KR20200082886A - Hard-coating composition, hard-coating film and method for preparating the hard-coating film - Google Patents

Abstract

The present invention relates to a hard coating composition, a hard coating film and a method for producing a hard coating film, the hard coating composition according to an embodiment of the present invention is a particle composite, an oligomer composite or a composite comprising the two; 6 monomers; And a photoinitiator.

Description

Hard coating composition, hard coating film and method for manufacturing hard coating film {HARD-COATING COMPOSITION, HARD-COATING FILM AND METHOD FOR PREPARATING THE HARD-COATING FILM}

The present invention relates to a hard coating composition, a hard coating film and a method for producing a hard coating film.

Hard coating films are used for purposes such as surface protection in image display devices such as liquid crystal displays, electroluminescence (EL) displays, plasma displays (PDs), and field emission displays (FEDs).

There is an increasing demand and interest in optical plastic substrates having strength or scratch resistance corresponding to tempered glass while securing flexibility and impact resistance. Typically, optical plastic substrates such as polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyacrylate (PAR), polycarbonate (PC), polyimide (PI), etc. There is a polymer plastic substrate having flexibility compared to glass. Such a polymer plastic substrate has insufficient hardness, scratch resistance, impact resistance, etc., compared to tempered glass used as a window substrate for display protection. In order to solve this problem, various attempts have been made to supplement physical properties by coating a hard coating composition on a plastic substrate.

In general, most of the hard coating composition uses an acrylic-based polyfunctional monomer or polymer, and by adding a photoinitiator to them, the polymer is formed by heat or UV to have a hard coating property. However, they have high hardness properties, but are not suitable for next-generation displays that require flexible properties due to insufficient flexibility as well as disadvantages such as curl caused by shrinkage during curing. In order to solve this shrinkage problem, an improvement method such as adding an acrylic urethane polymer or coating both sides of a film substrate has been studied, but the improvement in curl characteristics is minimal, or cracking occurs easily during transport or coating seams. Deformation may occur, and this results in reduced adhesion to the material, resulting in easy fall off even in slight contact.

Not only high hardness and good scratch resistance, but also 3 to 6 functions as a research on hard coating films that do not crack due to moderate flexibility without curling at the edge of the film during the manufacturing process or use. A high-hardness hard coating composition including a monomer for a binder, an inorganic particle, a photoinitiator, and an organic solvent containing a sex acrylate-based monomer has been studied. However, in the case of such a high-hardness hard coating composition, there was a problem in that bending resistance, in particular, high temperature and high humidity and low temperature resistance to bending, or curling occurred after curing.

The present invention is to solve the above-mentioned problems, the object of the present invention is to improve the film curl properties, can provide excellent hardness and flexibility, a hard coating composition, a hard coating film and a method for producing a hard coating film Is to do.

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the present invention, particle synthesis, oligomer synthesis or a composite comprising the two; 6 monomers; And a photoinitiator; to provide a hard coating composition.

According to one embodiment, the particle composition, the oligomer composition, each, a silica precursor; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; And catalyst; may be to include.

According to one embodiment, the silica precursor is tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TETRAETHYL ORTHOSILICATE; TEOS) tetrapropyl ortho Tetrapropyl orthosilicate (TPOS), tetrabutyl orthosilicate (TBOS), tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane (methyltriethoxysilane), methyl tripropoxysilane, dimethyldimethoxysilane, dimethyldi ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, di Phenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, ethyltri ethoxysilane, propyltrimethoxysilane (propyltrimethoxysilane), vinyltrimethoxysilane, vinyltriethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltrimethoxysilane (N-(3 -acry loxy-2-hydroxypropyl)-3-aminopropyltrimethoxysilane), N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane (N-(3-ac ryloxy-2-hydroxypropyl)-3-aminopropyltriethox ysilane), N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl tripropoxysilane (N-(3-acryloxy-2-hydroxypropyl)-3 -aminopropyl tripropoxysilane), 3-acryloxypropylmethylbis(trimethoxy)silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrie 3-acryloxypropyltriethoxysilane, 3-acryloxypropyl tripropoxysilane, 3-(metal)acryloxypropyl trimethoxysilane (3-(meth)acryloxypropyltrimethoxysilane), 3-(metal) Acryloxypropyl triethoxysilane (3-(meth)acryloxypropyltriethoxysilane), 3-(meth)acryloxy propyltripropoxysilane (3-(meth)acryloxy propyltripropoxysilane), N-(2-aminoethic)- 3-aminopropyl trimethoxysilane (N-(2-aminoethyl)-3-aminopropylt rimethoxysilane), N-(2-aminoethyl)-3-aminopropyl triethoxysilane (N-(2-aminoethyl)-3 -aminopropyltriethox ysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltrimethoxysilane ( It may be one containing at least any one selected from the group consisting of chloropropyltriethoxysilane and cyltrimethoxysilane.

According to one embodiment, the silica precursor, 20% by weight to 30% by weight of the particle composition, the silica precursor may be 0.5% to 3% by weight of the oligomer composition.

According to one embodiment, the monomer containing the epoxy group, (3-glycidyloxypropyl) trimethoxysilane ((3-glycidyloxypropyl)trimethoxysilane; GPTMS), (3-glycidyloxypropyl) triethoxysilane ((3-glycidyloxypropyl)triethoxysilane; GPTES), 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane (2-(3, 4-epoxycyclohexyl)-ethyltrimethoxysilane) and 2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane (2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane). It may be.

According to one embodiment, the monomer containing the (meth)acrylate group is trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, trimethoxysilylpropyl acrylate and triethyl Methoxysilylpropyl acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylenepropyl tri(meth)acrylate, ethylene glycol di (Meth)acrylate, hexanediol di(meth)acrylate, ethyl (meth)acrylate, ethylhexyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, polycaprolactone modified (Meth)acrylate, hydroxyalkyl (meth)acrylate, urethane-modified acrylate oligomer containing 2 to 10 (meth)acrylate groups, epoxy acrylate oligomer and ether acrylate oligomer, 2-ethylhexyl (meth )Acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate , n-octyl (meth) acrylate, isooctyl (meth) acrylate and isononyl (meth) acrylate may include at least one selected from the group consisting of.

According to one embodiment, the epoxy group, (meth) acrylate group or a monomer comprising the two, 10 to 20% by weight of the particle composition, epoxy group, (meth) acrylate group, or both The monomer to be may be 0.5 to 3% by weight of the oligomer composition.

According to one embodiment, the solvent includes water, an organic solvent, or both, and the organic solvent is ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), isopropyl alcohol ( IPA), isopropyl alcohol propanol, isobutyl alcohol, hexanol, cyclohexanol, dimethylacetamide (DMAC), dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), triethylenephosphate (Triethylphosphate), trimethylphosphate, hexane, benzene, toluene, xylene, acetone, methyl ethyl ketone (MEK), ethyl isobutyl ketone (EIBK), methyl isobutyl ketone (MIBK), diethyl ketone, diisobutyl Ketone, ethyl acetate, butyl acetate, dioxane, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl Ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl Acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl Acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxyphene Tyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone , Ethyl isobutyl ketone, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, benzene, toluene, xylene, cyclohexanone, ethylene glycol, diethylene glycol, tetrahydrofuran, 1,4-dioxane and It may include at least one selected from the group consisting of glycerin.

According to one embodiment, the solvent, 49% by weight to 70% by weight of the particle composition, the solvent may be a 93% to 99% by weight of the oligomer composition.

According to one embodiment, the particle composition may be 0% to 10% by weight of the hard coating composition, and the oligomer composition may be 5% to 48% by weight of the hard coating composition.

According to one embodiment, the particle composition may include an acidic catalyst, and the oligomer composition may include an acidic catalyst and a basic catalyst.

According to one embodiment, the acidic catalyst is nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, chlorosulfonic acid, iodic acid, tartaric acid, perchloric acid, polyphosphoric acid, pyrophosphoric acid, para-toluic acid, trichloroacetic acid, formic acid, acetic acid and At least one selected from the group consisting of citric acid, the basic catalyst, sodium hydroxide, potassium hydroxide, ammonia, n-butylamine, di-n-butylamine, tri-n-butylamine, imidazole, perchloric acid It may include at least one selected from the group consisting of ammonium and barium hydroxide.

According to one embodiment, the acidic catalyst is 0.1 wt% to 1 wt% of the particle composition, the acidic catalyst and the basic catalyst, each, may be 0.1 wt% to 1 wt% of the oligomer composition.

According to one embodiment, the six-unit monomer is dipentaerythritol hexa acrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, aliphatic polyurethane hexaacrylate, silicone hexa It may be at least one selected from the group consisting of acrylate (silocone hexaacrylate), polyester hexaacrylate (polyester hexaacrylate) and polyethylene glycol hexaacrylate (Polyethyleneglycol Hexaacrylate).

According to one embodiment, the six-stage monomer may be 40 to 93% by weight of the hard coating composition.

According to one embodiment, the photoinitiator, an onium salt-based, diazonium salt-based, sulfonium salt-based compounds and photocationic initiators selected from imidazole-based; And thioxanthone, phosphorus, triazine, benzophenone, benzoin, oxime, propanone, amino ketone, ketone, benzoin ether acetophenone, anthraquinone and aromatic phosphine oxide compounds It may be to include at least one selected from the group consisting of; radical photoinitiator.

According to one embodiment, the mass ratio of the photocationic initiator to the radical photoinitiator may be 99: 0.1 to 0.1: 99.

According to one embodiment, the photoinitiator may be from 2% to 5% by weight of the hard coating composition.

Another aspect of the present invention comprises the steps of preparing a particle composite, an oligomer composite or a composite comprising both; The particle composite, the oligomer composite, or a composite comprising both; 6 monomers; And a photoinitiator; preparing a hard coating composition by mixing; And photo-curing the hard coating composition. It provides a method of manufacturing a hard coating film comprising a.

According to one embodiment, the particle composition is prepared by a sol-gel reaction, and the sol-gel reaction may be at a temperature of 0°C to 90°C and for 1 hour to 72 hours.

According to an embodiment, the particle composition may include a silica precursor; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; And an acidic catalyst; wherein the oligomer composite comprises: a silica precursor; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; Acid catalysts; And a basic catalyst; may be to include.

According to one embodiment, the step of preparing the oligomer composite comprises: a silica precursor; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; And an acidic catalyst; after mixing, the basic catalyst; may be mixed.

According to one embodiment, the step of photo-curing the hard coating composition, the hard coating composition is an ultraviolet lamp, a metal halide lamp, a mercury ultraviolet lamp, a high pressure mercury lamp, a mercury short arc lamp, a nitrogen laser, a transfer line acceleration device and It may be cured by a light source irradiated by at least one selected from the group consisting of radioactive elements.

Another aspect of the present invention provides a hard coating film formed using the hard coating composition.

According to one embodiment, the pencil hardness of the hard coating film may be 4H or more.

According to one embodiment, the curl by curing shrinkage of the hard coating film may be 40 mm or less.

According to an embodiment, the haze of the hard coating film may be 3% or less.

Another aspect of the present invention provides a flexible display provided with the hard coating film.

The hard coating composition of the present invention provides a hard coating film having excellent hardness while being excellent in curl characteristics due to less shrinkage during curing.

The hard coating film produced by the hard coating composition of the present invention is not formed by simply adding inorganic particles containing an epoxy terminal, but is physically reacted upon curing of the hard coating composition to form a cured portion of the coating. Mechanical properties such as wear resistance, scratch resistance, and pencil hardness can be improved.

The hard coating film of the present invention is applicable to a flexible display.

1 is a flow chart showing the manufacturing process of the hard coating film of the present invention.
2 is a TEM photograph of a hard coating film according to Example 6 of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, various changes may be made to the embodiments, and the scope of the patent application right is not limited or limited by these embodiments. It should be understood that all modifications, equivalents, or substitutes for the embodiments are included in the scope of rights.

The terms used in the examples are used for illustrative purposes only and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, the terms "include" or "have" are intended to indicate the presence of features, numbers, steps, actions, components, parts or combinations thereof described in the specification, one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person skilled in the art to which the embodiment belongs. Terms, such as those defined in a commonly used dictionary, should be interpreted as having meanings consistent with meanings in the context of related technologies, and should not be interpreted as ideal or excessively formal meanings unless explicitly defined in the present application. Does not.

In addition, in the description with reference to the accompanying drawings, the same reference numerals are assigned to the same components regardless of reference numerals, and redundant descriptions thereof will be omitted. In describing the embodiments, when it is determined that detailed descriptions of related known technologies may unnecessarily obscure the subject matter of the embodiments, the detailed descriptions will be omitted.

Hereinafter, the hard coating composition of the present invention, a hard coating film and a method of manufacturing the hard coating film will be described in detail with reference to examples and drawings. However, the present invention is not limited to these examples and drawings.

One aspect of the present invention, particle synthesis, oligomer synthesis or a composite comprising the two; 6 monomers; And a photoinitiator; to provide a hard coating composition.

The hard coating film produced by the hard coating composition of the present invention is not formed by simply adding inorganic particles containing an epoxy terminal, but is physically reacted upon curing of the hard coating composition to form a cured portion of the coating. Mechanical properties such as wear resistance, scratch resistance, and pencil hardness can be improved.

The hard coating composition of the present invention, a particle composite; 6 monomers; And a photoinitiator; or an oligomer composite; 6 monomers; And a photoinitiator, or a particle composite; Oligomer compounds; 6 monomers; And a photoinitiator.

According to one embodiment, the particle composition, the oligomer composition, each, a silica precursor; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; And catalyst; may be to include.

According to one side, the silica precursor is tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TETRAETHYL ORTHOSILICATE; TEOS) tetrapropyl orthosilicate (Tetrapropyl orthosilicate; TPOS), Tetrabutyl orthosilicate (TBOS), Tetramethoxysilane, Tetraethoxysilane, Methyltrimethoxysilane, Methyltriethoxysilane (Methyltriethoxysilane) methyltriethoxysilane, methyl tripropoxysilane, dimethyldimethoxysilane, dimethyldi ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyl Diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, ethyltri ethoxysilane, propyltrimethoxysilane ( propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltrimethoxysilane (N-(3- acry loxy-2-hydroxypropyl)-3-aminopropyltrimethoxysilane), N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (N-(3-acryl oxy-2-hydroxypropyl)-3-aminopropyltriethox ysilane), N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl tripropoxysilane (N-(3-acryloxy-2-hydroxypropyl)-3 -aminopropyl tripropoxysilane), 3-acryloxypropylmethylbis(trimethoxy)silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrie 3-acryloxypropyltriethoxysilane, 3-acryloxypropyl tripropoxysilane, 3-(metal)acryloxypropyl trimethoxysilane (3-(meth)acryloxypropyltrimethoxysilane), 3-(metal) Acryloxypropyl triethoxysilane (3-(meth)acryloxypropyltriethoxysilane), 3-(meth)acryloxy propyltripropoxysilane (3-(meth)acryloxy propyltripropoxysilane), N-(2-aminoethic)- 3-aminopropyl trimethoxysilane (N-(2-aminoethyl)-3-aminopropylt rimethoxysilane), N-(2-aminoethyl)-3-aminopropyl triethoxysilane (N-(2-aminoethyl)-3 -aminopropyltriethox ysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltrimethoxysilane ( It may include at least any one selected from the group consisting of chloropropyltriethoxysilane and cyltrimethoxysilane.

According to one embodiment, the silica precursor may be 20 to 30% by weight of the particle composition. If the silica precursor is less than 20% by weight of the particle composite, it is difficult to form particles, and if it exceeds 30% by weight, large particles are formed to generate haze when forming a coating film.

According to one embodiment, the silica precursor may be 0.5 wt% to 3 wt% of the oligomer composition. If the silica precursor is less than 0.5% by weight of the oligomer composite, resination is difficult, and if it exceeds 3% by weight, the molecular weight increases to form a polymer.

According to one embodiment, the monomer comprising the epoxy group may be a monomer, oligomer, polymer or block copolymer comprising a repeating unit comprising an epoxy functional silane group and/or a repeating unit comprising an epoxy functional silane. For example, the particle composite can be a product that is polymerized and bonded in a sol-gel reaction between epoxy functional silanes.

According to one embodiment, the monomer containing the epoxy group, the epoxy group can participate in photocuring can improve the wear resistance, at the same time, it is possible to suppress the curl of the hard coat film obtained by reducing the curing shrinkage of the hard coating composition .

According to one embodiment, the monomer containing the epoxy group is (3-glycidyloxypropyl) trimethoxysilane ((3-glycidyloxypropyl)trimethoxysilane; GPTMS), (3-glycidyloxypropyl) triethoxy Silane((3-glycidyloxypropyl)triethoxysilane; GPTES), 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane (2-(3 ,4-epoxycyclohexyl)-ethyltrimethoxysilane) and 2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane (2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane). It may be included.

According to one embodiment, the monomer containing the (meth)acrylate group, the terminal of the branched structure may be substituted for the (meth)acrylate group to be used for ultraviolet curing, the center of which is completely aliphatic and tertiary ester bond It has structural features that are made. Therefore, the monomer containing the (meth)acrylate group has a structural characteristic that has more functional groups compared to the molecular weight according to the increase in generation compared to the general multifunctional acrylate monomer, and the functional group is distributed at the ends, thereby bending the core portion upon curing. It can contribute to improving properties. Accordingly, a high hardness hard coating film with improved curl and flexibility can be obtained.

According to one embodiment, the monomer containing the (meth)acrylate group is trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, trimethoxysilylpropyl acrylate and triethyl Methoxysilylpropyl acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylenepropyl tri(meth)acrylate, ethylene glycol di (Meth)acrylate, hexanediol di(meth)acrylate, ethyl (meth)acrylate, ethylhexyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, polycaprolactone modified (Meth)acrylate, hydroxyalkyl (meth)acrylate, urethane-modified acrylate oligomer containing 2 to 10 (meth)acrylate groups, epoxy acrylate oligomer and ether acrylate oligomer, 2-ethylhexyl (meth )Acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate , n-octyl (meth) acrylate, isooctyl (meth) acrylate and isononyl (meth) acrylate may include at least one selected from the group consisting of.

According to one embodiment, the epoxy group, (meth) acrylate group or a monomer comprising the two may be 10 to 20% by weight of the particle composition. When the epoxy group, (meth)acrylate group, or a monomer containing both of them is included in less than 10% by weight of the particle composition, the epoxy functional group is insufficient to harden the hard coating composition, thereby improving the effect of improving hardness. It may be difficult to obtain and if it exceeds 20% by weight, it may deteriorate in particle formation.

According to one embodiment, the epoxy group, (meth) acrylate group or a monomer comprising the two may be 0.5 to 3% by weight of the oligomer composition. When the epoxy group, (meth)acrylate group, or a monomer containing the two is included in less than 3% by weight during the synthesis of the oligomer, it may be difficult to obtain a curl improving effect due to lack of an epoxy functional group, and more than 3% by weight Oligomer formation can be reduced.

According to one embodiment, the weight average molecular weight of the epoxy group, (meth)acrylate group or a monomer comprising the two is 1,000 or more; 1,000 to 500,000; 1,000 to 100,000; Or it may be 1,000 to 50,000 km. When included in the above range, it is possible to provide a hard coating composition having excellent hardness and light transmittance.

According to one embodiment, the solvent includes water, an organic solvent, or both, and the organic solvent is ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), isopropyl alcohol ( IPA), isopropyl alcohol propanol, isobutyl alcohol, hexanol, cyclohexanol, dimethylacetamide (DMAC), dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), triethylenephosphate (Triethylphosphate), trimethylphosphate, hexane, benzene, toluene, xylene, acetone, methyl ethyl ketone (MEK), ethyl isobutyl ketone (EIBK), methyl isobutyl ketone (MIBK), diethyl ketone, diisobutyl Ketone, ethyl acetate, butyl acetate, dioxane, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl Ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl Acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl Acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxyphene Tyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone , Ethyl isobutyl ketone, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, benzene, toluene, xylene, cyclohexanone, ethylene glycol, diethylene glycol, tetrahydrofuran, 1,4-dioxane and It may include at least one selected from the group consisting of glycerin.

According to one embodiment, the solvent, 49% by weight to 70% by weight of the particle composition, the solvent may be a 93% to 99% by weight of the oligomer composition. If the solvent is less than 49% by weight of the particle composite and the oligomer composite, the particle dispersion stability is poor, thereby reducing the formation of a uniform coating film, and if it is more than 70% by weight, it is difficult to adjust the thickness of the film, the curing time is delayed, and drying Staining may result in poor appearance. When the solvent is included in the content range of the particle composite and the oligomer composite, an appropriate viscosity and fluidity for coating on the substrate of the hard coating composition may be secured, and a hard coating composition having excellent hardness and flexibility may be provided.

According to one embodiment, the particle composition may be 0 to 10% by weight of the hard coating composition. When the particle composition is less than 0% by weight of the hard coating composition, mechanical properties such as abrasion resistance, scratch resistance, and pencil hardness may not be sufficient, and when it is more than 10% by weight, the refractive index of the film prepared from the hard coating composition is misaligned Haze may occur, and not only the optical properties may deteriorate, but also the mechanical properties may deteriorate.

According to one embodiment, the oligomer composition may be 5% to 48% by weight of the hard coating composition. When the oligomer composition is less than 5% by weight of the hard coating composition, it is difficult to obtain an improvement effect of the film curl phenomenon upon curing, and when it is more than 48% by weight, it may be difficult to secure excellent light transmittance and hardness.

According to one embodiment, the particle composition may include an acidic catalyst, and the oligomer composition may include an acidic catalyst and a basic catalyst.

According to one embodiment, the acidic catalyst is nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, chlorosulfonic acid, iodic acid, tartaric acid, perchloric acid, polyphosphoric acid, pyrophosphoric acid, para-toluic acid, trichloroacetic acid, formic acid, acetic acid and At least one selected from the group consisting of citric acid, the basic catalyst, sodium hydroxide, potassium hydroxide, ammonia, n-butylamine, di-n-butylamine, tri-n-butylamine, imidazole, perchloric acid It may include at least one selected from the group consisting of ammonium and barium hydroxide.

According to an embodiment, the acidic catalyst may be 0.1 wt% to 1 wt% of the particle composition. If the acidic catalyst is less than 0.1% by weight of the particle composition, there may be a problem that particle formation is not possible, and if it is more than 1% by weight, particles having a large size may be formed, which may cause haze during coating. have.

According to one embodiment, each of the acidic catalyst and the basic catalyst, may be 0.1% to 1% by weight of the oligomer composition. The acidic catalyst and the basic catalyst, respectively, may have a problem that the speed of the sol-gel (SOL-GEL) reaction is slower and oligomer formation is difficult when it is less than 0.1% by weight of the oligomer composition, and when it is more than 1% by weight, the sol-gel There may be a problem of gelation due to an increase in the reaction rate of (SOL-GEL).

According to one embodiment, the acidic catalyst can increase the hydrolysis rate by increasing the reactivity of silane and water under acidic conditions, and increase the polymerization reaction rate between silanes. That is, the acidic catalyst can increase the reaction rate of the sol-gel reaction and cause polymerization. The basic catalyst may be to control the gelation reaction in addition to the acidic catalyst.

According to one embodiment, the six-unit monomer is dipentaerythritol hexa acrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, aliphatic polyurethane hexaacrylate, silicone hexa It may be at least one selected from the group consisting of acrylate (silocone hexaacrylate), polyester hexaacrylate (polyester hexaacrylate) and polyethylene glycol hexaacrylate (Polyethyleneglycol Hexaacrylate).

According to one embodiment, the six-stage monomer may be 40 to 93% by weight of the hard coating composition. When the amount of the six-stage monomer is less than 40% by weight of the hard coating composition, there is a fear that photo-curing may not be sufficiently performed, and a problem that the hardness decreases may occur. If it is more than 93% by weight, curls and cracks may occur in the hard coating film prepared by the hard coating composition.

According to one embodiment, the photoinitiator may include a photocationic initiator, a radical photoinitiator, or both.

According to one embodiment, the photocationic initiator may include at least one selected from the group consisting of onium salt-based, diazonium salt-based, sulfonium salt-based compounds, and imidazole-based. For example, the photocationic initiator, diphenyliodonium, 4-methoxydiphenyliodonium, bis(4-methylphenyl)iodonium, bis (4-tert-butylphenyl) iodonium (bis(4-tert-butylphenyl)iodonium), bis(dodecylphenyl)iodonium, bis(dodecylphenyl)iodonium), (4-methylphenyl)[(4-(2- Diaryl iodonium, triphenylsulfonium, diphenyl-4-thiophenylphenylsulfonium, such as methylpropyl)phenyl)iodinium(4-methylphenyl)[(4-(2-methylpropyl)phenyl)iodonium] triarylsulfonium such as (diphenyl-4-thiophenylphenylsulfonium), diphenyl-4-thiophenoxyphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide( bis [4- (diphenylsulfonio) phenyl] sulfide) of a cation and hexafluoro such as phosphate (PF ₆ ^-), tetrafluoroborate (BF ₄ ^-), anti-hexafluoro-Mo carbonate (SbF ₆ ^-), hexafluorophosphate are Senate (AsF ₆ ^-), hexachloro antimonate (SbCl ₆ ^-), and onium salts containing anions such as, triarylsulfonium perfluoroalkyl sulfonate, triarylsulfonium triflate, triaryl alcohol Phonium nona plate, diaryl iodonium nona plate, succinimidyl triflate, 2,6-dinitrobenzyl sulfonate, and the like.

According to one embodiment, a photocationic initiator; And thioxanthone, phosphorus, triazine, benzophenone, benzoin, oxime, propanone, amino ketone, ketone, benzoin ether acetophenone, anthraquinone and aromatic phosphine oxide compounds It may be to include at least one selected from the group. For example, the radical photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylanono acetophenone , 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone , 2-hydroxy-2-methyl-1-phenylpropan-1one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane- 1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, 4,4-diaminobenzophenone, p-phenylbenzophenone, 4,4' -Diethylaminobenzophenone, 4,4-dimethoxyacetophenone, dichlorobenzophenone, 3-methylacetophenone, 4-knoacetophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2- t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Benzyldimethylketal, acetophenone dimethylketal, p-dimethylamino benzoic acid ester, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], bis(2,4, 6-trimethylbenzoyl)-phenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]2-morpholinpropanone- 1, diphenylketone benzyldimethylketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenylketone, dimethoxy-2-phenylatotophenone, fluorene, triphenylamine , Carbazole, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, 2-benzyl-2- (Dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, benzoin methyl ether, benzoin isopropyl ether, anisoin methyl ether, 2-methyl-2-hydroxypropy Ophenone, bis(2, 4, 6-trimethylbenzoyl)phenyl phosphine oxide, 2-naphthalene-sulfonyl chloride, 1-phenyl-1,2-propanedione-2( O-ethoxycarbonyl) oxime, and the like.

According to one embodiment, the mass ratio of the photocationic initiator to the radical photoinitiator may be 99: 0.1 to 0.1: 99. When included in the mixing ratio, it can absorb various wavelengths to promote reactivity to increase the curing rate, and improve the light transmittance and curl properties after curing of the hard coating composition.

According to one embodiment, the photoinitiator may be from 2% to 5% by weight of the hard coating composition. If the photoinitiator is less than 2% by weight of the hard coating composition, hardening of the hard coating composition is not sufficiently achieved and thus it is difficult to secure an appropriate hardness, and when it exceeds 5% by weight, cracks and hard coating layers after curing of the hard coating composition by curing shrinkage Peeling, etc. may occur.

The hard coating composition according to an embodiment of the present invention may further include an additive, and the additive may include one or more selected from the group consisting of a leveling agent, a UV stabilizer, and a heat stabilizer, but is not limited thereto. , It may further include additives commonly used in the art.

According to one embodiment, the leveling agent may be added to impart smoothness and coatability of the coating film when coating the hard coating composition. The leveling agent may be a commercially available silicone leveling agent, a fluorine leveling agent, an acrylic polymer leveling agent, etc., for example, BYK-323, BYK-331, BYK-333, BYK- 337, BYK-373, BYK-375, BYK-377, BYK-378, TEGO Glide 410, TEGO Glide 411, TEGO Glide 415, TEGO Glide 420, TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, TEGO Glide 450, TEGO Glide 455, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, 3M's FC-4430, FC-4432, Shin-Etsu KY-1203, etc. can be used, but are not limited to this. Does not.

According to one embodiment, since the surface of the cured coating film is decomposed by continuous UV exposure, and discolored and deteriorates well, the UV stabilizer may be added for the purpose of protecting the coating film by blocking or absorbing such ultraviolet light. The ultraviolet stabilizers are classified into absorbers, quenchers, and hindered amine light stabilizers (HALS) according to the mechanism of action. Also, depending on the chemical structure, it can be classified into phenyl salicylates (absorbent), benzophenone (absorbent), benzotriazole (absorbent), nickel derivatives (quenching agent), and radical scavengers. Can. In the present invention, the ultraviolet stabilizer that does not significantly change the initial color of the coating film is not particularly limited.

According to one embodiment, the thermal stabilizer is a commercially applicable product, and the primary heat stabilizer may be a polyphenol-based, a secondary heat stabilizer, a phosphite-based, or a lactone-based, respectively, or may be used in combination.

Another aspect of the invention, the step of preparing a particle composite; Preparing an oligomer composite; The particle composite, the oligomer composite or a composite comprising the two; 6 monomers; And a photoinitiator; preparing a hard coating composition by mixing; And photo-curing the hard coating composition. It provides a method of manufacturing a hard coating film comprising a.

1 is a flow chart showing the manufacturing process of the hard coating film of the present invention. Referring to FIG. 1, the manufacturing process of the hard coating film of the present invention includes a composite production step 110, a hard coating composition production step 120, and a hard coating composition photocuring step 130.

According to one embodiment, the composite production step 110 includes preparing a particle composite, an oligomer composite or a composite comprising both.

According to one embodiment, the manufacturing step of the particle composite is to prepare a particle composite, wherein the particle composite comprises: a silica precursor; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; And acid catalyst; may be to include. Since the specific type of each composition is described above, detailed description is omitted.

According to one embodiment, the particle composition is prepared by a sol-gel reaction, and the sol-gel reaction may be at a temperature of 0°C to 90°C and for 1 hour to 72 hours. For example, silica precursor; Epoxy group, (meth) acrylate group or a monomer comprising the two; by mixing or dissolving them in a solvent to prepare a reaction mixture, the reaction mixture is heated to 30 ℃ to 90 ℃, and the heated reaction mixture The sol-gel reaction may be performed by adding an acid catalyst to prepare a particle composite.

According to one embodiment, the manufacturing step of the oligomer composition is to prepare an oligomer composite, wherein the oligomer composite comprises: a silica precursor; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; Acid catalysts; And a basic catalyst; may be to include. Since the specific type of each composition is described above, detailed description is omitted.

According to one embodiment, the step of preparing the oligomer composite comprises: a silica precursor; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; And an acidic catalyst; after mixing, the basic catalyst; may be mixed. For example, silica precursor; Epoxy group, (meth) acrylate group or a monomer comprising the two; by mixing or dissolving them in a solvent to prepare a reaction mixture, the reaction mixture is heated to 30 ℃ to 90 ℃, and the heated reaction mixture After adding an acid catalyst, a basic catalyst may be sequentially added to prepare an oligomer composite. The basic catalyst may be added to control the gelation reaction.

According to one embodiment, the hard coating composition production step 120 may be to mix the particle composite, the oligomer composite, a six-step monomer and a photoinitiator.

According to an embodiment, in the step 130 of photo-curing the hard coating composition, the hard coating composition may include an ultraviolet lamp, a metal halide lamp, a mercury ultraviolet lamp, a high pressure mercury lamp, a mercury short arc lamp, a nitrogen laser, and a transfer line. It may be cured by a light source irradiated by at least one selected from the group consisting of an accelerator and a radioactive element.

According to one embodiment, the irradiation amount of the light source is an integrated exposure amount at an ultraviolet wavelength of about 365 nm, and may be 50 mJ/cm ² to 5000 mJ/cm ² . When dose a, 50 mJ / cm ² is less than, and the curing can be the hardness of the hard coating layer decreases not be sufficiently achieved in some cases have the hard coating layer colored in the case exceeds 5000 mJ / cm ² that transparency may decrease.

Another aspect of the present invention provides a hard coating film formed using the hard coating composition. The hard coating film, while having excellent hardness and flexibility, has a high light transmittance.

The hard coating film according to an embodiment of the present invention may be a coating layer comprising a cured product of the hard coating composition described above on one or both sides of a transparent substrate. Any transparent polymer film may be used as the transparent substrate.

As used herein, the expression "transparent" means that the transmittance of visible light is 70% or more, for example, 80% or more, and specifically 80% to 100%. In addition, it may also include a case where the entire area is not transparent and the aperture ratio is 60% or more.

According to one embodiment, the polymer film may be prepared by a film forming method or an extrusion method according to a molecular weight and a film manufacturing method, and may be used regardless of a commercially available transparent polymer film, for example, triacetyl cellulose, Acetyl cellulose butylate, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose or polyester, polystyrene, polyamide, polyetherimide, polyacrylic, polyimide, polyethersulfone, Polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene tere And various transparent polymer substrates such as phthalate, polybutylene terephthalate, polyethylene naphthalate, and polycarbonate.

According to one embodiment, when applied to a crystalline polymer substrate, engineering plastic substrate, a polymer substrate whose surface has been changed to hydrophilicity by hydrolysis or saponification, it is possible to increase adhesion without deteriorating mechanical properties after coating, and the polymer substrate When the plasma or corona treatment is performed to coat the hard coating composition of the present invention, adhesion may be further increased.

According to an embodiment, the thickness of the transparent substrate is not particularly limited, but may be 8 μm to 1000 μm, specifically 40 μm to 100 μm. When the thickness of the base film is within the above range, the strength of the film is high, and the processability is excellent, the phenomenon that transparency is lowered can be prevented, and the weight of the hard coating film is reduced.

The hard coating film according to an embodiment of the present invention can be prepared by applying and curing the hard coating composition of the present invention on one or both surfaces of a transparent substrate to form a coating layer.

The hard coating composition according to an embodiment of the present invention is suitably coated using a known method such as a die coater, air knife, reverse roll, spray, blade, casting, gravure, micro gravure, spin coating, etc. (Coating Process) ) Is possible.

According to one embodiment, after the hard coating composition is applied to the transparent substrate, the volatiles are evaporated to dry at a temperature of 30° C. to 150° C. for 10 seconds to 1 hour, more specifically 30 seconds to 10 minutes. And then irradiating a light source irradiated by at least one selected from the group consisting of ultraviolet lamps, metal halide lamps, mercury ultraviolet lamps, high pressure mercury lamps, mercury short arc lamps, nitrogen lasers, transfer line accelerators, and radioactive elements. Harden. The irradiation amount of the light source may be specifically 50 mJ/cm ² to 5000 mJ/cm ² .

According to one embodiment, the thickness of the coating layer to be formed may be specifically 3 μm to 200 μm, specifically 5 μm to 100 μm, and more specifically 10 μm to 30 μm. When the thickness of the coating layer is included within the above range, it is possible to manufacture a hard coating film having excellent hardness and flexible properties, thinning, and almost no curling.

According to one embodiment, the pencil hardness of the hard coating film may be 4H or more.

According to one embodiment, the curl by curing shrinkage of the hard coating film may be 40 mm or less.

According to an embodiment, the haze of the hard coating film may be 3% or less.

The hard coating film of the present invention has a high hardness and high durability with little flexibility while introducing flexibility by introducing a silane having an epoxy functional group with low shrinkage during curing.

Another aspect of the present invention provides a flexible display provided with the hard coating film. The hard coating film is excellent in hardness and flexibility and has high light transmittance, and thus can be applied to a flexible display.

In addition to the flexible display, the hard coating of the present invention can also be attached to a polarizing plate, a touch sensor, and the like.

The hard coating film according to an embodiment of the present invention may be used in a reflective, transmissive, semi-transmissive LCD or various driving type LCDs such as TN, STN, OCB, HAN, VA, and IPS. In addition, the hard coating film according to an embodiment of the present invention can be used in various image display devices such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, electronic paper, and the like.

Hereinafter, the present invention will be described in more detail by examples. However, the following examples are only for illustrating the present invention, and the contents of the present invention are not limited to the following examples.

Preparation of particle composites

Tetraethyl orthosilicate (TEOS) 24 wt% and 3-(glycidylpropyl)trimethoxysilane (GPRMS) 11 wt% were added to 57 wt% of n-butanol and stirred. After sufficient stirring, 7.5% by weight of distilled water was added and stirred for 20 minutes. Next, after the temperature was raised to 80° C., the reaction proceeded for 1 hour and 30 minutes when the temperature stabilized. .

Preparation of oligomer compounds

0.1% by weight of nitric acid was added to 93% by weight of ethanol and stirred to increase the temperature to 60°C. After sufficient stirring, tetraethyl orthosilicate (TEOS) 0.6 wt%, 3-(glycidylpropyl) trimethoxysilane (GPRMS) 3 wt% mixed solution was added, and after 1 minute and 30 seconds, ammonia water 2.9 wt. % (Including distilled water) and the reaction was carried out for 3 hours.

Preparation of hard coating composition

0 to 10% by weight of the prepared particle composition, 5 to 48% by weight of oligomer, 40 to 93% by weight of dipentaerythritol hexaacrylate as a 6-unit monomer, and 5% by weight of cationic initiator Omnicat-250 for 1 hour It was stirred to prepare a photo-curable hard coating composition.

Preparation of hard coating film

The hard coating composition was coated on a 100 μm PET film substrate using a bar coater and dried at 80° C. for 1 minute to evaporate the solvent, followed by photocuring with a UV curing machine to form a coating layer. After curing was completed, a hard coating film coated with a thickness of 20 μm was obtained.

[Comparative Examples, Examples 1 to 5]

Comparative examples, the hard coating films of Examples 1 to 5 were prepared by including 6 monomers, oligomer compounds, and curing agents in numerical values shown in Table 1 below.

[Examples 6 to 10]

The hard coating films of Examples 6 to 10 were prepared by including 6 monomers, oligomer compounds, and particle compositions in numerical values shown in Table 2 below.

6 steps
Monomer Oligomer Hardener Hardness Curl
(mm) Example 1 95% 5% 5% of solid content 4H >50 Example 2 90% 10% 4H >40 Example 3 80% 20% 4H 24 Example 4 70% 30% 4H 9 Example 5 60% 40% 4H 8.3 Comparative example 50% 50% 2H 35

6 steps
Monomer Oligomer particle
(Compared to monomer + oligomer) Hardness Curl
(mm) Example 6 60% 40% 0% 4H 8.3 Example 7 3% 4H 10 Example 8 5% 5H 15 Example 9 7% 5H 17 Example 10 10% 4H 30

Property evaluation

Table 1 shows the pencil hardness and film curl of the hard coating films prepared in Examples and Comparative Examples.

(1) pencil hardness

The surface hardness of the hard coating film was measured using a pencil hardness tester (KP-M5000M, KEE-PAE TRADING CO). According to the pencil hardness test described in ASTM D 3363, the surface hardness was confirmed when a standard pencil was tilted at 45° under a constant load (750 g) and scratches were applied at a rate of 50 mm/min. 5 times per pencil hardness.

(2) Film curl

The hard coating film was cut to a size of 10 cm × 10 cm to prepare a test piece. After standing at 25°C 48 RH% for 24 hours, the height average of the four corners from the bottom was measured. The rise length (mm) of the test piece from the glass plate at four corners was measured. The average value of these measurements was used as an indicator of curl evaluation.

Referring to Table 1 above, it can be seen that the hard coating films of Examples 1 to 5 did not add a particle composite, but maintained only hardness and improved curl even if only the oligo composite was added. However, as in the comparative example, when the mixing ratio of the 6-unit monomer and oligomer compound is 50%: 50%, it can be confirmed that the hardness is lowered and a lot of curling occurs.

Looking at Table 2, it can be seen that the hard coating film prepared by using the hard coating compositions according to Examples 6 to 10 of the present invention suppresses curl generation when the particle composite is added and has excellent hardness.

2 is a TEM photograph of a hard coating film according to Example 6 of the present invention. As shown in Figure 2, it can be seen that the particles are formed on the hard coating film. The hard coating film prevents a lot of curls by the particles and the hardness can be improved.

As described above, although the embodiments have been described by the limited drawings, those skilled in the art can apply various technical modifications and variations based on the above. For example, even if the described techniques are performed in a different order than the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or replaced by another component or equivalent Appropriate results can be achieved.

Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (28)

Particle composites, oligomeric composites, or composites comprising both;
6 monomers; And
Photoinitiators;
Containing,
Hard coating composition.
According to claim 1,
The particle composite, oligomer composite, each,
Silica precursors;
Epoxy groups, (meth)acrylate groups, or monomers comprising both;
solvent; And
catalyst;
That includes,
Hard coating composition.
According to claim 2,
The silica precursor includes: tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TETRAETHYL ORTHOSILICATE; TEOS) tetrapropyl orthosilicate (Tetrapropyl orthosilicate; TPOS) ), Tetrabutyl Orthosilicate (TBOS), Tetramethoxysilane, Tetraethoxysilane, Methyltrimethoxysilane, Methyltriethoxysilane, Methyltriethoxysilane Methyl tripropoxysilane, dimethyldimethoxysilane, dimethyldi ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane ), diphenyldiethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, ethyltri ethoxysilane, propyltrimethoxysilane, vinyl tree Methoxysilane (vinyltrimethoxysilane), vinyl triethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl trimethoxysilane (N-(3-acry loxy-2- hydroxypropyl)-3-aminopropyltrimethoxysilane), N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane (N-(3-acryloxy-2-hydr) oxypropyl)-3-aminopropyltriethox ysilane), N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl tripropoxysilane (N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl tripropoxysilane) , 3-acryloxypropylmethylbis(trimethoxy)silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane (3 -acryloxypropyltriethoxysilane, 3-acryloxypropyl tripropoxysilane, 3-(metal)acryloxypropyl trimethoxysilane, 3-(meth)acryloxypropyl Triethoxysilane (3-(meth)acryloxypropyltriethoxysilane), 3-(meth)acryloxy propyltripropoxysilane (3-(meth)acryloxy propyltripropoxysilane), N-(2-aminoethic)-3-aminopropyl Trimethoxysilane (N-(2-aminoethyl)-3-aminopropylt rimethoxysilane), N-(2-aminoethyl)-3-aminopropyl triethoxysilane (N-(2-aminoethyl)-3-aminopropyltriethox ysilane) , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane and site It includes at least any one selected from the group consisting of cyltrimethoxysilane,
Hard coating composition.
According to claim 2,
The silica precursor, 20 to 30% by weight of the particle composition,
The silica precursor is 0.5% to 3% by weight of the oligomer composition,
Hard coating composition.
According to claim 2,
The monomer containing the epoxy group,
(3-glycidyloxypropyl) trimethoxysilane (GPTMS), (3-glycidyloxypropyl) triethoxysilane (GPTES), 3- 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 2-(3, 4-Epoxycyclohexyl)-ethyl triethoxysilane (2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane)) to include at least one selected from the group consisting of,
Hard coating composition.
According to claim 2,
The monomer containing the (meth)acrylate group,
Trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, trimethoxysilylpropyl acrylate and triethoxysilylpropyl acrylate, dipentaerythritol hexa(meth)acrylate, penta Erythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylenepropyl tri(meth)acrylate, ethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, ethyl (meth) )Acrylate, ethylhexyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, polycaprolactone modified (meth)acrylate, hydroxyalkyl (meth)acrylate, (meth) Urethane-modified acrylate oligomers containing 2 to 10 acrylate groups, epoxy acrylate oligomers and ether acrylate oligomers, 2-ethylhexyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate and It includes at least one selected from the group consisting of isononyl (meth)acrylate,
Hard coating composition.
According to claim 1,
Epoxy group, (meth) acrylate group, or a monomer comprising the two, 10 to 20% by weight of the particle composition,
Epoxy group, (meth) acrylate group or a monomer comprising the two, 0.5 to 3% by weight of the oligomer composition,
Hard coating composition.
According to claim 1,
The solvent includes water, an organic solvent or both,
The organic solvent is ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), isopropyl alcohol (IPA), isopropyl alcohol propanol, isobutyl alcohol, hexanol, cyclohexanol, dimethylacetic acid Amide (DMAC), dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), triethylenephosphate, trimethylphosphate, hexane, benzene, toluene, xylene, acetone, methyl Ethyl ketone (MEK), ethyl isobutyl ketone (EIBK), methyl isobutyl ketone (MIBK), diethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, dioxane, diethyl ether, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Propyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol mono Methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate -Methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxy Butyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3 -Methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate , 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, benzene, toluene, xyl To include at least one selected from the group consisting of ren, cyclohexanone, ethylene glycol, diethylene glycol, tetrahydrofuran, 1,4-dioxane and glycerin,
Hard coating composition.
According to claim 1,
The solvent is 49% to 70% by weight in the particle composition,
The solvent is 93% to 99% by weight of the oligomer composition,
Hard coating composition.
According to claim 1,
The particle composition is 0% to 10% by weight of the hard coating composition,
The oligomer composition is 5% to 48% by weight of the hard coating composition,
Hard coating composition.
According to claim 2,
The particle composition includes an acidic catalyst,
The oligomer composition, which includes an acidic catalyst and a basic catalyst,
Hard coating composition.
The method of claim 11,
The acid catalyst is selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, chlorosulfonic acid, iodic acid, tartaric acid, perchloric acid, polyphosphoric acid, pyrophosphoric acid, para-toluic acid, trichloroacetic acid, formic acid, acetic acid and citric acid. At least any one of which,
The basic catalyst, at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, n-butylamine, di-n-butylamine, tri-n-butylamine, imidazole, ammonium perchlorate, barium hydroxide To include,
Hard coating composition.
The method of claim 11,
The acid catalyst, 0.1 to 1% by weight of the particle composition,
The acidic catalyst and the basic catalyst, each of which is 0.1% to 1% by weight of the oligomer composition,
Hard coating composition.
According to claim 1,
The six monomers are dipentaerythritol hexa acrylate, dipentaerythritol hexamethacrylate, aliphatic polyurethane hexaacrylate, and silicone hexaacrylate. , It includes at least one selected from the group consisting of polyester hexaacrylate (polyester hexaacrylate) and polyethylene glycol hexaacrylate (Polyethyleneglycol Hexaacrylate),
Hard coating composition.
According to claim 1,
The 6-monomer is 40 to 93% by weight of the hard coating composition,
Hard coating composition.
According to claim 1,
The photoinitiator,
A photocationic initiator selected from an onium salt system, a diazonium salt system, a sulfonium salt system compound, and an imidazole system; And
Thioxanthone, phosphorus, triazine, benzophenone, benzoin, oxime, propanone, amino ketone, ketone, benzoin ether acetophenone, anthraquinone and aromatic phosphine oxide compounds Radical photoinitiator;
It comprises at least one selected from the group consisting of,
Hard coating composition.
The method of claim 16,
The mass ratio of the photocationic initiator to the radical photoinitiator is 99: 0.1 to 0.1: 99 is mixed,
Hard coating composition.
According to claim 1,
The photoinitiator is 2% to 5% by weight of the hard coating composition,
Hard coating composition.
A hard coating film formed using the hard coating composition according to any one of claims 1 to 18.
The method of claim 19,
The pencil hardness of the hard coating film is 4H or more,
Hard coating film.
The method of claim 19,
The hard coating film is cured by curing shrinkage (curl) is 40 mm or less,
Hard coating film.
The method of claim 19,
The haze of the hard coating film is 3% or less,
Hard coating film.
Preparing a particle composite, an oligomeric composite, or a composite comprising both;
The particle composite, the oligomer composite or a composite comprising the two; 6 monomers; And a photoinitiator; preparing a hard coating composition by mixing; And
Photocuring the hard coating composition;
Containing,
Method of manufacturing a hard coating film.
The method of claim 23,
The step of preparing the particle composite is prepared by a sol-gel reaction,
The sol-gel reaction is a temperature of 0 ℃ to 90 ℃ and is made for 1 hour to 72 hours,
Method of manufacturing a hard coating film.
The method of claim 23,
The particle composition may include a silica precursor; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; And an acidic catalyst;
The oligomer composite may include a silica precursor; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; Acid catalysts; And a basic catalyst;
Method of manufacturing a hard coating film.
The method of claim 20,
The step of preparing the oligomer composite,
Silica precursors; Epoxy groups, (meth)acrylate groups, or monomers comprising both; solvent; And an acidic catalyst; after mixing, the basic catalyst;
Method of manufacturing a hard coating film.
The method of claim 20,
The step of photocuring the hard coating composition,
The hard coating composition is a UV lamp, a metal halide lamp, a mercury UV lamp, a high pressure mercury lamp, a mercury short arc lamp, a nitrogen laser, a transfer line accelerator, and a light source irradiated by at least one selected from the group consisting of radioactive elements To be cured by
Method of manufacturing a hard coating film.
Flexible display provided with a hard coating film according to claim 19.

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