KR20160063073A - Composition for making hard coating layer - Google Patents

Abstract

The present invention relates to a composition for forming hard coating layers. More specifically, the present invention relates to a composition for hard coating layers, which includes: an epoxy siloxane resin of which the weight-average molecular weight is 500-30,000, and the polydispersity index is 2.0-4.0; a (meth)acrylate-based polymeric compound; a photocationic initiator; and a radical initiator. According to the present invention, the composition has remarkably improved hardness and excellent flexibility, thereby forming the hard coating layers having minimized curling properties.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for forming a hard coat layer,

The present invention relates to a composition for forming a hard coat layer.

BACKGROUND ART [0002] Recently, a thin display device using a flat panel display device such as a liquid crystal display or an organic light emitting diode (OLED) display has received great attention. Particularly, these thin display devices are realized in the form of a touch screen panel, and are characterized by being portable not only in a smart phone, a tablet PC, but also in various wearable devices It is widely used in various smart devices.

These portable touch screen panel based display devices have a window cover for display protection on a display panel in order to protect the display panel from scratches or external impacts, and in most cases, the tempered glass for display is used as a window cover. Tempered glass for displays is thinner than ordinary glass, but is characterized by high strength and scratch resistance.

However, since the tempered glass has a disadvantage that it is not suitable for weight reduction of a portable device due to its heavy weight, it is difficult to realize an unbreakable property because it is vulnerable to an external impact, and is not bendable, It is not suitable as a flexible display material having a foldable function.

In recent years, studies on optical plastic covers having strength or scratch resistance corresponding to tempered glass, while ensuring flexibility and impact resistance, have been made variously. Polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyacrylate (PAR), polycarbonate (PC) , Polyimide (PI), polyamide (PA), and the like. However, these polymer plastic substrates not only lack physical properties in terms of hardness and scratch resistance as compared with tempered glass used as a window cover for display protection, but also have insufficient impact resistance. Therefore, various attempts have been made to complement the physical properties required by coating the composite resin composition on these plastic substrates.

In the case of a general hard coating, a composition comprising a resin containing a photo-curable functional group such as (meth) acrylate or epoxy and a curing agent or a curing catalyst and other additives is used. Particularly, In the case of a composite resin, it can be coated on an optical plastic substrate film to be used as a display protection window having improved hardness and scratch resistance.

However, in the case of the general (meth) acrylate or epoxy high functionality photocurable composite resin, hardness corresponding to the tempered glass is hardly realized, curl phenomenon due to shrinkage occurs largely during curing, It is not suitable as a protective window substrate to be applied to a flexible display.

Korean Patent Laid-Open Publication No. 2013-74167 discloses a plastic substrate.

Korea Patent Publication No. 2013-74167

The present invention aims to provide a composition capable of forming a hard coat layer having a significantly improved hardness.

It is an object of the present invention to provide a composition capable of forming a hard coat layer having excellent flexibility.

It is an object of the present invention to provide a hard coating film having the hard coating layer.

1. An epoxy siloxane resin having a weight average molecular weight of 500 to 30,000 and a polydispersion index (PDI) of 2.0 to 4.0; (Meth) acrylate-based polymerizable compound; Photo cationic initiators; And a photo radical initiator.

2. The composition for forming a hard coat layer according to 1 above, wherein the siloxane resin has a weight average molecular weight of 1,000 to 20,000.

3. The composition for forming a hard coat layer according to 1 above, wherein the siloxane resin has a weight average molecular weight of 5,000 to 15,000.

4. The composition for forming a hard coat layer according to 1 above, wherein the siloxane resin has an epoxy equivalent of 3.0 to 6.3 mmol / g.

5. The composition for forming a hard coat layer according to 1 above, wherein the (meth) acrylate-based polymerizable compound is at least one of a (meth) acrylate oligomer and a (meth) acrylate monomer.

6. The composition for forming a hard coat layer according to 1 above, wherein the epoxy siloxane resin and the (meth) acrylate based polymerizable compound are contained in a weight ratio of 5 to 40: 60 to 95.

7. The composition for forming a hard coat layer according to 1 above, further comprising at least one thermosetting agent selected from the group consisting of amine-based, imidazole-based, acid anhydride-based and amide-based thermosetting agents.

8. A hardcoat film comprising a substrate having a hardcoat layer formed on at least one side thereof with a composition for forming a hardcoat layer of any one of items 1 to 7 above.

9. An image display device comprising the hard coating film of the above 8.

The compositions of the present invention can form hard coat layers having significantly improved hardness.

The composition of the present invention can form a hard coating layer having excellent flexibility and minimized curl. Accordingly, the hard coating film having the hard coating layer of the present invention can secure excellent flexibility without having a separate curling inhibiting layer.

1 is a schematic cross-sectional view of a hard coat film having a hard coat layer formed from the composition for forming a hard coat layer of the present invention.
Figure 2 schematically illustrates one embodiment of performing a flexure test on a hardcoat film having a hardcoat layer formed from the composition for forming a hardcoat layer of the present invention.
Figure 3 schematically illustrates one embodiment of performing a flexure test on a hardcoat film having a hardcoat layer formed from the composition for forming a hardcoat layer of the present invention.

The present invention relates to an epoxy siloxane resin having a weight average molecular weight of 500 to 30,000 and a polydispersity index (PDI) of 2.0 to 4.0; (Meth) acrylate-based polymerizable compound; Photo cationic initiators; And a photo radical initiator, to thereby form a hard coat layer having a remarkably improved hardness and excellent flexibility, whereby curl is minimized.

<Composition for forming a hard coat layer>

The composition for forming a hard coat layer of the present invention includes an epoxy siloxane resin, a (meth) acrylate based polymerizable compound, a photo cationic initiator, and a photo radical initiator.

In the present specification, the epoxy siloxane resin means a siloxane resin having an epoxy group, and the epoxy group may be an alicyclic epoxy group, an aliphatic epoxy group, an aromatic epoxy group, or a mixture thereof.

The epoxy siloxane resin according to the present invention has a weight average molecular weight of 500 to 30,000, preferably 1,000 to 20,000, and more preferably 5,000 to 15,000 from the viewpoint of ensuring high hardness and fairness at the same time.

The polydispersity index (PDI) of the epoxy siloxane resin is 2.0 to 4.0. If the polydispersity index is less than 2.0, it is difficult to simultaneously satisfy both the hardness and ductility of the hard coat layer. If the polydispersity index is more than 4.0, the physical properties relating to ductility will be overexpressed.

The composition for forming a hard coat layer of the present invention can remarkably improve the hardness by using an epoxy siloxane resin having a weight average molecular weight and a polydispersity index within the above specific range. In addition, the flexibility is also remarkably improved, so that warpage deformation can be suppressed.

The epoxy equivalent of the epoxy siloxane resin is not particularly limited, and may be, for example, from 3.0 to 6.3 mmol / g. When the equivalent of the epoxy group is within the above range, dense crosslinking occurs at the time of polymerization, and the hardness can be remarkably improved.

The epoxy siloxane resin according to the present invention can be produced by hydrolysis and condensation reaction between an alkoxysilane having an epoxy group alone or an alkoxysilane having an epoxy group and a different alkoxysilane in the presence of water.

The following Schemes 1 to 3 schematically show the hydrolysis and condensation reaction of alkoxysilane in the presence of water and a catalyst.

[Reaction Scheme 1]

[Reaction Scheme 2]

[Reaction Scheme 3]

In the above Reaction Schemes 1 to 3, R is a linear or branched alkyl group having 1 to 7 carbon atoms, R 'is a straight or branched chain alkyl group having 1 to 20 carbon atoms, an epoxy group-containing cycloalkyl group having 3 to 8 carbon atoms, An alkenyl group having 3 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an acrylic group, a methacrylic group, a halogen group, an amino group, a mercapto group, an ether group, an ester group, a carbonyl group, , A nitro group, a sulfone group and an alkyd group.

The above reaction scheme 1 shows that the alkoxy group of the starting alkoxysilane is hydrolyzed by water to form a hydroxyl group. The hydroxyl group formed by this reaction forms a siloxane bond through a condensation reaction between hydroxyl groups or alkoxy groups of other silanes, as shown in Reaction Scheme 2 or Reaction Scheme 3. Therefore, the weight average molecular weight and the molecular weight distribution (PDI) of the finally formed siloxane compound can be controlled by controlling the reaction rate, and the reaction temperature, the amount of the catalyst, the type, the solvent and the like can be main factors.

A catalyst is used to prepare an epoxy siloxane resin having a weight average molecular weight of 2,000 to 15,000 and a polydispersity index of 2.0 to 4.0 by using the above reaction formula. Examples of usable catalysts include acid catalysts such as hydrochloric acid, acetic acid, hydrogen fluoride, nitric acid, sulfuric acid chlorosulfonic acid, iodic acid, and phosphorous acid; Base catalysts such as ammonia, potassium hydroxide, sodium hydroxide, barium hydroxide, imidazole, n-butylamine, di-n-butylamine, tri-n-butylamine, ammonium perchlorate and tetramethyl-ammonium hardoxide; And ion exchange resins such as Amberite IRA-400 and IRA-67, and combinations thereof.

Although the amount of the catalyst is not particularly limited, about 0.0001 to about 0.01 part by weight may be added to about 100 parts by weight of the alkoxysilane for the acid catalyst and the base catalyst, and about 1 to about 100 parts by weight of the ion- To about 10 parts by weight may be added, but the present invention is not limited thereto.

The hydrolysis and condensation reaction may be carried out by stirring at room temperature for about 12 hours to about 7 days. In order to accelerate the reaction, stirring may be performed at about 60 ° C to about 100 ° C for about 2 hours to about 72 hours , But may not be limited thereto.

As shown in Reaction Schemes 1 to 3, when the reaction occurs, alcohols and water, which are byproducts, are produced. By eliminating them, the reverse reaction can be reduced and the reaction can be regulated. Also, when the reaction is completed, the alcohol and water remaining in the siloxane resin may be removed by applying a condition of about 60 ° C to about 100 ° C under reduced pressure for about 10 minutes to about 60 minutes, but the present invention is not limited thereto.

The alkoxysilane having an epoxy group used in the preparation of the epoxy siloxane resin according to one embodiment of the present invention can be illustrated by the following formula:

[Chemical Formula 1]

R ¹ _n Si (OR ² ) _4-n

(Wherein R &lt; ¹ &gt; is a linear or branched alkyl group having 1 to 6 carbon atoms which is substituted with an epoxy cycloalkyl group or an oxiranyl group having 3 to 6 carbon atoms,

R ² is a linear or branched alkyl group having 1 to 7 carbon atoms,

and n is an integer of 1 to 3).

The alkoxysilane represented by the general formula (1) is not particularly limited, and examples thereof include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane , 3-glycidoxypropyltrimethoxysilane, and the like. These may be used alone or in combination of two or more.

In one embodiment of the present invention, the epoxy siloxane resin may be prepared from an alkoxysilane having an epoxy group alone, but may also be prepared through hydrolysis and condensation reaction between an alkoxysilane having an epoxy group and a different alkoxysilane. But may not be limited.

The alkoxysilane may be at least one selected from the alkoxysilanes represented by the following general formula (2)

(2)

R ³ _m Si (OR ⁴ ) _4-m ;

(Wherein R ³ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, May contain at least one functional group selected from the group consisting of a halogen atom, an amino group, a mercapto group, an ether group, an ester group, a carbonyl group, a carboxyl group, a vinyl group, a nitro group, a sulfone group and an alkyd group,

R ⁴ is a linear or branched alkyl group having 1 to 7 carbon atoms, and m is an integer of 0 to 3).

The alkoxysilane represented by Formula 2 is not particularly limited and includes, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxy Silane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, ethyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxy Silane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-acryloxy-2- hydroxypropyl) 3-acryloxypropylmethylbis (trimethoxy) silane, Acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- Propyltriethoxysilane, 3- (meth) acryloxypropyltripropoxysilane, N- (aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-aminoethyl- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and the like. These may be used alone or in combination of two or more.

The composition for forming a hard coat layer of the present invention uses a (meth) acrylate-based polymerizable compound together with the above epoxy siloxane resin.

The epoxy group of the epoxy siloxane resin is polymerized by cationic polymerization and the (meth) acrylate based polymerizable compound is polymerized by radical polymerization. The inventors of the present invention have found that, in the case of a hard coating layer having a cationic polymerizable monomer, And a hard coat layer having a (meth) acrylate-based polymerizable compound was observed to be formed by radical polymerization.

In the present specification, the term &quot; static &quot; refers to curl when the hard coating layer has a hard coating layer formed thereon, and curl refers to curl when concaved toward the substrate side.

Accordingly, the composition for forming a hard coat layer of the present invention can form a hard coat layer that minimizes curl generation by offsetting both the static and the countercurrent by using the epoxy siloxane resin together with the (meth) acrylate based polymerizable compound.

As the (meth) acrylate-based polymerizable compound, a (meth) acrylate-based oligomer and a (meth) acrylate-based monomer may be used.

As the (meth) acrylate oligomer, epoxy (meth) acrylate, urethane (meth) acrylate and the like are generally used, and urethane (meth) acrylate is more preferable.

Urethane (meth) acrylate can be produced by reacting a compound having a hydroxyl group in a molecule with a compound having a polyfunctional (meth) acrylate and an isocyanate group in the presence of a catalyst.

Specific examples of the (meth) acrylate having a hydroxy group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl Lactone ring-opening hydroxyacrylate, pentaerythritol tri / tetra (meth) acrylate mixture, and dipentaerythritol penta / hexa (meth) acrylate mixture. These may be used alone or in combination of two or more.

Specific examples of the compound having an isocyanate group include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatododecane, Diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) cyclohexane, trans-1,4-cyclohexane diisocyanate, Diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethyl xylene-1, Diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenyl isocyanate), 4,4'-oxybis (phenylisocyanate), hexamethylene diisocyanate , Trifunctional isocyanate derived from trimethylene propanol adduct, toluene diisocyanate It may be a carbonate or the like. These may be used alone or in combination of two or more.

The (meth) acrylate monomer is a commonly used photocurable functional group having in its molecule an unsaturated group such as a (meth) acryloyl group, a vinyl group, a styryl group or an allyl group, and among them, a (meth) acryloyl group It is more preferable to have a photocurable functional group.

Specific examples of the monomer having a (meth) acryloyl group include neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) (Meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipropylene glycol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra , Dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acrylate such as tripentaerythritol hexa (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (meth) acrylate, stearyl (meth) acrylate, tetrahydroperfuryl ) Acrylate, phenoxyethyl (meth) acrylate, isobonol (meth) acrylate, and the like. These may be used alone or in combination of two or more.

The content ratio of the epoxy siloxane resin to the (meth) acrylate based polymerizable compound is not particularly limited and may be suitably selected for curl suppression. For example, the epoxy siloxane resin and the (meth) To 40: 60 to 95 by weight. When the content ratio is within the above range, the curl suppressing effect can be maximized.

The photo cationic initiator may be any photo cationic initiator widely used in the art capable of forming a cation by light irradiation, and may be an onium salt and / or an organic metal salt, but is not limited thereto. Diaryl iodonium salts, triarylsulfonium salts, aryldiazonium salts, iron-arene complexes and the like can be used. These may be used alone or in combination of two or more.

The content of the photo cationic initiator is not particularly limited and may be, for example, 0.01 to 20 parts by weight based on 100 parts by weight of the epoxy siloxane resin. When the content of the photo cationic initiator is within the above range, the curing efficiency of the composition can be kept excellent, and deterioration of physical properties due to the remaining components after curing can be prevented.

The photo radical initiator may be any photo radical initiator widely used in the art capable of forming radicals by light irradiation. Examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, hydroxydimethylacetophenone, dimethylaminoacetophenone, dimethoxy-2-phenylacetophenone, 3-methylacetophenone, 2,2- 2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane, 4-methoxyacetophenone, Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, Benzoquinone, 4,4'-diaminobenzophenone, 4,4'-di (2-hydroxyethoxy) phenyl- Ethyl anthraquinone, 2-t-butyl anthraquinone, 2-amino anthraquinone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, diphenylketonobenzyldimethylketal, acetophenone dimethylketal, p-dimethylaminobenzoic acid ester , 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, fluorene, triphenylamine, carbazole, and the like. These may be used alone or in combination of two or more.

The content of the photo-radical initiator is not particularly limited and may be, for example, 0.01 to 20 parts by weight based on 100 parts by weight of the (meth) acrylate-based polymerizable compound. When the content of the photo-radical initiator is within the above range, the curing efficiency of the composition can be kept excellent, and deterioration of physical properties due to the remaining components after curing can be prevented.

If the content of the radical photoinitiator is less than 0.01 part by weight, the curing rate may become slow and the curing may be difficult to proceed. If the content of the radical photoinitiator is more than 20 parts by weight, the molecular weight of the photopolymerized polymer may be decreased.

The composition for forming a hard coat layer of the present invention further comprises a solvent.

The solvent according to the present invention is not particularly limited and solvents known in the art may be used. Examples of the solvent include alcohols (methanol, ethanol, isopropanol, butanol, methylcellulose, ethylsorbox, etc.) (Hexane, heptane, octane, etc.), benzene series (benzene, toluene, xylene, etc.), and the like Can be used. These may be used alone or in combination of two or more.

The content of the solvent according to the present invention is not particularly limited and may be, for example, 10 to 80 parts by weight based on 100 parts by weight of the epoxy siloxane resin. When the content is less than 10 parts by weight, the workability is deteriorated due to the high viscosity. If the content is more than 80 parts by weight, it is difficult to control the thickness of the coating film during the thick film coating operation, Can fall.

If necessary, the composition for forming a hard coat layer of the present invention may further comprise a thermosetting agent.

The thermosetting agent is a component that makes the hard coat layer made of the composition of the present invention have better hardness and bending properties.

The thermosetting agent may be an amine-based, imidazole-based, acid anhydride-based or amide-based thermosetting agent, and an acid anhydride-based thermosetting agent may be preferably used in view of preventing discoloration and realizing high hardness. These may be used alone or in combination of two or more.

Specific examples of the amine-based thermal curing agent include piperidine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol , Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di (1-methyl-2-aminocyclohexyl) methane, mensenediamine, isophoronediamine, Diaminododecylhexylmethane, 1,3-diaminomethylcyclohexane, xylene diamine, metaphenylene diamine, diaminodiphenylmethane, and diaminodiphenyl sulfone.

Specific examples of the imidazole-based thermosetting agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, ethylimidazole, isopropylimidazole, 2,4-dimethylimidazole, Methyl-2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate and adduct imidazole adduct ) And the like.

Specific examples of the acid anhydride-based thermosetting agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tris trimellitate, maleic anhydride, tetrahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylmethanetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl Cyclohexene dicarboxylic anhydride, chlorendic anhydride anhydride anhydride, anhydrous glutaric acid, methylnadonic anhydride, dichlorosuccinic acid anhydride, and benzophenone tetracarboxylic anhydride.

Among the acid anhydride-based thermosetting agents, thermosetting agents represented by the following formulas (1) to (15) are particularly preferable. These may be used alone or in combination of two or more.

(Wherein n is an integer of 0 to 5, X is an oxygen atom or a methylene group, Ra, Rb, Rc and Rd are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, An alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 18 carbon atoms).

Specific examples of the amide-based thermosetting agent include sulfanilamide, dicyandiamide, polyamide and the like.

The content of the thermosetting agent is not particularly limited and may be, for example, 5 to 30 parts by weight based on 100 parts by weight of the epoxy siloxane resin. When the content of the thermosetting agent is within the above range, the hardening efficiency of the composition is further improved and a hard coating layer having excellent hardness can be formed.

If necessary, the composition for forming a hard coat layer of the present invention may further comprise an inorganic filler for hardness improvement.

The inorganic filler is not particularly limited, and examples thereof include metal oxides such as silica, alumina and titanium oxide; Hydroxides such as aluminum hydroxide, magnesium hydroxide, and potassium hydroxide; Metal particles such as gold, silver, copper, nickel, and alloys thereof; Conductive particles such as carbon, carbon nanotube, and fullerene; Glass; ceramic; And the like, preferably silica. These may be used alone or in combination of two or more.

The particle size of the inorganic filler is not particularly limited, and may be, for example, an average particle diameter of 1 to 100 nm. If the average particle diameter is less than 1 nm, the effect of improving hardness is insufficient. If the average particle diameter is more than 100 nm, it may act as foreign matter of the hard coating layer. Preferably an average particle diameter of 10 to 30 nm.

The content of the inorganic filler according to the present invention is not particularly limited and may be, for example, 0.1 to 5 parts by weight based on 100 parts by weight of the epoxy siloxane resin. If the content is less than 0.1 part by weight, the effect of improving the hardness is insignificant. If the content is more than 5 parts by weight, the coating property may be lowered due to an increase in viscosity.

If necessary, the composition for forming a hard coat layer of the present invention may further comprise a lubricant for improving winding efficiency, blocking resistance, abrasion resistance and scratch resistance.

The type of the lubricant according to the present invention is not particularly limited, and examples thereof include waxes such as polyethylene wax, paraffin wax, synthetic wax or montan wax; Synthetic resins such as silicone resins and fluorine resins; And the like. These may be used alone or in combination of two or more.

The content of the lubricant according to the present invention is not particularly limited and may be, for example, 0.1 to 5 parts by weight based on 100 parts by weight of the epoxy siloxane resin. When the content is within the above range, excellent transparency can be maintained while excellent blocking resistance, abrasion resistance and scratch resistance are imparted.

In addition, if necessary, additives such as an antioxidant, a UV absorber, a light stabilizer, a thermal polymerization inhibitor, a lubricant, a surfactant, a lubricant, and an antifouling agent may be further added.

<Hard Coating Film>

The present invention also provides a hard coating film 100 comprising a substrate 110 having a hard coating layer 120 formed on at least one side thereof with the composition for forming the hard coating layer.

The substrate 110 according to the present invention is preferably excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy and the like. For example, a polyester resin such as polyethylene terephthalate, polyethylene isophthalate and polybutylene terephthalate ; Cellulose-based resins such as diacetylcellulose and triacetylcellulose; Polycarbonate resin; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene-based resins such as polystyrene acrylonitrile-styrene copolymer; Polyolefin resins such as polyolefin resins having polyethylene, polypropylene, cyclo or norbornene structure, and ethylene propylene copolymers; Polyimide resin; Polyaramid based resin; Polyether sulfone type resin; A sulfone-based resin, or the like. These resins may be used alone or in combination of two or more.

The thickness of the substrate 110 is not particularly limited, and may be, for example, 10 to 250 mu m.

The hard coating layer 120 is formed by applying the composition for forming the hard coating layer and curing the coating. The coating is performed by a known method such as die coater, air knife, reverse roll, spray, blade, casting, gravure, .

In the case of curing, the method is not particularly limited, and can be performed, for example, by photocuring or thermosetting alone, or by a method such as thermosetting after photo-curing or photo-curing after thermosetting.

The thickness of the hard coat layer 120 is not particularly limited, and may be, for example, 10 to 100 占 퐉. When the thickness is within the above range, the hard coating layer 120 having almost no curling phenomenon and having excellent hardness can be obtained.

The hard coat layer 120 according to the present invention is formed of the composition for forming the hard coat layer and has a remarkably improved hardness. The hardness may vary depending on the content, the kind, etc. of the individual composition, but may be not less than 5H in pencil hardness, and a maximum of 9H or more in the case of using the respective compositions in the preferable amounts.

In addition, the flexibility is remarkably improved and the warpage is very small.

Since the hard coating film 100 of the present invention has a hard coating layer 120 having a very high surface hardness and excellent flexibility at the same time and is lighter than the tempered glass and has excellent impact resistance, Can be preferably used.

The present invention also provides an image display apparatus having the hard coating film (100).

The hard coating film 100 can be used as an outermost window substrate of an image display device, and the image display device can be used for various image display devices such as a liquid crystal display device, an electroluminescence display device, a plasma display device, .

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples.

Manufacturing example  One

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H2O, Sigma-Aldrich) 250 mL 2 neck flask. Then, 0.1 mL of tetramethylammonium hydroxide was added to the mixture, and 100 mL of methyl ethyl ketone was added thereto, followed by stirring at 60 DEG C for 36 hours. Thereafter, the resultant was filtered using a 0.45 mu m Teflon filter to obtain an alicyclic epoxy siloxane resin. The molecular weight of the alicyclic epoxy siloxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  2

(TMS), phenyltrimethoxysilane (PTMS, Sigma-Aldrich), water (H ₂ O, Sigma-Aldrich) and 12.32 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane g: 12.02 g: 2.70 g (0.05 mol: 0.05 mol: 0.15 mol) were mixed and placed in a 250 mL 2 neck flask. Then, 0.1 mL of tetramethylammonium hydroxide was added to the mixture, and 50 mL of methyl ethyl ketone was added thereto, followed by stirring at 80 DEG C for 24 hours. Thereafter, the resultant was filtered using a 0.45 mu m Teflon filter to obtain an alicyclic epoxy siloxane resin. The molecular weight of the alicyclic epoxy siloxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  3

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H2O, Sigma-Aldrich) 100 mL 2 neck flask. Then, 0.1 mL of tetramethylammonium hydroxide was added to the mixture as a catalyst, and the mixture was stirred at 80 DEG C for 24 hours. Thereafter, the resultant was filtered using a 0.45 mu m Teflon filter to obtain an alicyclic epoxy siloxane resin. The molecular weight of the alicyclic epoxy siloxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  4

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H2O, Sigma-Aldrich) 100 mL 2 neck flask. Then, 0.1 mL of tetramethylammonium hydroxide was added to the mixture, and 100 mL of methyl ethyl ketone was added thereto, followed by stirring at 60 DEG C for 36 hours. Thereafter, the resultant was filtered using a 0.45 mu m Teflon filter to obtain an alicyclic epoxy siloxane resin. The molecular weight of the alicyclic epoxy siloxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  5

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H2O, Sigma-Aldrich) 100 mL 2 neck flask. 1.0 mL of tetramethylammonium hydroxide was added to the mixture, followed by stirring at 70 캜 for 36 hours. Thereafter, the resultant was filtered using a 0.45 mu m Teflon filter to obtain an alicyclic epoxy siloxane resin. The molecular weight of the alicyclic epoxy siloxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  6

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H2O, Sigma-Aldrich) 100 mL 2 neck flask. Then, 0.2 mL of tetramethylammonium hydroxide was added to the mixture, and 50 mL of methyl ethyl ketone was added thereto, followed by stirring at 60 DEG C for 36 hours. Thereafter, the resultant was filtered using a 0.45 mu m Teflon filter to obtain an alicyclic epoxy siloxane resin. The molecular weight of the alicyclic epoxy siloxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  7

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H2O, Sigma-Aldrich) 100 mL 2 neck flask. Then, 0.5 mL of tetramethylammonium hydroxide was added to the mixture, and the mixture was stirred at 80 DEG C for 36 hours. Thereafter, the resultant was filtered using a 0.45 mu m Teflon filter to obtain an alicyclic epoxy siloxane resin. The molecular weight of the alicyclic epoxy siloxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  8

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H2O, Sigma-Aldrich) 100 mL 2 neck flask. Then, 0.05 mL of tetramethylammonium hydroxide was added to the mixture, and 50 mL of methyl ethyl ketone was added thereto, followed by stirring at 50 ° C for 72 hours. Thereafter, the resultant was filtered using a 0.45 mu m Teflon filter to obtain an alicyclic epoxy siloxane resin. The molecular weight of the alicyclic epoxy siloxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  9

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H2O, Sigma-Aldrich) 100 mL 2 neck flask. Then, 0.5 mL of tetramethylammonium hydroxide was added to the mixture, and the mixture was stirred at 70 DEG C for 24 hours. Thereafter, the resultant was filtered using a 0.45 mu m Teflon filter to obtain an alicyclic epoxy siloxane resin. The molecular weight of the alicyclic epoxy siloxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  10

Phenyltrimethoxysilane (PTMS, Sigma-Aldrich) and water (H ₂ O, Sigma-Aldrich) were added to a solution of 11.09 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, g: 13.22 g: 2.70 g (0.045 mol: 0.055 mol: 0.15 mol) were mixed and placed in a 250 mL 2 neck flask. Then, 0.1 mL of tetramethylammonium hydroxide was added to the mixture, and 50 mL of methyl ethyl ketone was added thereto, followed by stirring at 50 ° C for 72 hours. Thereafter, the resultant was filtered using a 0.45 mu m Teflon filter to obtain an alicyclic epoxy siloxane resin. The molecular weight of the alicyclic epoxy siloxane resin was measured by gel permeation chromatography (GPC).

division Mn Mw PDI (Mw / Mn) Equivalent amount of epoxy group (mmol / g) Production Example 1 650 1980 3.05 6.3 Production Example 2 2300 5500 2.39 6.3 Production Example 3 3645 11745 3.22 6.3 Production Example 4 972 2430 2.50 6.3 Production Example 5 4210 8700 2.07 6.3 Production Example 6 1740 6800 3.91 6.3 Production Example 7 1771 5500 3.11 5.2 Production Example 8 2590 10500 4.05 6.3 Production Example 9 2804 5206 1.86 6.3 Production Example 10 1700 5000 2.94 2.84

Example  And Comparative Example

A composition for forming a hard coat layer having the composition and the content shown in Table 2 was prepared.

division Epoxy siloxane resin (Meth) acrylate-based polymerizable compound
(A) Photo cationic initiator
(B) Photo radical initiator
(C) Heat curing agent
(D) menstruum
(E) ingredient Weight portion ingredient Weight portion Weight portion Weight portion Weight portion Weight portion Example 1 Production Example 1 15 A-1 85 2 3 5 35 Example 2 Production Example 2 15 A-1 85 2 3 5 35 Example 3 Production Example 3 15 A-1 85 2 3 5 35 Example 4 Production Example 4 15 A-1 85 2 3 5 35 Example 5 Production Example 5 15 A-1 85 2 3 5 35 Example 6 Production Example 6 15 A-2 85 2 3 5 35 Example 7 Production Example 7 15 A-3 85 2 3 5 35 Example 8 Production Example 3 5 A-1 95 2 3 5 35 Example 9 Production Example 3 40 A-1 60 2 3 5 35 Example 10 Production Example 1 15 A-1 85 2 3 - 35 Example 11 Production Example 1 3 A-1 97 2 3 5 35 Example 12 Production Example 1 50 A-1 50 2 3 5 35 Example 13 Production Example 10 15 A-1 85 2 3 5 35 Comparative Example 1 Production Example 8 15 A-1 85 2 3 5 35 Comparative Example 2 Production Example 9 15 A-1 85 2 3 5 35 Comparative Example 3 Production Example 1 100 - - 10 - 5 35 Comparative Example 4 - - A-1 100 - 5 5 35 A-1: Dipentaerythritol hexaacrylate
A-2: U-15HA (Shin Nakamura, 15-functional urethane acrylate)
A-3: EA-1010 (bisphenol A epoxy acrylate, Shin-Nakamura)
B: (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate
C: 1-hydroxycyclohexyl phenyl ketone
D: methyl-5-norbornene-2,3-dicarboxylic anhydride
E: methyl ethyl ketone

Experimental Example

The composition for forming a hard coat layer of the above Examples and Comparative Examples was applied to a 125um PET film (SKC) using Meyer bar, cured at 100 ° C for 10 minutes, UV-irradiated at 1 J / cm ² using a high pressure mercury lamp, And cured for 10 minutes to prepare a hardcoat film having a hard coat layer of 50 mu m in thickness.

(1) Measurement of pencil hardness

The hardness of the hard coat layer was measured using a pencil hardness meter according to JIS K5600.

(2) Flexibility  evaluation

As shown in FIG. 2, the prepared hard coating film was warped to a cylinder having a bottom radius of R ₁ at 180 ° so that the hard coating layer was inwardly displaced to the inside, and thereafter, a warping trace remained or unevenness, whitening, Gt; R &lt; ₁ &gt;

As shown in FIG. 3, a minimum radius R ₂ was recorded in which a hard coating layer was wound around the cylinder at a base radius of R _{2 at} an angle of 180 ° with respect to the base, and no bending deformation was observed.

(3) Curl measurement

Each hard coating film was cut into 10 cm x 10 cm and stored in a chamber having a temperature of 25 ° C and a relative humidity of 50% for 12 hours, and then placed on a plane, and the maximum value of the distance of one side of each corner from the plane was measured. + In the case of anormal, and - in the case of a backlash.

division Pencil hardness Flexibility (mm) Curl amount (mm) R ₁ R ₂ Example 1 9H 4 10 + 3 Example 2 9H 6 13 + 4 Example 3 9H 9 15 3 Example 4 9H 10 23 + 2 Example 5 9H 8 15 2 Example 6 9H 8 16 + 5 Example 7 8H 10 25 + 3 Example 8 9H 15 30 + 9 Example 9 7H 3 8 5 Example 10 6H 10 16 5 Example 11 8H 21 36 + 13 Example 12 6H 6 13 9 Example 13 7H 15 32 + 20 Comparative Example 1 5H 21 47 6 Comparative Example 2 5H 23 43 15 Comparative Example 3 6H 12 28 123 Comparative Example 4 6H 32 83 Not measurable

Referring to Table 3, it was confirmed that the hard coat layer prepared from the composition of Example exhibited both excellent hardness and flexural strength, and that the curl and the counterbalance were canceled each other and the curl amount was very small.

However, it was confirmed that the hard coat layer prepared from the composition of the comparative example had poor hardness and bending property or had a very large amount of curl.

100: hard coating film 110: substrate
120: hard coat layer

Claims (9)

An epoxy siloxane resin having a weight average molecular weight of 500 to 30,000 and a polydispersion index (PDI) of 2.0 to 4.0; (Meth) acrylate-based polymerizable compound; Photo cationic initiators; And a photo radical initiator.
The composition for forming a hard coat layer according to claim 1, wherein the siloxane resin has a weight average molecular weight of 1,000 to 20,000.
The composition for forming a hard coat layer according to claim 1, wherein the siloxane resin has a weight average molecular weight of 5,000 to 15,000.
The composition for forming a hard coat layer according to claim 1, wherein the siloxane resin has an epoxy equivalent of 3.0 to 6.3 mmol / g.
The composition for forming a hard coat layer according to claim 1, wherein the (meth) acrylate-based polymerizable compound is at least one of a (meth) acrylate oligomer and a (meth) acrylate monomer.
The composition for forming a hard coat layer according to claim 1, wherein the epoxy siloxane resin and the (meth) acrylate based polymerizable compound are contained in a weight ratio of 5 to 40: 60 to 95.
The composition for forming a hard coat layer according to claim 1, further comprising at least one thermosetting agent selected from the group consisting of amine-based, imidazole-based, acid anhydride-based and amide-based thermosetting agents.
A hard coating film comprising a substrate having at least a hard coating layer formed from the composition for forming a hard coating layer according to any one of claims 1 to 7 on at least one side thereof.
An image display apparatus comprising the hard coating film of claim 8.

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