KR20080070349A - Anti-glare hard coating solution and hard coating film with high hardness using the same - Google Patents

Abstract

An anti-glare hard coating solution is provided to retain good physical properties needed for hard coating films, and to suppress a peeling-off or curling phenomenon of a hard coating layer. An anti-glare hard coating solution includes (A) 5-50wt% of organic-inorganic silica particles in which a multi-functional silane compound comprising multi-functional (meth)acrylate represented by the following formula 1 is chemically bound to hydroxyl groups on the surface of the silica particle, (B) 5-40wt% of multi-functional (meth)acrylate, (C) 0.1-10wt% of an initiator, and (D) 1-20wt% of silicon fine particles, based on 100wt% of the hard coating solution.

Description

Anti-glare hard coating solution and high hardness hard coating film using same {Anti-Glare Hard Coating Solution and Hard Coating Film With High Hardness Using the same}

The present invention relates to a hard coating liquid having high anti-glare 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 inorganic colloidal silica particles, have been used to improve the hardness and wear resistance of 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. In addition, the conventional hard coating film has a problem that the visibility of the display is lowered by the reflection of external light.

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 an anti-glare hard coating liquid having a uniform anti-glare property 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 the polyfunctional (meth) acrylate of the following [Formula 1] to the surface hydroxy group of a silica particle, (B) polyfunctional (meth) acryl An anti-glare hard coating liquid comprising the rate, (C) initiator, and (D) silicon fine particles is provided.

[Formula 1]

Wherein n is an integer of 1 to 3, R ₁ and R ₂ each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, and R ₃ is an aliphatic having 1 to 10 carbon atoms which may or may not include a hetero atom. Or an aromatic hydrocarbon, R ₄ is an aliphatic or aromatic hydrocarbon containing 1 to 15 carbon atoms, linear or branched or cyclic, with or without hetero atoms, and Y is a functional group Aliphatic or aromatic hydrocarbons containing or not containing 7 to 80 carbon atoms containing 2 to 10 (meth) acrylate 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 0.1 to 10% by weight, silicon fine particles 1 It provides an anti-glare hard coating solution characterized in that it comprises ~ 20% by weight.

In addition, the average particle diameter of the silicon fine particles provides an anti-glare hard coating liquid, characterized in that in the range of 1 ~ 10 ㎛.

In addition, Chemical Formula 1 provides an anti-glare hard coating liquid, characterized in that specified by the following formula (2).

[Formula 2]

Wherein n, R ₁ , R ₂ , R ₃ , and Y are the same as above, and R ₅ represents a linear, branched or cyclic C1-C13 hetero atom. Aliphatic or aromatic hydrocarbons, with or without).

The present invention also provides an anti-glare hard coating film having a hard coating layer formed by applying and curing the anti-glare hard coating solution on one or both surfaces on a transparent substrate.

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

The present invention also provides a high hardness hard coat film having a crosslinked hard coat layer, wherein the crosslinked hard coat layer has a structure in which silica particles are chemically covalently bonded to the crosslinked network and silicon fine particles independent of the crosslinked network are present at the same time. The thickness of the hard coating layer is 5 ~ 30㎛, provides an anti-glare hard coating film, characterized in that the curling characteristics are 15 mm 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).

[Formula 1]

Wherein n is an integer of 1 to 3, R ₁ and R ₂ each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, and R ₃ is an aliphatic having 1 to 10 carbon atoms which may or may not include a hetero atom. Or an aromatic hydrocarbon, R ₄ is an aliphatic or aromatic hydrocarbon containing 1 to 15 carbon atoms, linear or branched or cyclic, with or without hetero atoms, and Y is a functional group Aliphatic or aromatic hydrocarbons containing or not containing 7 to 80 carbon atoms containing 2 to 10 (meth) acrylate groups.

The present invention also provides a polarizing plate provided with the anti-glare hard coating film.

The present invention also provides a display device provided with the anti-glare hard coating film.

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

First, an anti-glare hard coating liquid is demonstrated.

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 A polyfunctional (meth) acrylate, (C) initiator, and (D) silicone microparticles | fine-particles are included.

[Formula 1]

Wherein n is an integer of 1 to 3, R ₁ and R ₂ each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, and R ₃ is an aliphatic having 1 to 10 carbon atoms which may or may not include a hetero atom. Or an aromatic hydrocarbon, R ₄ is an aliphatic or aromatic hydrocarbon containing 1 to 15 carbon atoms, linear or branched or cyclic, with or without hetero atoms, and Y is a functional group Aliphatic or aromatic hydrocarbons containing or not containing 7 to 80 carbon atoms containing 2 to 10 (meth) acrylate 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, n is an integer of 1-3, R <_1> , R <_2> represents a C1-C10 aliphatic or aromatic hydrocarbon each independently, R <_3> has a C1-C10 aliphatic containing or without a hetero atom, or An aromatic hydrocarbon, R ₄ is a linear, branched or cyclic C1-C15 aliphatic or aromatic hydrocarbon, with or without hetero atoms, and Y is functional group 2 Aliphatic or aromatic hydrocarbons containing or not containing 7 to 80 heteroatoms containing 10 (meth) acrylate groups.

Although not limited, it will be described in more detail as an example R ₁ , R ₂ is a methyl group, ethyl group, isopropyl group, propyl group, butyl group, phenyl group, etc., R ₃ is methyl group, ethyl group, isopropyl group, propyl group , A butyl group, a pentyl group, or a structure in which a hetero atom such as an ether bond is present in the combination thereof.

R ₄ is not limited, but it is preferable that the above formula (1) is selected to have the structure of formula (2) because the production method is simple and the effect is excellent.

[Formula 2]

Wherein n, R ₁ , R ₂ , R ₃ , and Y are the same as above, and R ₅ represents a linear, branched or cyclic C1-C13 hetero atom. Aliphatic or aromatic hydrocarbons, with or without).

That is, it is good to select the diisocyanate compound by R <_4> , and to make it manufacture by making the polyfunctional (meth) acrylate group (Y) in which a hydroxyl group exist, and an amine silane compound react. As a preferable example of a diisocyanate compound, 2, 4- toylene diisocyanate, 2, 6- toylene diisocyanate, 1, 3- xylene diisocyanate, 1, 4- xylene diisocyanate, 1, 5- naphthalene diisocyanate, m- Phenylene diisocyanate, p-phenylenedi isocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4 , 4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate thread) Fumarate, 6-isopropyl-1,3-phenyldiisocyanate, 4-diphenylpropane diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, tetramethylxylenediisocyanate, etc. are possible The.

Y represents an aliphatic or aromatic hydrocarbon containing or not containing 7 to 80 heteroatoms containing 2 to 10 (meth) acrylate groups. Although not limited, it is preferable to select a polyfunctional (meth) acrylate having a hydroxy group as an example of a reactor connecting R ₄ and Y represented by the formula (1).

Examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenyloxypropyl (meth). ) Acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acrylonyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexaneadiol mono (meth) ) Acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) Acrylates and the like. 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 can be included as a species or as a mixture. Its usage amount is 0.1 to 10% by weight per 100 weight of the hard coating solution. When less than 0.1% by weight, the curing rate is slow and when more than 10% by weight, the degree of crosslinking is lowered and the mechanical strength is lowered.

In the present invention, by adding silicon fine particles to the hard coating liquid to form surface irregularities, it is possible to provide excellent antifouling property and uniform anti-glare property.

The diameter of the silicon fine particles of the present invention dispersed in the hard coating solution is 0.5 to 10 ㎛, preferably 1 to 8 ㎛. If the particle diameter is less than 0.5 μm, the anti-glare effect is insignificant, and if the particle size is 10 μm or more, the surface may be roughened, resulting in deterioration of display quality. The addition amount of the silicon fine particles is 1 to 30% by weight, preferably 3 to 20% by weight based on 100% by weight of the hard coating solution. If the amount is less than 1% by weight, the anti-glare effect is insignificant, and if it is added more than 30% by weight, there is a problem that the whitening phenomenon of the film is increased.

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 hard coating solution of the present invention may further include a solvent, and the solvent may be used without limitation as 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 0.1 to 15% by weight may 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 an anti-glare hard coating film.

The anti-glare hard coating film according to the present invention exhibits anti-glare and has a cross-linked hard coating layer, characterized in that the silica particles are chemically covalently bonded in the cross-linking network of the cross-linked hard coating layer. For example, the anti-glare hard coating solution may be an anti-glare 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. In addition, the crosslinked hard coating layer has a structure in which the silica particles are chemically covalently bonded to the crosslinked network and silicon fine particles independent of the crosslinked network to simultaneously form surface irregularities using the silicon fine particles, thereby providing excellent antifouling properties and uniformity. Anti-glare property can be provided.

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 polycycloolefin, polyester, polystyrene, polyamide , Polyetherimide, polyacryl, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether Ether ketone, poly At least one selected from thermoplastic polymers such as lesulphone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, and epoxy may be used. Or a biaxially stretched film can be used.

Among them, preferably, a monoaxial or biaxially stretched polyester film having excellent transparency and heat resistance, a cycloolefin derivative film, a polymethyl methacrylate film, transparency, and optical properties that can cope with an enlargement of the film while being excellent in transparency and heat resistance Triacetyl cellulose and isobutyl ester cellulose films are suitably used in that they are not anisotropic. Although the thickness of a transparent base film is not restrict | limited, It is 8-1000 micrometers, Preferably it is 40-100 micrometers. If the transparent substrate film is 8 μm or less, the strength is lowered, resulting in poor workability. On the other hand, if the thickness is 1000 μm or more, transparency is reduced or the weight of the polarizing plate is increased.

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 0.1-50 micrometers normally with a humidity film, Preferably it is 1-30 micrometers, More preferably, it is 3-20 micrometers. After application, the composition is dried by evaporation of the volatiles for 1 second to 2 hours, preferably 5 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 anti-glare hard coating film prepared as described above has excellent high hardness, abrasion resistance, weather resistance, antifouling property, anti-glare property and optical high transparency, and is excellent in productivity due to the fast curing speed during its manufacture, and the film produced after curing The curling phenomenon is excellent at 15 mm or less.

The present invention also provides a polarizing plate having excellent physical properties formed by laminating the anti-glare hard coat film described above on at least one surface.

The polarizing plate is not particularly limited, but various kinds may be used. As a polarizing plate, the film polyvinyl which uniaxially stretched by adsorb | sucking dichroic substances, such as iodine and a dichroic dye, to hydrophilic polymer films, such as a polyvinyl alcohol-type film and an ethylene-vinyl acetate copolymerization partial saponification film, for example. And polyene-based alignment films such as alcohol dehydration products and polyvinyl chloride dehydrochlorination products. Among these, the polarizing plate which consists of dichroic substances, such as a polyvinyl alcohol-type film and iodine, is preferable. Although the thickness of these polarizing plates is not specifically limited, Generally, it is about 5-80 micrometers.

The present invention also provides a display device to which the above-described anti-glare hard coat film is applied. For example, by incorporating the polarizing plate having the anti-glare hard coat film of the present invention into a display device, various display devices of the present invention having excellent visibility can be manufactured. In addition, the anti-glare hard coat film of the present invention may be attached to the window of the display device. The hard coat film of the present invention can be preferably used in reflective, transmissive, semi-transmissive LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, and IPS type. In addition, the anti-glare 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 papers, and the like.

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.

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 .

Preparation of Colloidal Organic-Inorganic Silica Particles

(Manufacture example 1)

8.7 parts by weight of polyfunctional silane compound (synthesis example 1) containing polyfunctional (meth) acrylate, 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)

69.8 parts by weight of colloidal organic-inorganic silica particles (manufacturing example 1) (including solvent), dipentaerythritol penta / hexaacrylate (DPHA, manufactured by NK) 12.6 parts by weight, pentaerythritol tri / tetraacrylate (manufactured by NK) 12.6 weight 1.2 parts by weight of 1-hydroxycyclohexylphenyl ketone (manufactured by Shiba Gauge Co., Ltd.), 0.5 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1 (manufactured by Shiba Gauge Co.) , 3 parts by weight of 6 µm silicon particles and 0.3 part by weight of a glide 410 (manufactured by Daegu) were added and stirred for 1 hour. The product was coated on a transparent base film (80 μm, TAC) with a meyer bar to have a thickness of 14 μm 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 having applied the moisture film thickness of 9 micrometers on the transparent base film (80 micrometers, TAC).

(Comparative Example 1)

69.2 parts by weight of colloidal silica (MIBK-ST, Nissan Chemical), 29.7 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 After applying the hard coating liquid containing 0.1 parts by weight of the active agent (FC340, 3M Co. Ltd) on the transparent substrate film (80㎛, TAC) with a meyer bar so that the humidity film thickness is 14㎛ and dried at 70 ℃ for 1 minute, 720mJ / cm ^It was cured to ² to prepare a high hardness hard coat film.

(Comparative Example 2)

67.5 parts by weight of colloidal silica (MIBK-ST, Nissan Chemical), 28.9 parts by weight of dipentaerythritol penta / hexaacrylate (manufactured by NK Corporation), 1.0 part by weight of 1-hydroxycyclohexylphenyl ketone (manufactured by Shiba gauge Co., Ltd.), fluorine-based interface A hard coating liquid containing 0.1 parts by weight of active agent (FC340, 3M Co. Ltd), 2.5 parts by weight of 6 μm silicon fine particles, was coated on a transparent substrate film (80 μm, TAC) with a meyer bar so that the humidity film thickness was 14 μm. After drying for 1 minute at ℃, it was cured at 720mJ / cm ² to prepare a high-hardness hard coating film.

(Comparative Example 3)

It carried out similarly to the comparative example 2 except using 67.5 weight part of silica polyfunctional acrylate hybrid oligomers (4D5-15, DSM Co., Ltd.).

(Comparative Example 4)

It carried out similarly to the comparative example 2 except having used the 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 substrate film, a polarizing film was prepared using a hard coating film that went through a drying and UV curing process as a protective layer of the 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) transmittance and haze

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

(2) anti-glare

The transmission sharpness at the optical rod width of 2 mm in the transmission mode was measured using the transmission sharpness measuring instrument (ICM-1, the product made by Suga, Japan). The smaller the numerical value of the measurement data, the higher the anti-glare property. Here, less than 50% was evaluated as ○, 50% or more but less than 70%, △, 70% or more as X.

(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? 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 (antifouling)

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.

(8) weather resistance

After 300 hours using the Sunshine weatherability (Japan Suga tester), the state of the sample surface was visually observed.

A: no change in surface, B: surface is rough, C: surface is dissolved.

Table 1

Example 1 Example 2 Example 3 Example 4 Example 5 Total light transmittance (%) 91.4 90.2 91.2 91.3 90.2 Haze (%) 13.8 14.2 13.9 14.8 25.5 Anti-glare ○ ○ ○ ○ ○ Pencil hardness 3H 4H 3H 4H 2H Scratch resistance A ' A ' A ' A ' A ' Adhesion 100/100 100/100 100/100 100/100 100/100 curling Good Good Very good Good Very good Fingerprint Wipe A B A B A Weather resistance A A A A A

Table 2

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Total light transmittance (%) 92.3 90.4 90.4 90.1 Haze (%) 0.3 18.7 16.4 20.1 Anti-glare X ○ ○ ○ Pencil hardness H H 2H H Scratch resistance C C B D Adhesion 100/100 99/100 100/100 85/100 curling Bad Bad Bad Very bad Fingerprint Wipe C C B C Weather resistance B B B C

The anti-glare hard coating solution and the high-hardness hard coating film according to the present invention provides high hardness, adhesiveness, antifouling property, anti-glare property, wear resistance, weather resistance, and did not cause problems of curling phenomenon. In addition, the hard coating liquid of the present invention was excellent in productivity because of the fast curing speed.

Claims (10)

(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 An anti-glare hard coating liquid comprising a rate, (C) initiator, and (D) silicon fine particles. [Formula 1]

Wherein n is an integer of 1 to 3, R ₁ and R ₂ each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, and R ₃ is an aliphatic having 1 to 10 carbon atoms which may or may not include a hetero atom. Or an aromatic hydrocarbon, R ₄ is an aliphatic or aromatic hydrocarbon containing 1 to 15 carbon atoms, linear or branched or cyclic, with or without hetero atoms, and Y is a functional group Aliphatic or aromatic hydrocarbons containing or not containing 7 to 80 carbon atoms containing 2 to 10 (meth) acrylate 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, 0.1-10% by weight of the photoinitiator, Silicon microparticles are anti-glare hard coating liquid, characterized in that 1 to 20% by weight. The anti-glare hard coating liquid according to claim 1 or 2, wherein the average particle diameter of the silicon fine particles is in the range of 1 to 10 mu m. The anti-glare hard coating solution according to claim 1, wherein the chemical formula 1 is specified by the following chemical formula 2. [Formula 2]

Wherein n, R ₁ , R ₂ , R ₃ and Y are the same as above, and R ₅ is a linear, branched or cyclic C1-C13 hetero atom Aliphatic or aromatic hydrocarbons, with or without). An anti-glare hard coating film having a hard coating layer formed by applying and curing the anti-glare hard coating liquid according to any one of claims 1 to 4 on a transparent substrate. The anti-glare hard coating film of claim 5, wherein the transparent substrate is a triacetyl cellulose film or a cycloolefin derivative film. A high hardness hard coating film having a cross-linked hard coating layer, wherein the cross-linked hard coating layer is characterized in that a structure in which the silica particles are chemically covalently bonded to the crosslinked network and silicon fine particles independent of the crosslinked network are present at the same time. The thickness of the coating layer is 5 ~ 30㎛, anti-glare hard coating film, characterized in that the curling characteristics are 15mm or less. The anti-glare hard coating of claim 7, wherein a structure in which the multifunctional silane compound including the silica particles and the polyfunctional (meth) acrylate represented by Chemical Formula 1 is present in the crosslinked network is present. film. [Formula 1]

Wherein n is an integer of 1 to 3, R ₁ and R ₂ each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, and R ₃ is an aliphatic having 1 to 10 carbon atoms which may or may not include a hetero atom. Or an aromatic hydrocarbon, R ₄ is an aliphatic or aromatic hydrocarbon containing 1 to 15 carbon atoms, linear or branched or cyclic, with or without hetero atoms, and Y is a functional group Aliphatic or aromatic hydrocarbons containing or not containing 7 to 80 carbon atoms containing 2 to 10 (meth) acrylate groups. A polarizing plate provided with the anti-glare hard coat film of claim 7 or 8. A display device provided with the anti-glare hard coat film of claim 7.