KR20160057221A - Composition for making hard coating layer - Google Patents

Abstract

The present invention relates to a composition for forming a hard coating layer. More particularly, the composition for forming a hard coating layer can maintain a proper range of viscosity by comprising an epoxy siloxane resin having a weight average molecular weight of 800 to 30,000, a crosslinker containing a compound having a particular structure, and a photoinitiator, thereby embodying substantially improved hardening reactivity and spreadability. Also, the composition has excellent hardness and remarkable flexibility, thereby being capable of forming a hard coating layer of which curling is minimized.

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

It is an object of the present invention to provide a hard coating composition having a significantly improved hardening reactivity and coatability while maintaining an appropriate range of viscosity.

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. A composition for forming a hard coat layer comprising an epoxy siloxane resin having a weight average molecular weight of 800 to 30,000, a crosslinking agent containing a compound represented by the following formula (1) and a photoinitiator:

[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 5 carbon atoms,

X is a single bond; Carbonyl group; Carbonate group; Ether group; A thioether group; An ester group; Amide group; A linear or branched alkylene group, an alkylidene group, or an alkoxysilyl group having 1 to 18 carbon atoms; A cycloalkylene group or a cycloalkylidene group having 1 to 6 carbon atoms; Or a linking group thereof;

2. The composition for forming a hard coat layer according to 1 above, wherein the epoxy 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 epoxy 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 item 1, wherein the epoxy siloxane resin has a polydispersion index (PDI) of 2.0 to 4.0.

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

6. The composition for forming a hard coat layer according to 1 above, wherein the crosslinking agent is at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 10:

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(Wherein R is a straight or branched alkylene group having 1 to 8 carbon atoms,

l and m are each independently an integer of 1 to 30).

7. The composition for forming a hard coat layer according to 1 above, wherein the cross-linking agent is contained in an amount of 5 to 150 parts by weight based on 100 parts by weight of the epoxy siloxane resin.

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 composition of the present invention can realize a significantly improved hardening reactivity and application property by maintaining an appropriate range of viscosity.

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.

The present invention relates to a composition for forming a hard coat layer, and more particularly to a composition for forming a hard coat layer, which comprises an epoxy siloxane resin having a weight average molecular weight of 800 to 30,000, a crosslinking agent containing a compound having a specific structure and a photoinitiator, To a composition for forming a hard coat layer which can realize an improved hardening reactivity and coatability, has an excellent hardness, and is excellent in flexibility and can form a hard coat layer with minimized curl.

Hereinafter, the present invention will be described in detail.

< Hard coating layer  Composition for forming &gt;

The composition for forming a hard coat layer of the present invention comprises an epoxy siloxane resin, a photoinitiator and a heat curing agent containing an epoxy compound of a specific structure.

The composition for forming a hard coating layer according to the present invention significantly improves the curing reactivity and coatability by maintaining the viscosity of the composition in an appropriate range by using an epoxy compound having a specific structure as a crosslinking agent together with an epoxy siloxane resin having a specific weight average molecular weight . Further, the hardness of the hard coat layer made of the composition of the present invention can be remarkably improved, and at the same time, the flexibility can be remarkably improved to suppress the flexural deformation.

<Epoxy Siloxane Resin>

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

The epoxy siloxane resin according to the present invention may have 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 according to the present invention is not particularly limited and can be, for example, 2.0 to 4.0. When the polydispersity index of the resin is in the above range, hardness and ductility Are considered to be excellent. On the other hand, if the polydispersity index of the resin is less than 2.0, it is difficult to simultaneously satisfy both 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 epoxy equivalent of the epoxy siloxane resin according to the present invention is not particularly limited, and may be, for example, 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 acryl 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 of the finally formed siloxane compound can be controlled by controlling the reaction rate, and the reaction temperature, the amount of the catalyst, the kind, 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 500 to 30,000 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:

(11)

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 formula (11) 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 (12)

[Chemical Formula 12]

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 12 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.

<Cross-linking agent>

The crosslinking agent according to the present invention includes a compound represented by the following general formula (1), which promotes crosslinking and maintains a proper viscosity of the composition.

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 5 carbon atoms, and X is a single bond; Carbonyl group; Carbonate group; Ether group; A thioether group; An ester group; Amide group; A linear or branched alkylene group, an alkylidene group, or an alkoxysilyl group having 1 to 18 carbon atoms; A cycloalkylene group or a cycloalkylidene group having 1 to 6 carbon atoms; Or a linking group thereof.

In the present specification, the term "single bond" means a structure directly connected without any other functional group. For example, in the above formula (1), two cyclic epoxy structures are directly connected to each other. Means that two or more of the above-mentioned substituents are connected.

In the above formula (1), the substitution position of R ₁ and R ₂ is not particularly limited, but it is more preferably substituted at the position 3 with respect to the carbon to which the epoxy group is connected.

The above-mentioned compounds include a cyclic epoxy structure in the molecule. The epoxy structure is linear as shown in Formula 1, whereby the viscosity of the composition can be lowered to an appropriate range. This lowering of the viscosity not only improves the applicability of the composition but also improves the reactivity of the epoxy group and promotes the curing reaction. It is also believed that they can achieve high hardness through reaction with the epoxy siloxane resin of the present invention.

Specific examples of the compound used in the present invention include, but are not limited to, compounds represented by the following general formulas (2) to (10). These compounds may be used singly or in combination.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the formula, R is a straight or branched alkylene group having 1 to 8 carbon atoms, and 1 and m are each independently an integer of 1 to 30.

The content of the crosslinking agent according to the present invention is not particularly limited and may be, for example, 5 to 150 parts by weight based on 100 parts by weight of the epoxy siloxane resin. When the content of the crosslinking agent is within the above range, it is judged that the viscosity of the composition can be maintained in an appropriate range, and the coating property and the curing reactivity can be remarkably improved.

<Thermal curing agent>

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

The thermosetting agent of the present invention may include an amine type, an imidazole type, an acid anhydride type, an amide type thermosetting agent and the like. In view of preventing discoloration and realizing high hardness, an acid anhydride type thermosetting agent is further preferably used . 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.

<Photo initiator>

As the photoinitiator, a photo cationic initiator capable of initiating polymerization of the epoxy siloxane resin and the epoxy-based monomer may be used.

As the Gwangyang ionic initiator, for example, an onium salt and / or an organic metal salt may be used, but the present invention 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 photoinitiator is not particularly limited, and may be, for example, 1 to 15 parts by weight based on 100 parts by weight of the epoxy siloxane resin. If the content of the photoinitiator is within the above range, the curing efficiency of the composition can be maintained to be excellent, and deterioration of physical properties due to the remaining components after curing can be prevented.

<Solvent>

The composition for forming a hard coat layer of the present invention may further comprise 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.

<Additives>

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>

1, the present invention provides a hard coating film 100 including a substrate 110 having a hard coating layer 120 formed on at least one surface thereof with a composition for forming the hard coating layer, as shown in FIG.

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.

<Image Display Device>

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 (H ₂ O, Sigma-Aldrich) Mixed and placed in a 250 mL 2 neck flask. Then 0.1 mL of tetramethylammonium hydroxide was added to the mixture with 100 mL of the catalyst and MEK, and the mixture was stirred at 60 ° C for 36 hours. Thereafter, the solution was filtered using a 0.45 탆 Teflon filter to obtain a cyclic epoxy silsesquioxane resin. The molecular weight of the cyclic epoxy siloxane resin was measured by GPC (gel permeation chromatography).

Manufacturing example  2

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H ₂ O, Sigma-Aldrich) Mixed and placed in a 250 mL 2 neck flask. Then, 0.1 mL of tetramethylammonium hydroxide was added to the mixture with 50 mL of the catalyst and MEK, and the mixture was stirred at 70 DEG C for 24 hours. Thereafter, the solution was filtered through a 0.45 mu m Teflon filter to obtain a cyclic epoxy silsesquioxane resin. The molecular weight of the cyclic epoxy siloxane resin was measured by GPC (gel permeation chromatography).

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 solution was filtered through a 0.45 mu m Teflon filter to obtain a cyclic epoxy silsesquioxane resin. The molecular weight of the cyclic epoxy siloxane resin was measured by GPC (gel permeation chromatography).

Manufacturing example  4

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H ₂ O, Sigma-Aldrich) Mixed and placed in a 100 mL 2 neck flask. Then 0.1 mL of tetramethylammonium hydroxide was added to the mixture with 100 mL of the catalyst and MEK, and the mixture was stirred at 60 ° C for 36 hours. Thereafter, the solution was filtered through a 0.45 mu m Teflon filter to obtain a cyclic epoxy silsesquioxane resin. The molecular weight of the cyclic epoxy siloxane resin was measured by GPC (gel permeation chromatography).

Manufacturing example  5

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H ₂ O, Sigma-Aldrich) Mixed and placed in a 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 solution was filtered using a 0.45 mu m Teflon filter to obtain a cyclic epoxy siloxane resin. The molecular weight of the cyclic epoxy silsesquioxane 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 (H ₂ O, Sigma-Aldrich) Mixed and placed in a 100 mL 2 neck flask. Then 0.2 mL of tetramethylammonium hydroxide was added to the mixture with 50 mL of the catalyst and MEK, and the mixture was stirred at 60 ° C for 36 hours. Thereafter, the solution was filtered using a 0.45 mu m Teflon filter to obtain a cyclic epoxy siloxane resin. The molecular weight of the cyclic epoxy silsesquioxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  7

(HCI, Sigma-Aldrich), diphenylsilanediol (DPSD, TCI), water (H ₂ O, Sigma-Aldrich), 24.64 g: 2.164 g: 0.1 mol: 0.01 mol: 0.15 mol), and the mixture was placed in a 100 mL 2 neck flask. Then 0.2 mL of tetramethylammonium hydroxide was added to the mixture with 50 mL of the catalyst and MEK, and the mixture was stirred at 60 ° C for 36 hours. Thereafter, the solution was filtered using a 0.45 mu m Teflon filter to obtain a cyclic epoxy siloxane resin. The molecular weight of the cyclic epoxy silsesquioxane resin was measured by gel permeation chromatography (GPC).

Manufacturing example  8

24.64 g: 3.246 ( _{trade name} , manufactured by Sigma-Aldrich) was added to a solution of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI), diphenylsilanediol g: 0.1 mol: 0.015 mol: 0.15 mol), and the mixture was placed in a 100 mL 2 neck flask. Then 0.2 mL of tetramethylammonium hydroxide was added to the mixture with 50 mL of the catalyst and MEK, and the mixture was stirred at 60 ° C for 36 hours. Thereafter, the solution was filtered through a 0.45 mu m Teflon filter to obtain a cyclic epoxy silsesquioxane resin. The molecular weight of the cyclic epoxy siloxane resin was measured by GPC (gel permeation chromatography).

Manufacturing example  9

Diphenylsilanediol (DPSD, TCI), water (H ₂ O, Sigma-Aldrich) was added at 24.64 g: 10.82 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, g: 0.1 mol: 0.05 mol: 0.15 mol), and the mixture was placed in a 100 mL 2 neck flask. Then 0.2 mL of tetramethylammonium hydroxide was added to the mixture with 50 mL of the catalyst and MEK, and the mixture was stirred at 60 ° C for 36 hours. Thereafter, the solution was filtered through a 0.45 mu m Teflon filter to obtain a cyclic epoxy silsesquioxane resin. The molecular weight of the cyclic epoxy siloxane resin was measured by GPC (gel permeation chromatography).

Manufacturing example  10

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H ₂ O, Sigma-Aldrich) Mixed and placed in a 100 mL 2 neck flask. Then, 0.05 mL of tetramethylammonium hydroxide was added to the mixture with 50 mL of the catalyst and MEK, and the mixture was stirred at 70 ° C for 36 hours. Thereafter, the solution was filtered through a 0.45 mu m Teflon filter to obtain a cyclic epoxy silsesquioxane resin. The molecular weight of the cyclic epoxy siloxane resin was measured by GPC (gel permeation chromatography).

Manufacturing example  11

(0.1 mol: 0.15 mol) of 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H ₂ O, Sigma-Aldrich) Mixed and placed in a 100 mL 2 neck flask. Then, 0.5 mL of tetramethylammonium hydroxide was added to the mixture with 50 mL of the catalyst and MEK, and the mixture was stirred at 70 DEG C for 24 hours. Thereafter, the solution was filtered through a 0.45 mu m Teflon filter to obtain a cyclic epoxy silsesquioxane resin. The molecular weight of the cyclic epoxy siloxane resin was measured by GPC (gel permeation chromatography).

division Mn Mw PDI (Mw / Mn) Production Example 1 650 1980 3.05 Production Example 2 2300 5500 2.39 Production Example 3 3645 11745 3.22 Production Example 4 972 2430 2.50 Production Example 5 4210 8700 2.07 Production Example 6 1740 6800 3.91 Production Example 7 1771 5500 3.11 Production Example 8 3560 8560 2.40 Production Example 9 2590 10500 4.05 Production Example 10 2804 5206 1.86 Production Example 11 1210 5320 4.40

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 SSQ resin Cross-linking agent Photoinitiator menstruum ingredient Weight portion ingredient Weight portion ingredient Weight portion ingredient Weight portion Example 1 Production Example 1 50 A-1 5 B 5 D 35 Example 2 Production Example 2 50 A-1 5 B 5 D 35 Example 3 Production Example 3 50 A-1 5 B 5 D 35 Example 4 Production Example 4 50 A-1 5 B 5 D 35 Example 5 Production Example 5 50 A-1 5 B 5 D 35 Example 6 Production Example 6 50 A-1 5 B 5 D 35 Example 7 Production Example 7 50 A-1 5 B 5 D 35 Example 8 Production Example 8 50 A-1 5 B 5 D 35 Example 9 Production Example 2 50 A-1 77 B 5 D 35 Example 10 Production Example 2 50 A-1 One B 5 D 35 Example 11 Production Example 2 50 A-2 5 B 5 D 35 Example 12 Production Example 2 50 A-3 5 B 5 D 35 Example 13 Production Example 2 50 A-4 5 B 5 D 35 Example 14 Production Example 9 50 A-1 5 B 5 D 35 Example 15 Production Example 10 50 A-1 5 B 5 D 35 Example 16 Production Example 11 50 A-1 5 B 5 D 35 Comparative Example 1 Production Example 1 50 - - B 5 D 35 Comparative Example 2 Production Example 2 50 - - B 5 D 35 Comparative Example 3 Production Example 3 50 E 5 B 5 D 35

A-2:

A-3:

A-4:

B: (4-메틸페닐)[4-(2-메틸프로필)페닐]아이오도늄 헥사플루오로포스페이트
D: 메틸에틸케톤
E:

A-1:

A-2:

A-3:

A-4:

B: (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate
D: methyl ethyl ketone
E:

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 70 ° C for 3 minutes, irradiated with UV at 1 J / cm 2 using a high pressure mercury lamp, Followed by curing for one minute to obtain a hard coat layer having a thickness of 50 mu m.

(1) Measurement of pencil hardness

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

(2) Viscosity evaluation

Samples prepared from the above Examples and Comparative Examples were loaded at 0.5 ml at 25 ° C using a RVDV-2T CP Viscometer manufactured by Brookfield Viscometer, and the viscosity of the composition was measured.

division Pencil hardness Viscosity Example 1 9H 52.4 Example 2 9H 59.6 Example 3 9H 68.2 Example 4 9H 57.8 Example 5 9H 64.9 Example 6 9H 62.4 Example 7 8H 59.6 Example 8 8H 63.1 Example 9 6H 18.0 Example 10 6H 48.4 Example 11 8H 83.9 Example 12 8H 82.6 Example 13 8H 80.7 Example 14 7H 67.2 Example 15 6H 59.9 Example 16 6H 57.8 Comparative Example 1 4H 435.5 Comparative Example 2 4H 532.7 Comparative Example 3 3H 172.7

Referring to Table 3, the hard coating composition according to the present invention exhibits excellent hardness and low viscosity. However, it was confirmed that the hard coat layer prepared from the comparative composition had poor hardness characteristics or increased viscosity. Therefore, it can be confirmed that the hard coat layer composition of the present invention is superior in all of hardness and viscosity to the comparative examples.

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

Claims (9)

A composition for forming a hard coat layer comprising an epoxy siloxane resin having a weight average molecular weight of 800 to 30,000, a crosslinking agent containing a compound represented by the following formula (1), and a photoinitiator:
[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 5 carbon atoms,
X is a single bond; Carbonyl group; Carbonate group; Ether group; A thioether group; An ester group; Amide group; A linear or branched alkylene group, an alkylidene group, or an alkoxysilyl group having 1 to 18 carbon atoms; A cycloalkylene group or a cycloalkylidene group having 1 to 6 carbon atoms; Or a linking group thereof;
The composition for forming a hard coat layer according to claim 1, wherein the epoxy 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 epoxy 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 epoxy siloxane resin has a polydispersion index (PDI) of 2.0 to 4.0.
The composition for forming a hard coat layer according to claim 1, wherein the epoxy 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 cross-linking agent is at least one selected from the group consisting of compounds represented by the following Chemical Formulas (2) to (10)
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(Wherein R is a straight or branched alkylene group having 1 to 8 carbon atoms,
l and m are each independently an integer of 1 to 30).
The composition for forming a hard coat layer according to claim 1, wherein the crosslinking agent is contained in an amount of 5 to 150 parts by weight based on 100 parts by weight of the epoxy siloxane resin.
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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