound, 0.1 to 65 parts by weight of a fluoro (meth) acrylate oligomer, and 5 to (meth) acrylate monomers based on 100 parts by weight of the total composition for forming a hard coating layer. It may contain 70 parts by weight.

The hard coating layer may have a pencil hardness of 7H or more.

The hard coating layer may have a water contact angle (at 25 ° C.) of 90 to 130 ° and an oil contact angle (at 25 ° C.) of 60 to 90 °.

The hard coating film may be provided to replace the display device protective tempered glass or to replace the polarizer integrated tempered glass.

The hard coating film may be provided in a display device selected from the group consisting of a mobile phone, a smart window, and a touch screen panel.

In addition, the present invention provides a polarizing plate that is provided with the hard coating film.

The hard coating film according to the present invention has an excellent transparency and has the same surface hardness as glass (pencil hardness 7H or more), and has the advantage of antifouling properties of water contact angle, oil contact angle and fingerprint wiping properties.

Therefore, the disadvantages of the conventional tempered glass can prevent damage, can achieve a light weight of the product can be variously applied to the product that was using the tempered glass.

In particular, the present invention may be suitably used to replace tempered glass for protecting display devices such as mobile phones, smart windows, and touch screen panels, or to replace tempered glass integrated with a polarizing plate.

The present invention relates to a hard coating film for tempered glass having excellent surface hardness and stain resistance.

Hereinafter, the present invention will be described in detail.

The hard coating film for tempered glass replacement of the present invention contains a polysilsesquioxane compound, a fluorine (meth) acrylate oligomer, and a (meth) acrylate monomer, and a hard coating layer having a thickness of 10 to 80 μm is provided. Preferably, the hard coating layer has a thickness of 10 to 50㎛.

If the thickness of the hard coating layer is less than 10㎛ may not be given enough hardness may cause cracks and scratches due to external impact, if the thickness exceeds 80㎛ may not be enough flexibility and flexibility due to workability and handleability may be reduced. .

Polysilsesquioxane compounds are included to impart hardness improvement and elasticity. The polysilsesquioxane compound may be represented by Formula 1 or Formula 2. The polysilsesquioxane compound is a structure in which an organic component is connected to a ceramic structure made of silicon and oxygen. The organic component may be selected from organic molecules such as acrylate, aryl, alkyl, amino, ester, epoxy, vinyl, fluorocarbon, and the like. Preferably, the above-described multifunctional (meth) acrylate oligomer and (meth) It is preferable to introduce the same acrylate group as the polymerization reactive group of the acrylate monomer.

[Formula 1]

[Formula 2]

(In Formula 1 or Formula 2, R is an aliphatic or aromatic hydrocarbon having 2 to 80 carbon atoms containing 2 to 20 (meth) acrylate groups may or may not include a hetero atom.)

Preferably, R preferably comprises 5 to 15 (meth) acrylate groups. When the (meth) acrylate group is included in the above range, staining in an environment such as high temperature and high humidity can be prevented.

The polysilsesquioxane represented by Formula 1 or Formula 2 may be prepared using trichlorosilane having three hydrolyzable reactors as a monomer, and prepared using trialkoxysilane. The production method using the silane triol produced in the middle of reaction is known. In this case, when the polysilsesquioxane is prepared using the above compounds, it may be prepared through a heat-condensation polymerization method. In the case of a commercially available product as the polysilsesquioxane represented by the formula (1) or (2), MA0736 (Hybrideplastic, Inc., Cage type) or Vitolane ^® SF1000MA (TWI, Ladder type) can be used.

The polysilsesquioxane compound is preferably contained 0.1 to 50 parts by weight, and more preferably 5 to 20 parts by weight based on 100 parts by weight of the total composition for forming a hard coat film. If the content is less than 0.1 parts by weight of the hard coating film having a sufficient hardness may be difficult to produce and if it exceeds 50 parts by weight is advantageous for hardness and curling, but may cause cracks in the hard coating layer during the operation of the post-process.

Fluorine (meth) acrylate oligomer is added to ensure excellent pollution prevention and anti-fingerprint, a compound having three or more isocyanate groups in the molecule, fluoro alcohol and 2-hydroxyethyl (meth) represented by the following formula (3) The acrylate may be polymerized.

[Formula 3]

(In Formula 3, Y is H or F, and n and m are each an integer of 0 to 200).

The compound having three or more isocyanate groups in the molecule is isocyanurate trifunctional isocyanate derived from 1,4-diisocyanatobutane, isocyanurate trifunctional isocyanate derived from 1,6-diisocyanatohexane. , Isocyanurate trifunctional isocyanate derived from 1,8-diisocyanatooctane, isocyanurate trifunctional isocyanate derived from 1,12-diisocyanatodecane, 1,5-diisocyanato-2 Isocyanurate trifunctional isocyanate derived from -methylpentane, isocyanurate trifunctional isocyanate derived from trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) cyclohexane Isocyanurate trifunctional isocyanate derived from isocyanurate type trifunctional isocyanate derived from trans-1,4-cyclohexene diisocyanate, Isocyanurate trifunctional isocyanate derived from 4,4'-methylenebis (cyclohexyl isocyanate), isocyanurate trifunctional isocyanate derived from isophorone diisocyanate, toluene-2,4-diisocyanate Isocyanurate trifunctional isocyanate, isocyanurate trifunctional isocyanate derived from toluene-2,6-diisocyanate, isocyanurate trifunctional isocyanate derived from xylene-1,4-diisocyanate , Isocyanurate trifunctional isocyanate derived from tetramethylxylene-1,3-diisocyanate, isocyanurate trifunctional isocyanate derived from 1-chloromethyl-2,4-diisocyanate, 4,4 Isocyanurate trifunctional isocyanates derived from '-methylenebis (2,6-dimethylphenylisocyanate), 4,4'-oxybis (pe) Isocyanurate-type trifunctional isocyanate derived from nyl isocyanate), trifunctional isocyanate derived from hexamethylene diisocyanate, trimethane propanol adduct toluene diisocyanate, 1,6-diisocyanatohexane trifunctional biuret type compound, and the like. Compounds selected from the group consisting of can be used.

Preferably is a trifunctional isocyanate derived from hexamethylene diisocyanate, trimethane propanol adduct toluene diisocyanate, isocyanurate type trifunctional isocyanate derived from isophorone diisocyanate with a compound having three or more isocyanate groups in the molecule, One selected from hexamethylene diisocyanate biuret isocyanate can be used.

Fluoro alcohol represented by the formula (3) is specifically 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,3-pentafluoro-1 -Propanol, 2,2,3,4,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, 2,2,3,3 , 4,4,5,5-octafluoro-1-pentanol, 2,2,3,3,4,4,5,5,5-nonanfluoro-1-pentanol, 2,2,3,3 And compounds selected from the group consisting of 4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol and the like.

The reaction of the compound having three or more isocyanate groups in the molecule, and the fluoro alcohol and 2-hydroxyethyl (meth) acrylate represented by the following formula (3) is preferably reacted in the presence of a solvent. The solvent is not particularly limited but ether, ketone, etc. may be preferably used in consideration of compatibility. More preferably, a fluorine-based solvent may be used as the solvent, and in particular, hydrofluorocarbon and hydrofluoroether may be used, and commercially available Batrell XF (CF ₃ CHFCHFCF ₂ CF ₃ ) manufactured by DuPont, Nippon Zeon Corporation At least one selected from the group consisting of zeolala H (heptafluorocyclopentane), HFE-7100 (C ₄ F ₉ OCH ₃ ) from 3M, 7200 (C ₄ F ₉ OC ₂ H ₅ ), and the like may be used.

The fluorine (meth) acrylate oligomers preferably include one or more selected from compounds of the following Chemical Formulas 4 to 11.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

(In Formulas 4 to 11, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Rf is represented by the following formula (12).)

[Formula 12]

(Y in Formula 12 is each independently H or F, n and m are each an integer of 0 to 200.)

The fluorine (meth) acrylate is preferably contained 0.1 to 65 parts by weight, more preferably 5 to 40 parts by weight based on 100 parts by weight of the total composition for forming a hard coat film. If the content is less than 0.1 parts by weight, it is difficult to produce an antifouling and fingerprint wiping effect, and if it exceeds 65 parts by weight, there is a problem of poor workability due to poor compatibility.

A (meth) acrylate monomer is included in order to improve the hardness improvement and curling characteristic of a hardened layer.

The (meth) acrylate monomers can be used without limitation those generally used in the art. Preferably, the (meth) acrylate monomer is dipentaerythritol penta / hexa (meth) acrylate, pentaerythritol tri / tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, (meth) acrylic ester, Trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol (Meth) acrylate, 1, 3- butanediol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth ) Acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (meth) acrylate, stearyl It may include at least one selected from the group consisting of (meth) acrylate, tetrahydroperfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornol (meth) acrylate, and the like.

The amount of the (meth) acrylate monomer is not limited, but is preferably contained 5 to 70 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the total composition for forming a hard coat film. When the content is less than 5 parts by weight, or more than 70 parts by weight, it may be difficult to exhibit the effect of sufficient hardness improvement.

The hard coat film of the present invention contains a photoinitiator and a solvent in addition to the polysilsesquioxane compound, fluorine (meth) acrylate oligomer and (meth) acrylate monomer to prepare a composition for forming a hard coat film. The photoinitiator and the solvent are components that can be removed in the process of curing the film after forming the hard coating layer, and in particular, the solvent is preferably used when diluting the prepared composition for forming the hard coating layer.

The photoinitiator may be applied without limitation as long as it is generally used in the art. The photoinitiator may be used at least one selected from the group consisting of hydroxy ketones, amino ketones and hydrogen decyclic photoinitiator.

Specific examples of the photoinitiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morphopropanone-1, diphenyl ketone benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl -1-one, 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloacetophenone, 4 At least one selected from the group consisting of, 4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenyl ketone, benzophenone, and the like can be used.

The photoinitiator is preferably contained 0.1 to 10 parts by weight based on 100 parts by weight of the total composition for forming a hard coat film. If the content is less than 0.1 parts by weight, the curing rate of the hard coating composition may be slow, and if it exceeds 10 parts by weight, cracks may occur in the hard coating layer cured by over curing.

Solvent can be used without limitation so long as it is known as a solvent in the hard coating composition of the art.

Examples of the solvent include alcohols (methanol, ethanol, isopropanol, butanol, methylcellulose, ethyl solusorb, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, Cyclohexanone, etc.), hexane-based (hexane, heptane, octane, etc.), benzene-based (benzene, toluene, xylene, etc.) and the like can be used. The solvents exemplified above may be used alone or in combination of two or more.

The solvent may be added in an amount of 0.1 to 90 parts by weight based on 100 parts by weight of the total composition for forming a hard coat film. If the content is less than 0.1 parts by weight, the viscosity may be high and workability may be lowered. If the content is more than 90 parts by weight, the curing process may take a lot of time and may be economically inferior.

Hard coating film according to the present invention is a group consisting of antioxidants, UV absorbers, light stabilizers, leveling agents, surfactants, antifouling agents generally used in the art within the range that does not lower the effect of the present invention in addition to the above components. It may further comprise one or two or more selected from.

The present invention is applied to one or both sides of the transparent base material composition for forming the hard coating layer and then cured to prepare a hard coating film having a hard coating layer on the transparent base material.

The transparent substrate may be any film as long as it is a transparent plastic film. Examples of the transparent substrate include cycloolefin derivatives having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene monomer, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, and isobutyl Cellulose selected from ester cellulose, propionyl cellulose, butyryl cellulose or acetyl propionyl cellulose, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyether sulfone, poly Sulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate , Polybutyl Terephthalate, may be used polyethylene naphthalate, polycarbonate, polyurethane, may be used one selected from among epoxy, non-stretched uniaxially or biaxially stretched film.

Among them, a monoaxial or biaxially stretched polyester film having excellent transparency and heat resistance, but a cycloolefin derivative film capable of coping with an enlargement of the film while being excellent in transparency and heat resistance, and having no transparency and optical anisotropy Acetylcellulose film can be suitably used.

8-1000 micrometers is preferable and, as for the thickness of the said transparent base material, More preferably, it is 40-100 micrometers.

Application of the composition for forming a hard coat layer may be performed in a suitable manner such as die coater, air knife, reverse roll, spray, blade, casting, gravure and spin coating.

After applying the hard coat layer-forming composition, it is dried by evaporation of volatiles for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes at a temperature of 30 to 150 ℃. Thereafter, UV light is cured by irradiation. The irradiation amount of the UV light is about 0.01 to 10 J / cm ² , preferably 0.1 to 2 J / cm ² .

The hard coating layer according to the present invention is excellent in hardness with a pencil hardness of 7H or more, a water resistance contact angle (at 25 ° C.) of 90 to 130 °, and oil resistance contact angle (at 25 ° C.) of 60 to 90 °.

In addition, the present invention provides a polarizing plate of excellent physical properties formed by laminating the above-described hard coating film on at least one surface of the polarizer.

In addition, the present invention provides a display device to which the above-described hard coating film is applied.

In particular, the hard coating film of the present invention exhibits high hardness and high antifouling property can be easily used when applied as a substitute for tempered glass, specifically, can be used for replacing the protective glass protection glass or a polarizing plate integrated tempered glass.

For example, an image display device having a polarizing plate on which a hard coat film of the present invention is formed may be provided. In addition, an image display apparatus in which the hard coat film of the present invention is attached to a window of the image display apparatus may be provided.

The hard coating film of the present invention can be preferably used in reflective, transmissive, transflective LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, IPS type, and the like. In addition, the hard coat film of the present invention can be preferably used in various display devices such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, electronic paper, and the like.

Hereinafter, preferred examples are provided to help the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. It is natural that such variations and modifications fall within the scope of the appended claims.

Synthesis Example : Fluorine (meth) acrylate Oligomer

Synthesis Example  One: Oligomer  A

20 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), derived from isophorone diisocyanate 24 parts by weight of trifunctional isocyanate (degussa), 6 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane (Aldrich), dibutyl 0.1 parts by weight of tindilaurate was added and the reactor temperature was raised to 50 ° C. and stirred for 2 hours. When 2260 cm <^{-1> which} is a characteristic peak of an isocyanate of an infrared spectral spectrum disappeared completely, reaction was complete | finished and the compound which is 50 weight% of solid content was obtained.

Synthesis Example  2: Oligomer  B

10 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), derived from isophorone diisocyanate 22 parts by weight of trifunctional isocyanate (Degussa), 18 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane (Ildrich), di 0.1 parts by weight of butyl tin dilaurate was added and the reactor temperature was raised to 50 ° C. and stirred for 2 hours. When 2260 cm <^{-1> which} is a characteristic peak of an isocyanate of an infrared spectral spectrum disappeared completely, reaction was complete | finished and the compound which is 50 weight% of solid content was obtained.

Synthesis Example  3: Oligomer  C

20 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), derived from hexamethyldiisocyanate 24 parts by weight of trifunctional isocyanate (BASF), 6 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane (Aldrich), dibutyl 0.1 parts by weight of tindilaurate was added and the reactor temperature was raised to 50 ° C. and stirred for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely to obtain a compound having a solid content of 50% by weight.

Synthesis Example  4: Oligomer  D

13 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), derived from hexamethyldiisocyanate 22 parts by weight of trifunctional isocyanate (BASF), 15 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane, dibutyl tin dilaurate 0.1 Part by weight was added and the reactor temperature was raised to 50 ° C. and stirred for 2 hours. When 2260 cm ^{-1, which} is the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely, the reaction was terminated to obtain a compound having a solid content of 50% by weight.

Synthesis Example  5: Oligomer  E

20 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), trimethanepropanol adduct toluene 18 parts by weight of diisocyanate (Aekyung Chemical Co., Ltd.), 6 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane, and 0.1 parts by weight of dibutyl tin dilaurate Added and the reactor temperature was raised to 50 ° C. and stirred for 2 hours. When 2260 cm <^{-1> which} is the characteristic peak of isocyanate of an infrared spectral spectrum disappeared completely, reaction was complete | finished and the solid content of 50 weight% compound was obtained.

Synthesis Example  6: Oligomer  F

15 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), trimethanepropanol adduct toluene 20 parts by weight of diisocyanate (Aekyung Chemical Co., Ltd.), 15 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane, and 0.1 parts by weight of dibutyl tin dilaurate Added and the reactor temperature was raised to 50 ° C. and stirred for 2 hours. When 2260 cm <^{-1> which} is a characteristic peak of an isocyanate of an infrared spectral spectrum disappeared completely, reaction was complete | finished and the compound which is 50 weight% of solid content was obtained.

Synthesis Example  7: Oligomer  G

2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI) 20 parts by weight, hexamethylene diisocyanate biuret type 23 parts by weight of isocyanate (BASF), 7 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane, and 0.1 parts by weight of dibutyl tin dilaurate And the reactor temperature was raised to 50 ℃ and stirred for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely to obtain a product having a solid content of 50% by weight.

Synthesis Example  8: Oligomer  H

2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI) 12 parts by weight, hexamethylene diisocyanate biuret type 23 parts by weight of isocyanate (BASF), 15 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane, and 0.1 parts by weight of dibutyl tin dilaurate And the reactor temperature was raised to 50 ℃ and stirred for 2 hours. When 2260 cm <^{-1> which} is a characteristic peak of an isocyanate of an infrared spectral spectrum disappeared completely, reaction was complete | finished and the compound which is 50 weight% of solid content was obtained.

Example  1 and Comparative example  1-3: Hard coating  Composition

To prepare a hard coating composition using the composition of Table 1.

division
(Part by weight) Example 1 Comparative example One 2 3 4 5 6 7 8 9 10 11 12 13 One 2 Fluorine (meth) acrylate A 10 - - - - - - - 20 - - - 10 - - B - 10 - - - - - - - 30 - One - - - C - - 10 - - - - - - - - - - - - D - - - 10 - - - - - - 61 - - - - E - - - - 10 - - - - - - - - - - F - - - - - 10 - - - - - - - - - G - - - - - - 10 - - - - - - - - H - - - - - - - 10 - - - - - - - MCF350-5 - - - - - - - - - - - - - One 10 MA0736 10 10 10 10 10 10 10 10 10 5 5 10 - 10 10 Vitolane ^® SF1000MA - - - - - - - - - - - - 10 - - Acrylate
Monomer 35 35 35 35 35 35 35 35 27 25 10 44 35 44 30 menstruum MIBK 20 20 20 20 20 20 20 20 18 18 - 20 20 20 25 MEK 23 23 23 23 23 23 23 23 23 20 22 23 23 23 23 ore
Initiator I-184 One One One One One One One One One One One One One One One I-907 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 additive BYK-378 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 MCF 350-5: Fluoropolymer (Dainippon Ink)
Acrylate monomer: pentaerythritol tri / tetraacrylate (Miwon Corporation, M340)
MA0736: polysilsesquioxane (Hybrideplastic, Cage type)
Vitolane ^? F1000MA: Polysilsesquioxane (TWI, Ladder type)
MEK: methyl ethyl ketone
MEC: Methyl Cellulose Solution
I-184: 1-hydroxycyclohexyl phenyl ketone (Shiba Corporation)
I-907: 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1 (Shiba Corporation)
BYK-378: Silicone Modified Oil (BYK)

Example  2 : Hard Coating Film

After stirring the hard coating composition prepared in Example 1 and Comparative Examples 1 to 3 for 1 hour with a Meyer Bar (a kind of gravure coater) so that the thickness on the transparent substrate film (80㎛, TAC) as shown in Table 2 below It was then applied and dried at 70 ° C. for 1 minute. Thereafter, a hard coating film including a hard coating layer formed by curing at 500 mJ / cm ² was prepared.

division Hard Coating Composition Thickness (㎛) Example 2-1 Example 1-1 30 Example 2-2 Example 1-2 30 Example 2-3 Example 1-3 30 Example 2-4 Example 1-4 30 Example 2-5 Example 1-5 30 Example 2-6 Example 1-6 30 Example 2-7 Example 1-7 30 Example 2-8 Example 1-8 30 Example 2-9 Example 1-9 30 Example 2-10 Example 1-10 30 Example 2-11 Example 1-11 30 Example 2-12 Example 1-12 30 Example 2-13 Example 1-1 10 Example 2-14 Example 1-1 50 Example 2-15 Example 1-1 70 Example 2-16 Example 1-13 30 Comparative Example 4 Comparative Example 1 30 Comparative Example 5 Comparative Example 2 30 Comparative Example 6 Comparative Example 3 30

Experimental Example

The physical properties of Example 2 and Comparative Example 4-6 were measured as follows and the results are shown in Table 3 below.

One. Total light transmittance

The total light transmittance (Total Transmittance) was measured by using a spectrophotometer (HZ-1, manufactured by Suga Japan Co., Ltd.) toward the light source D65.

2.pencil hardness

The hard coating layer of the prepared hard coating film was subjected to a 500g load with a pencil hardness tester (PHT, manufactured by Korea Stone Industries, Inc.), and the pencil hardness was measured. The pencil was made 5 times per one pencil hardness using Mitsubishi products. If there were two or more gases, it was determined to be defective, and pencil hardness was indicated by a pencil before the failure occurred.

[Assessment Methods]

Kiss: 0 OK

Kiss: 1 OK

Ges: 2 or more NG

3. Scratch resistance

Scratch resistance was tested by reciprocating 10 times under 1 kg / (2 cm × 2 cm) using a steel wool tester (WT-LCM100, manufactured by Korea Protec). Steel wool used # 0000.

[Assessment Methods]

A: 0 scratches

A ': 1 to 10 scratches

B: 11 to 20 scratches

C: 21 to 30 scratches

D: 31 or more scratches

4.Waterproof Contact angle

After dropping water droplets onto the film surface at room temperature (25 ° C.), the contact angle with respect to the water droplets was measured after 1 minute using a contact angle measuring instrument (KSV Co., Ltd. CAM100). The contact angle was measured 5 times with the same sample to the left and right contact angle of the water droplets and used the average value.

5. Oil Contact angle

After dropping oleic acid on the surface of the film at room temperature (25 ° C.), the contact angle with respect to oleic acid was measured using a contact angle measuring instrument (CAM 100 of KSV) after 1 minute. The contact angle was measured 5 times with the same sample of the left and right contact angle of oleic acid and used the average value.

6.fingerprint Wipeability

Fingerprint marks on the coated surface of the film were gently wiped 10 times by ten testers with clean paper (ULTIMA II, Hansong), and the wiping property was visually evaluated.

[Assessment Methods]

A: No wipe marks remained.

B: A little wipe left.

C: A lot of wipe marks remain.

division Total light transmittance
(%) Pencil hardness
(H) Scratch resistance Fingerprint Wipe Water contact angle
(°) Contact angle
(°) Example 2-1 92 9 A A 110 75 Example 2-2 92 9 A A 109 76 Example 2-3 92 9 A A 108 77 Example 2-4 92 9 A A 109 76 Example 2-5 91 9 A A 109 77 Example 2-6 91 9 A A 110 75 Example 2-7 92 9 A A 109 77 Example 2-8 91 9 A A 108 74 Example 2-9 91 9 A A 114 85 Example 2-10 91 7 A A 118 86 Example 2-11 92 7 A A 120 90 Example 2-12 91 8 B A 95 81 Example 2-13 90 7 A A 108 82 Example 2-14 92 9 A A 108 76 Example 2-15 90 9 A A 110 76 Example 2-16 92 9 A A 110 75 Comparative Example 4 89 6 B C 76 54 Comparative Example 5 87 5 B B 96 63 Comparative Example 6 91 4 B B 65 45

As shown in Table 3, the hard coating film of Examples 2-1 to 2-16 according to the present invention is excellent in pencil hardness, scratch resistance, fingerprint wiping resistance as well as the degree of contamination resistance compared to Comparative Examples 4 to 6 It can be confirmed that the water contact angle and the milk contact angle can be confirmed in general.

Claims (10)

Polysilsesquioxane compound;
A fluorine (meth) acrylate oligomer polymerized with a compound having three or more isocyanate groups in a molecule, a fluoro alcohol of the following formula (3) and 2-hydroxyethyl (meth) acrylate; And
A (meth) acrylate monomer; containing a hard coating layer having a hardness of 7H or more and a hard coating layer having a thickness of 10 to 80㎛, wherein the fluoro (meth) acrylate oligomer is a At least one selected from compounds of Formulas 4 to 11,
The polysilsesquioxane compound is a hard coating film for replacing the tempered glass of the formula (2):
[Formula 2]

(In Formula 2, R is an aliphatic or aromatic hydrocarbon having 2 to 80 carbon atoms containing 2 to 20 (meth) acrylate groups, and may or may not include a hetero atom).
[Formula 3]

(Y in Formula 3 is H or F, n and m are each an integer of 0 to 200)
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

(In Formulas 4 to 11, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Rf is represented by the following formula 12)
[Formula 12]

(In Formula 12, Y is each independently H or F, n and m are each an integer of 0 to 200).
The hard coating film of claim 1, wherein the hard coating layer has a thickness of 10 to 50 µm.
delete delete The method according to claim 1, wherein the hard coating layer is 0.1 to 50 parts by weight of the polysilsesquioxane compound, 0.1 to 65 parts by weight of fluorine (meth) acrylate oligomer, and (meth) acryl with respect to 100 parts by weight of the composition for forming a hard coating layer Hard coating film for tempered glass substitute containing 5 to 70 parts by weight of late monomer.
delete The hard coating film of claim 1, wherein the hard coating layer has a water resistance contact angle (at 25 ° C) of 90 to 130 ° and an oil resistance contact angle (at 25 ° C) of 60 to 90 °.
The hard coating film of claim 1, wherein the hard coating film is provided to replace the display device protective tempered glass or to replace the polarizer integrated tempered glass.
The hard coating film of claim 8, wherein the hard coating film is provided in a display device selected from the group consisting of a mobile phone, a smart window, and a touch screen panel.
Claim 1, 2, 5, and the polarizing plate is provided with any one of the hard coating film of 7 to 9.