KR20080062355A - Hard coating solution and hard coating film with high hardness using the same - Google Patents

Abstract

A hard coating solution, and a hard coating film formed by using the hard coating solution are provided to improve hardness, folding endurance, weather resistance, transparency and abrasion resistance. A hard coating solution comprises an organic/inorganic silica particle which is formed by chemically bonding a multifunctional silane compound containing a multifunctional (meth)acrylate represented by the formula 1 to the surface hydroxyl group of a silica particle; a multifunctional (meth)acrylate; an initiator; and a solvent, wherein R1 is a C1-C6 alkyl group or an aryl group; R2 is a C1-C5 alkyl group; R3 is a linear, branched or cyclic C1-C15 aliphatic or aromatic hydrocarbon group containing or not containing a hetero atom; and Y is a (meth)acrylate group having a functionality of 2-10.

Description

Hard Coating Liquid and Hard Coating Film Using the Same {Hard Coating Solution and Hard Coating Film With High Hardness Using the same}

The present invention relates to a hard coating liquid and a high hardness hard coating film using the same.

BACKGROUND ART Conventionally, hard coating films are used for various surface protection panels such as liquid crystal displays (LCDs), plasma displays (PDPs), CRTs, electroluminescent displays (ELs), and the like. In addition to hard coating properties, it may also provide resistance to marking by fingerprints, markers, and the like, and / or ease of removal (ie, antifouling).

As a material for forming the hard coating film, UV curable acrylic hard coating materials such as polyester, acrylate, urethane acrylate, and epoxy acrylate have sufficient surface protection properties to have as a hard coating film when the organic material alone is used. It did not represent. Therefore, various organic-inorganic coating liquids including colloidal silica particles, which are inorganic, have been used to improve high hardness and wear resistance to hard coating films.

However, the problem of precipitation of colloidal silica particles whose silica surface is modified with organic material or silane, the problem of stability due to gel generation, the degree of curing, optical transparency and adhesion still fall short of the requirements of the hard coating film for display device protection. .

In addition, in the conventional hard coating film, when the thickness is increased to improve the hardness, the hardness of the obtained hard coating film is improved. On the contrary, the hard coating layer is peeled off, and the end of the hard coating film is rolled due to curing shrinkage and hot / wet shrinkage. There is a problem that the rising curl becomes large and the handling aptitude is lowered.

The present invention has been made to solve the above problems, while maintaining the general physical properties required for hard coating films, such as for display device protection, and can provide a high-hardness hard coating film, peeling, curl (curl) of the hard coating layer It is an object of the present invention to provide a hard coating liquid capable of suppressing the occurrence of a phenomenon and a high hardness hard coating film using the same.

The present invention for achieving the above object,

(A) The organic-inorganic silica particle which chemically couple | bonded the polyhydroxy silane compound containing polyfunctional (meth) acrylate of the following [Formula 1] to the surface hydroxyl group of a silica particle, (B) polyfunctional (meth) It provides the hard coating liquid containing an acrylate, (C) initiator, and (D) solvent.

[Formula 1]

Wherein R ₁ represents an alkyl group having 1 to 6 carbon atoms or an aryl group, R ₂ represents an alkyl group having 1 to 5 carbon atoms, and R ₃ represents a linear, branched or cyclic C 1 ˜15 aliphatic or aromatic hydrocarbons, with or without hetero atoms, and Y represents a (meth) acrylate having 2 to 10 functional groups.)

In addition, with respect to 100 weight of the hard coating solution, the organic-inorganic silica particles are 5 to 50% by weight, the polyfunctional (meth) acrylate is 5 to 40% by weight, the photoinitiator is characterized in that it comprises 0.1 to 10% by weight It provides a hard coating liquid.

The present invention also provides a high hardness hard coating film having a hard coating layer formed by applying the hard coating liquid to a transparent substrate.

In addition, the transparent substrate provides a hard coating film, characterized in that the triacetyl cellulose film or cycloolefin-based derivative film.

In another aspect, the present invention is a high-hardness hard coating film having a cross-linked hard coating layer, characterized in that the silica particles are chemically covalently bonded in the cross-linked network of the cross-linked hard coating layer, the thickness of the hard coating layer is 5 ~ 30 It provides a high hardness hard coat film, characterized in that the μm, the curling property is 15mm or less.

In addition, the cross-linked network provides a hard coat film, characterized in that the structure is chemically bonded to the silica particles and the polyfunctional silane compound including the polyfunctional (meth) acrylate of the formula (1).

Hereinafter, the present invention will be described in more detail.

First, the hard coating solution will be described.

The hard coating solution according to the present invention is an organic-inorganic silica particle chemically bonded to a polyhydroxy silane compound containing a polyfunctional (meth) acrylate of the following [Formula 1] to the surface hydroxy group of (A) silica particles, (B And polyfunctional (meth) acrylate, (C) initiator, and (D) solvent.

[Formula 1]

Wherein R ₁ represents an alkyl group having 1 to 6 carbon atoms or an aryl group, R ₂ represents an alkyl group having 1 to 5 carbon atoms, and R ₃ represents a linear, branched or cyclic C 1 ˜15 aliphatic or aromatic hydrocarbons, with or without hetero atoms, and Y represents a (meth) acrylate having 2 to 10 functional groups.)

In the present invention, the organic-inorganic silica particles are prepared by chemically bonding a polyfunctional silane compound containing the polyfunctional (meth) acrylate of the above [Formula 1] to a silica particle surface hydroxy group. The organic-inorganic silica particles are not limited but may be included in an amount of 5 to 50 wt% based on 100 wt% of the hard coating solution.

The silica particles used in the preparation of the organic-inorganic silica particles are not limited, but it is preferable to use a colloidal silica sol dispersed in an organic solvent. As the organic solvent, methyl ethyl ketone as ketones, isopropanol, methanol and the like can be used as methyl isobutyl ketone alcohols. Of these, methyl isobutyl ketone is preferred in view of dispersibility and stability.

Commercially available colloidal silica sol includes methyl ethyl ketone silicazol (MEK-ST, manufactured by Nissan Chemical, average particle size of 22 nm, silica content of 30%), silica powder particles (aerosil TT600, aerosil agent, particle average size of 40 nm), Methyl isobutyl ketone silicazol (MIBK-ST, Nissan Chemical, average particle size 22nm, silica content 30%), isopropanol silicazol (IPA-ST, Nissan Chemical, particle average size 22nm, silica content 30 %) Etc. are mentioned. Any one or more of these can be used.

In addition, the average particle diameter of the colloidal silica particles is not limited, but may be used in the range of 10nm ~ 100nm and when used in the cured transparent film is preferably 10nm ~ 50nm. When the particle diameter of the number average particle exceeds 100 nm, transparency may fall or coating surface state may be unsatisfactory. In addition, when the particle diameter is less than 10 nm, it can be found that the hard hardness of the coating is deteriorated.

The polyfunctional silane compound containing polyfunctional (meth) acrylate couple | bonded with the hydroxyl group of the said silica particle surface is represented by said [Formula 1].

In formula, R <_1> represents a C1-C6 alkyl group or an aryl group, R <_2> represents a C1-C5 alkyl group, R <_3> is linear, branched or cyclic C1-C1-C 15, an aliphatic or aromatic hydrocarbon, with or without hetero atoms, and Y represents a (meth) acrylate having 2 to 10 functional groups.

In more detail, R ₁ may be methyl, ethyl, isopropyl, propyl, butyl or phenyl, and R ₂ may be methyl, ethyl, isopropyl, propyl, butyl or pentyl. ₃ is 2,4-toylene diisocyanate, 2,6-toylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylenedi isocyanate, p- Phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenyl Rendiisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate thread) fumarate, 6- Isopropyl-1,3-phenyldiiso Cyanate, 4-diphenylpropane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, tetramethylxylene diisocyanate and the like. Y is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate , 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acrylonyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate Neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate Etc. are possible. As used herein, (meth) acrylate refers to acrylate or / and methacrylate. The polyfunctional silane compound including the silica particles to the polyfunctional (meth) acrylate is not limited, but may be used in a ratio of 5: 1 to 1: 4 by weight.

As a polyfunctional (meth) acrylate of this invention contained in the said hard-coating liquid, For example, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, di-, Trimethylolpropane tetra (meth) acrylate, (meth) acrylic ester, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tree (meth) Acrylate, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexane Diol 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 (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. can be used And it may contain one or more of the above polyfunctional (meth) acrylates. Its amount is not limited, but is 5 to 40% by weight, preferably 10 to 30% by weight per 100 weight of the hard coating solution.

As the photoinitiator of the present invention contained in the hard coating solution may be selected without limitation as long as the initiator can be used in the art, for example, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholine Propanone-1, diphenyl ketone benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylacetophenone, anthraquinone, flu Orene, triphenylamine, carbazole, 3-methylacetophenone, 4-chloroacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, and the like. It may contain more than one species. Its usage amount is 0.1 to 10% by weight per 100 weight of the hard coating solution. If less than 0.1% by weight, the curing speed is slow and more than 10% by weight is uneconomical.

In addition, photostimulants can be used together with photoinitiators, for example, triethylamine, diethylamine, methyldiethanolamine, ethanolamine, 4-dimethylamino-benzoic acid, isoamyl-4-dimethylaminobenzoate, and the like. This can be used.

The solvent may be used without limitation, known as a solvent of the hard coating solution in the art. For example, alcohols (methanol, ethanol, isopropanol, butanol, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, etc.) are preferable, and 100 weight of the hard coating liquid 10 to 75% by weight, preferably 30 to 60% by weight can be added. Preferably, a solvent present in the colloidal silica particles to be used is preferably used as a solvent for the hard coating solution.

In addition to the above materials, antioxidants, UV absorbers, light stabilizers, thermal polymerization inhibitors, leveling agents, surfactants, lubricants, antifouling agents and the like may be used together in the hard coating solution.

The present invention also provides a high hardness hard coat film.

The high hardness hard coat film according to the present invention includes a crosslinked hard coat layer, and the silica particles are chemically covalently bonded in the crosslinked network of the crosslinked hard coat layer. For example, the above-mentioned hard coating liquid may be a high hardness hard coating film coated on a transparent substrate. The silica particles are bonded and crosslinked with the polyfunctional silane compound of Chemical Formula 1 to chemically covalently bond the silica particles in the crosslinking network, thereby providing high hardness, and solving the peeling and curling phenomenon, thereby improving reliability.

As the transparent substrate, any film can be used as long as it is a transparent plastic film. For example, a cycloolefin derivative having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene monomer, cellulose, Diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose or polyester, polystyrene, polyamide, polyetherimide , Polyacryl, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, poly Ether sulfone, polymethyl At least one selected from thermoplastic polymers such as acrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, epoxy, and the like can be used. Can be used.

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 is suitably used. Although the thickness of a transparent base film is not restrict | limited, It is 8-1000 micrometers, Preferably it is 40-100 micrometers.

In the present invention, the coating of the hard coating film may be applied by a suitable method such as die coater, air knife, reverse roll, spray, blade, casting, gravure and spin coating.

The coating thickness of a coating liquid is 0.1-200 micrometers normally, Preferably it is 5-40 micrometers, More preferably, it is 5-35 micrometers. After application, the composition is dried by evaporation of volatiles for 1 second to 2 hours, preferably 10 seconds to 1 hour at a temperature of 30 ~ 150 ℃. After curing by irradiation with UV light. The irradiation amount of UV light is about 0.01-10 J / cm ² , preferably 0.1-2 J / cm ² .

The thickness of the hard coating layer is not limited, but is preferably in the range of 5 to 30 μm, more preferably in the range of 10 to 25 μm, and when the curling property is adjusted to 15 mm or less, a hard coating film of high hardness can be obtained. have.

The high hardness hard coat film prepared as described above has excellent high hardness, abrasion resistance, weather resistance, and optical high transparency, and has a high curing speed at the time of its manufacture, and thus has high productivity, and the film produced after curing does not generate curling phenomenon. Did.

The present invention will be further illustrated by the following examples, which are only specific examples of the present invention, and are not intended to limit or limit the protection scope of the present invention.

Synthesis of Polyfunctional Silane Compounds Containing Polyfunctional (meth) acrylates

Synthesis Example 1

20.6 parts by weight of isophorone diisocyanate was slowly added dropwise to a solution of 14.2 parts by weight of bis [3- (trimethoxysilyl) propyl] amine and 0.2 part by weight of dibutyl tin diallanate at 0 ° C for 1 hour. After stirring this solution at 25 degreeC for 30 minutes, 71.4 weight part of pentaerythritol triacrylate was slowly added dropwise at 30 degreeC for 1 hour. After dropping, the temperature was raised to 60 ° C. and stirred for 3 hours.

The infrared spectral absorption peak of the product can confirm that [-N- (C = O) -NH-] is 1720cm ^-1 and the [-O- (C = O) -NH-] peak is 1660cm ^-1 .

Synthesis Example 2

20.6 parts by weight of isophorone diisocyanate was slowly added dropwise to a solution of 14.2 parts by weight of bis [3- (trimethoxysilyl) propyl] amine and 0.2 part by weight of dibutyl tin diallanate at 0 ° C for 1 hour. After stirring this solution at 25 degreeC for 30 minutes, 125.6 weight part of dipentaerythritol penta / hexaacrylates was slowly added dropwise at 30 degreeC for 1 hour. After dropping, the temperature was raised to 60 ° C. and stirred for 3 hours.

The infrared spectral absorption peak of the product can confirm that [-N- (C = O) -NH-] is 1720cm ^-1 and the [-O- (C = O) -NH-] peak is 1660cm ^-1 .

Synthesis Example 3

20 parts by weight of 1,6-diisocyanatohexane was slowly added dropwise to the solution of 18.28 parts by weight of bis [3- (trimethoxysilyl) propyl] amine and 0.1 parts by weight of dibutyl tin diallanate at 0 ° C. for 1 hour. After stirring this solution at 25 degreeC for 30 minutes, 91.5 weight part of pentaerythritol triacrylate was slowly added dropwise at 30 degreeC for 1 hour. After dropping, the temperature was raised to 60 ° C. and stirred for 3 hours.

The infrared spectral absorption peak of the product can confirm that [-N- (C = O) -NH-] is 1720cm ^-1 and the [-O- (C = O) -NH-] peak is 1660cm ^-1 .

Synthesis Example 4

20 parts by weight of 1,6-diisocyanatohexane was slowly added dropwise to the solution of 18.28 parts by weight of bis [3- (trimethoxysilyl) propyl] amine and 0.1 parts by weight of dibutyl tin diallanate at 0 ° C for 1 hour. The solution was stirred at 25 ° C. for 30 minutes, and then 160.09 parts by weight of dipentaerythritol penta / hexaacrylate was slowly added dropwise at 30 ° C. for 1 hour. After dropping, the temperature was raised to 60 ° C. and stirred for 3 hours.

Infrared absorption spectrum peak of the product peak [-N- (C = O) -NH- ] 1720cm -1 and [-O- (C = O) -NH- ] is 1660cm ^- can confirm the ^first.

Preparation of Colloidal Organic-Inorganic Silica Particles

(Manufacture example 1)

8.7 parts by weight of a polyfunctional silane compound containing polyfunctional (meth) acrylate (Synthesis Example 1), 91.3 parts by weight of methyl isobutyl ketone silicazol (MIBK-ST, Nissan Chemical, 30% silica), 0.2 parts by weight of methanol, and 0.1 weight part of distilled water was stirred for 3 hours in 80 degreeC and nitrogen gas atmosphere. 1.4 weight part of methyl ortho-permates were added, and it stirred at 80 degreeC and nitrogen gas atmosphere for 1 hour, and obtained colloidal organic-inorganic silica particle.

(Manufacture example 2)

It carried out similarly to manufacture example 1 except using the product manufactured by the synthesis example 2 as a polyfunctional silane compound compound containing polyfunctional (meth) acrylate.

(Manufacture example 3)

It carried out similarly to manufacture example 1 except using the product manufactured by the synthesis example 3 as a polyfunctional silane compound compound containing polyfunctional (meth) acrylate.

(Manufacture example 4)

It carried out similarly to the manufacture example 1 except using the product manufactured by the synthesis example 4 as a polyfunctional silane compound compound containing a polyfunctional (meth) acrylate.

(Example 1)

Colloidal organic-inorganic silica particles (Preparation Example 1) 70 parts by weight (including solvent), dipentaerythritol penta / hexaacrylate (DPHA, manufactured by NK) 12.5 parts by weight, pentaerythritol tree / tetraacrylate (manufactured by NK) 12.5 Parts by weight, 1 part by weight of 1-hydroxycyclohexylphenyl ketone (manufactured by Shiba Gauge Co., Ltd.), 0.4 part by weight of 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1 (manufactured by Shiba Gauge Co.) In addition, 0.1 weight part of lard 2200N (made by Daegu Co., Ltd.) and 0.1 weight part of the leveling agent were made to stir for 1 hour. The product was coated on a transparent substrate film (80 μm, TAC) to a thickness of 20 μm by a Meyer bar and dried at 70 ° C. for 1 minute, and then cured at 720 mJ / cm ² to prepare a hard coating film.

(Example 2)

The same procedure as in Example 1 was carried out except that the product prepared in Preparation Example 2 was used as the colloidal organic-inorganic silica particles.

(Example 3)

The same process as in Example 1 was carried out except that the product prepared in Preparation Example 3 was used as the colloidal organic-inorganic silica particles.

(Example 4)

The same procedure as in Example 1 was carried out except that the product prepared in Preparation Example 4 was used as the colloidal organic-inorganic silica particles.

(Example 5)

It carried out similarly to Example 1 except apply | coating to thickness of 25 micrometers on a transparent base film (80 micrometers, TAC).

(Comparative Example 1)

70 parts by weight of colloidal silica (MIBK-ST, Nissan Chemical), 30 parts by weight of dipentaerythritol penta / hexaacrylate (manufactured by NK Corporation), 1 part by weight of 1-hydroxycyclohexylphenyl ketone (manufactured by Shiba gauge Co., Ltd.), fluorine-based interface The hard coating solution containing 0.1 parts by weight of the active agent (FC340, 3M Co. Ltd) was applied on a transparent substrate film (80 μm, TAC) with a meyer bar so as to have a thickness of 20 μm and dried at 70 ° C. for 1 minute, and then to 720 mJ / cm ² . Curing to prepare a high hardness hard coat film.

(Comparative Example 2)

It carried out similarly to the comparative example 1 except using 70 weight part of silica polyfunctional acrylate hybrid oligomers (4D5-15, DSM Co., Ltd.).

(Comparative Example 3)

It carried out similarly to the comparative example 1 except having used a siloxane type surfactant (BYK-325, BIC-Chemical company) as a fluorine type surfactant.

After preparing a hard coating solution of each of the above Examples and Comparative Examples and applying it to a transparent base film, a polarizing film was prepared by using a hard coating film that has undergone drying and ultraviolet curing as a protective layer of an iodine-based absorbing dichroic polarizing film. The polarizing film which has the high surface protection function of the practicality which maintained the said characteristic was obtained.

Property evaluation

(1) surface smoothness

The coated surface of the film is observed in the direction of inclination of 20 to 30 degrees by shining with electric light, and the presence or absence of wrinkles or wrinkles that is thought to be caused by the uniformity (microscopic) of the surface layer or the surface property of the hard coating layer is observed. Confirmed.

A: There is no micro aggregation in the surface layer, and it is uniform, and unevenness | corrugation and a wrinkle are not recognized by a hard coat layer.

B: Although microscopic aggregation is seen in the surface layer, it is very mild and unevenness | corrugation and a wrinkle are not recognized by a hard coat layer.

C: Although micro aggregates are seen in the surface layer, irregularities and wrinkles are not observed in the hard coat layer.

D: Microscopic aggregation is remarkable in the surface layer, and irregularities and wrinkles are also seen in the hard coat layer.

(2) transmittance and haze

Total light transmittance and total haze were measured using a spectrophotometer (HZ-1, manufactured by Suga Japan).

(3) pencil hardness

Pencil hardness was measured using a pencil hardness tester (PHT, manufactured by Seokbo Science, Inc.) under a 500g load. The pencil was made 5 times per pencil hardness using Mitsubishi products. If there were two or more gases, it was determined to be defective.

Kiss: 0 OK

Kiss: 1 OK

Ges: 2 or more NG

(4) scratch resistance

The scratch resistance was tested by using a steel wool tester (WT-LCM100, manufactured by Protec Co., Ltd.) for 10 reciprocations at 1 kg / (2 cm × 2 cm).

Steel wool used # 0000.

A: 0 scratches

A ': 1 to 10 scratches

B: 11-20 scratches

C: 21-30 scratches

D: 31 or more scratches

(5) adhesion

Eleven straight lines were drawn on the coated surface of the film at intervals of 1 mm each to form 100 squares, and then three peel tests were conducted using a tape (CT-24, Nichi Nippon Corp.). Three 100 squares were tested and averaged.

The adhesion was recorded as follows.

Adhesion = n / 100

n: number of rectangles that do not peel out of the entire rectangle

100: total number of squares

Therefore, when none of the peeling was recorded as 100/100.

(6) curling

The sample cut into the square shape of A4 size (29.7 X 21.0 cm) was placed on a flat glass plate with the coated surface of the film facing up, and the distance from the square glass plate was measured at 25 ° C. and 50% RH, and then averaged. Was taken as a measured value.

Very good: 0 to 15 mm, good: 15 to 30 mm, poor: 30 to 50 mm, very poor: more than 50 mm.

(7) fingerprint wiping

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

A: No wipe marks remained. B: A little wipe left. C: Wipe marks remained.

Table 1

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Hard Coating Thickness (㎛) 20 20 20 20 25 20 20 20 Surface smoothness A A A A A B B A Total light transmittance (%) 91.5 90.8 91.3 91.1 90.4 90.4 90.4 90.1 Pencil hardness 5 H 6 H 5 H 6 H 7 H 3 H 4 H 3 H Adhesion 100/100 100/100 100/100 100/100 100/100 99/100 100/100 85/100 curling Good Good Good Good Good Bad Bad Very bad Fingerprint Wipe A B A B A C B C Haze 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.4

The hard coating liquid and the high hardness hard coating film according to the present invention provide excellent surface smoothness, high hardness, adhesion, and antifouling properties, and do not cause a problem of curling phenomenon. In addition, the hard coating liquid of the present invention was excellent in productivity because of the fast curing speed.

Claims (6)

(A) The organic-inorganic silica particle which chemically couple | bonded the polyhydroxy silane compound containing the polyfunctional (meth) acrylate of the following [Formula 1] to the surface hydroxy group of a silica particle, (B) polyfunctional (meth) acryl Hard coating liquid containing the rate, (C) initiator, and (D) solvent. [Formula 1]

Wherein R ₁ represents an alkyl group having 1 to 6 carbon atoms or an aryl group, R ₂ represents an alkyl group having 1 to 5 carbon atoms, and R ₃ represents a linear, branched or cyclic C 1 ˜15 aliphatic or aromatic hydrocarbons, with or without hetero atoms, and Y represents a (meth) acrylate having 2 to 10 functional groups.) The method according to claim 1, wherein the organic-inorganic silica particles are contained in an amount of 5-50% by weight, 5-40% by weight of the polyfunctional (meth) acrylate, and 0.1-10% by weight of the photoinitiator, based on 100% by weight of the hard coating solution. Hard coating liquid, characterized in that. A high hardness hard coat film having a hard coat layer formed by applying the hard coat liquid of claim 1 to a transparent substrate. The hard coating film of claim 3, wherein the transparent substrate is a triacetyl cellulose film or a cycloolefin derivative film. A high hardness hard coat film having a crosslinked hard coat layer, characterized in that the silica particles are chemically covalently bonded in the crosslinked network of the crosslinked hard coat layer, The hard coating layer has a thickness of 5 ~ 30㎛, high hardness hard coating film, characterized in that the curling characteristics are 15mm or less. The hard coating film of claim 5, wherein a structure in which the multifunctional silane compound including the silica particles and the polyfunctional (meth) acrylate of Formula 1 is chemically bonded to the crosslinked network is present. [Formula 1]

Wherein R ₁ represents an alkyl group having 1 to 6 carbon atoms or an aryl group, R ₂ represents an alkyl group having 1 to 5 carbon atoms, and R ₃ represents a linear, branched or cyclic C 1 ˜15 aliphatic or aromatic hydrocarbons, with or without hetero atoms, and Y represents a (meth) acrylate having 2 to 10 functional groups.)