KR102655508B1 - 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 manufacturing a hard coating film. The hard coating composition according to an embodiment of the present invention includes a particle composite, an oligomer composite, or a composite containing both; 6-unit monomer; and a photoinitiator.

Description

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

The present invention relates to hard coating compositions, hard coating films, and methods for producing hard coating films.

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

Demand for and interest in optical plastic substrates that secure flexibility and impact resistance while also having strength or scratch resistance equivalent to tempered glass is increasing. Typically, optical plastic substrates are reinforced with polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyacrylate (PAR), polycarbonate (PC), and polyimide (PI). There is a polymer plastic substrate that is more flexible than glass. These polymer plastic substrates have insufficient hardness, scratch resistance, and impact resistance compared to tempered glass used as a window substrate for display protection. In order to solve this problem, various attempts are being made to improve the physical properties by coating the plastic substrate with a hard coating composition.

In general, hard coating compositions mostly use acrylic-based multifunctional monomers or polymers, and hard coating properties are achieved by adding a photoinitiator to these to form a polymer by heat or UV. However, although they have high hardness characteristics, they have disadvantages such as curl phenomenon due to shrinkage during curing, as well as insufficient flexibility, so they are not suitable for next-generation displays that require flexible characteristics. To solve this shrinkage problem, improvement methods such as adding acrylic urethane polymer or coating both sides of the film substrate are being studied, but the improvement in curl characteristics is minimal, cracks easily occur during bending or transport, and coating joints are damaged. Deformation may occur, and as a result, the adhesion to the material is reduced, resulting in the material falling off easily at the slightest contact.

Research into a hard coating film that not only has high hardness and good scratch resistance, but also does not cause curling of the film edges during the manufacturing process or use, and has appropriate flexibility to prevent cracks, has been developed to provide 3 to 6 sensory properties. A high-hardness hard coating composition containing a binder monomer containing an acrylate-based monomer, inorganic particles, a photoinitiator, and an organic solvent was studied. However, in the case of such high hardness hard coating compositions, there was a problem of poor bending resistance, especially high temperature, high humidity and low temperature bending resistance, or curling after curing.

The present invention is to solve the above-mentioned problems, and the purpose of the present invention is to provide a hard coating composition, a hard coating film, and a method for producing a hard coating film, which has improved film curl properties and can exhibit excellent hardness and flexibility. It is done.

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

One aspect of the present invention is a particle composite, an oligomeric composite, or a composite containing both; 6-unit monomer; And a photoinitiator; It provides a hard coating composition containing a.

According to one embodiment, the particle composite and the oligomeric composite each include a silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; and a catalyst.

According to one embodiment, the silica precursor is tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TETRAETHYL ORTHOSILICATE (TEOS)), tetrapropyl ortho Silicate (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-aminopropyltriethoxysilane (N-(3-acryloxy-2-hydroxypropyl)- 3-aminopropyltriethox ysilane), N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl tripropoxysilane (N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl tripropoxysilane), 3- 3-acryloxypropylmethylbis(trimethoxy)silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane , 3-acryloxypropyl tripropoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(metal)acryloxypropyltriethoxy Silane (3-(meth)acryloxypropyltriethoxysilane), 3-(meth)acryloxy propyltripropoxysilane, N-(2-aminoethic)-3-aminopropyl trimethoxy Silane (N-(2-aminoethyl)-3-aminopropylt rimethoxysilane), N-(2-aminoethyl)-3-aminopropyltriethoxysilane (N-(2-aminoethyl)-3-aminopropyltriethox ysilane), 3- 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane and citrimethoxysilane It may contain at least one selected from the group consisting of (cyltrimethoxysilane).

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

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

According to one embodiment, the monomers containing the (meth)acrylate group include trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, trimethoxysilylpropyl acrylate, and triethoxysilylpropyl acrylate. Toxysilylpropyl acrylate, dipentaerythol hexa(meth)acrylate, pentaerythol tetra(meth)acrylate, pentaerythol tri(meth)acrylate, trimethylene propyl 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.

According to one embodiment, the monomer containing an epoxy group, a (meth)acrylate group, or both is 10% to 20% by weight of the particle composite, and includes an epoxy group, a (meth)acrylate group, or both. The monomer may be present in an amount of 0.5% to 3% by weight in the oligomer composite.

According to one embodiment, the solvent includes water, an organic solvent, or both, and the organic solvent includes ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), and isopropyl alcohol ( IPA), isopropyl alcohol propanol, isobutyl alcohol, hexanol, cyclohexanol, dimethylacetamide (DMAC), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), triethylene phosphate (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-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, xylene, cyclo It may include at least one selected from the group consisting of hexanone, ethylene glycol, diethylene glycol, tetrahydrofuran, 1,4-dioxane, and glycerin.

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

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

According to one embodiment, the particle composite may include an acidic catalyst, and the oligomer composite 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 It contains at least one selected from the group consisting of citric acid, and the basic catalyst is sodium hydroxide, potassium hydroxide, ammonia, n-butylamine, di-n-butylamine, tri-n-butylamine, imidazole, and perchloric acid. It may contain at least one selected from the group consisting of ammonium and barium hydroxide.

According to one embodiment, the acidic catalyst may be 0.1% to 1% by weight of the particle composite, and the acidic catalyst and the basic catalyst may each be 0.1% to 1% by weight of the oligomer composite.

According to one embodiment, the 6-unit monomer is dipentaerythritol hexa acrylate, dipentaerythritol hexamethacrylate, aliphatic polyurethane hexaacrylate, and silicone hexaacrylate. It may include at least one selected from the group consisting of acrylate (silocone hexaacrylate), polyester hexaacrylate, and polyethylene glycol hexaacrylate.

According to one embodiment, the 6-unit monomer may be 40% to 93% by weight of the hard coating composition.

According to one embodiment, the photoinitiator is a photocationic initiator selected from onium salts, diazonium salts, sulfonium salts, and imidazoles; and thioxanthone-based, phosphorus-based, triazine-based, benzophenone-based, benzoin-based, oxime-based, propanone-based, amino ketone-based, ketone-based, benzoin ether acetophenone-based, anthraquinone-based and aromatic phosphine oxide-based compounds. It may include at least one selected from the group consisting of a 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 2% to 5% by weight of the hard coating composition.

Another aspect of the present invention includes preparing a particle composite, an oligomeric composite, or a composite containing both; the particle composite, the oligomer composite, or a composite containing both; 6-unit monomer; and a photoinitiator; preparing a hard coating composition by mixing; and photocuring the hard coating composition. It provides a method for producing a hard coating film, including a step.

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

According to one embodiment, the particle composite includes a silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; and an acidic catalyst; and the oligomer composite includes a silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; acid catalyst; and a basic catalyst.

According to one embodiment, the step of preparing the oligomer composite includes: a silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; and an acidic catalyst; and then mixing the basic catalyst.

According to one embodiment, the step of photocuring the hard coating composition includes 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 accelerator, and It may be hardened 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 hard coating film may have a pencil hardness of 4H or higher.

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

According to one embodiment, the hard coating film may have a haze of 3% or less.

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

The hard coating composition of the present invention provides a hard coating film with excellent curl characteristics and excellent hardness due to low shrinkage upon curing.

In the hard coating film manufactured by the hard coating composition of the present invention, inorganic particles containing epoxy terminals are not simply physically added, but are formed in the hardened portion of the coating by chemically reacting when the hard coating composition is cured. 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 flexible displays.

1 is a flowchart showing the manufacturing process of the hard coating film of the present invention.
Figure 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 attached drawings. However, various changes can be made to the embodiments, so the scope of the patent application is not limited or limited by these embodiments. It should be understood that all changes, equivalents, or substitutes for the embodiments are included in the scope of rights.

The terms used in the examples are for descriptive purposes only and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by a person of ordinary skill in the technical field to which the embodiments belong. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and unless explicitly defined in the present application, should not be interpreted in an ideal or excessively formal sense. No.

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

Hereinafter, the hard coating composition, hard coating film, and manufacturing method of the hard coating film of the present invention 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 is a particle composite, an oligomeric composite, or a composite containing both; 6-unit monomer; And a photoinitiator; It provides a hard coating composition containing a.

In the hard coating film manufactured by the hard coating composition of the present invention, inorganic particles containing epoxy terminals are not simply physically added, but are formed in the hardened portion of the coating by chemically reacting when the hard coating composition is cured. Mechanical properties such as wear resistance, scratch resistance, and pencil hardness can be improved.

The hard coating composition of the present invention is a particle composite; 6-unit monomer; and a photoinitiator; or an oligomeric composite; 6-unit monomer; and a photoinitiator, or a particle composite; oligomeric composite; 6-unit monomer; and a photoinitiator.

According to one embodiment, the particle composite and the oligomeric composite each include a silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; and a catalyst.

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, methyl tripropoxysilane, dimethyldimethoxysilane, dimethyldi ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyl Dimethoxysilane, 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-acryloxy-2-hydroxypropyl)-3 -aminopropyltriethox ysilane), N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl tripropoxysilane (N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl tripropoxysilane), 3-acryl 3-acryloxypropylmethylbis(trimethoxy)silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyl tripropoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(metal)acryloxypropyltriethoxysilane (3-(meth)acryloxypropyltriethoxysilane), 3-(meth)acryloxy propyltripropoxysilane), N-(2-aminoethic)-3-aminopropyl trimethoxysilane (N-(2-aminoethyl)-3-aminopropylt rimethoxysilane), N-(2-aminoethyl)-3-aminopropyltriethoxysilane (N-(2-aminoethyl)-3-aminopropyltriethox ysilane), 3-amino 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane and citrimethoxysilane ( It may contain at least one selected from the group consisting of cyltrimethoxysilane)

According to one embodiment, the silica precursor may be 20% to 30% by weight of the particle composite. 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 and haze is generated when forming a coating film.

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

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

According to one embodiment, the monomer containing the epoxy group can improve wear resistance because the epoxy group can participate in photocuring, and can suppress curling of the hard coat film obtained by reducing the curing shrinkage rate of the hard coating composition. .

According to one embodiment, the monomer containing the epoxy group is (3-glycidyloxypropyl)trimethoxysilane (GPTMS), (3-glycidyloxypropyl)triethoxy Silane ((3-glycidyloxypropyl)triethoxysilane; GPTES), 3-glycidoxypropylmethyldiethoxysilane (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 include

According to one embodiment, the monomer containing the (meth)acrylate group can be used for ultraviolet curing by replacing the terminal of the branched structure with a (meth)acrylate group, and the center is completely aliphatic and formed by a tertiary ester bond. It has structural characteristics. Therefore, the monomer containing the (meth)acrylate group has the structural characteristic of having more functional groups compared to the molecular weight as the generation increases compared to the general multifunctional acrylate monomer, and the core portion is bent during curing due to the distribution of functional groups at the terminals. It can contribute to improving characteristics. As a result, a high hardness hard coating film with improved curl and flexibility can be obtained.

According to one embodiment, the monomers containing the (meth)acrylate group include trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, trimethoxysilylpropyl acrylate, and triethoxysilylpropyl acrylate. Toxysilylpropyl acrylate, dipentaerythol hexa(meth)acrylate, pentaerythol tetra(meth)acrylate, pentaerythol tri(meth)acrylate, trimethylene propyl 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.

According to one embodiment, the monomer containing an epoxy group, a (meth)acrylate group, or both may be 10% by weight to 20% by weight of the particle composite. When the monomer containing the epoxy group, (meth)acrylate group, or both is included in less than 10% by weight of the particle composite, the curing of the hard coating composition is not sufficient due to the lack of the epoxy functional group, thereby reducing the effect of improving hardness. It may be difficult to obtain and may inhibit particle formation if it exceeds 20% by weight.

According to one embodiment, the monomer containing the epoxy group, (meth)acrylate group, or both may be 0.5% by weight to 3% by weight of the oligomer composite. If the monomer containing the epoxy group, (meth)acrylate group, or both is included in less than 3% by weight during the oligomer synthesis, it may be difficult to obtain a curl improvement effect due to the lack of the epoxy functional group, and if it is more than 3% by weight, Oligomer formation may be reduced.

According to one embodiment, the weight average molecular weight of the monomer containing an epoxy group, a (meth)acrylate group, or both is 1,000 or more; 1,000 to 500,000; 1,000 to 100,000; Or it may be 1,000 to 50,000. If it is within the above range, a hard coating composition with excellent hardness and light transmittance can be provided.

According to one embodiment, the solvent includes water, an organic solvent, or both, and the organic solvent includes ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), and isopropyl alcohol ( IPA), isopropyl alcohol propanol, isobutyl alcohol, hexanol, cyclohexanol, dimethylacetamide (DMAC), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), triethylene phosphate (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-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, xylene, cyclo It may include at least one selected from the group consisting of hexanone, ethylene glycol, diethylene glycol, tetrahydrofuran, 1,4-dioxane, and glycerin.

According to one embodiment, the solvent may be 49% to 70% by weight of the particle composite, and the solvent may be 93% to 99% by weight of the oligomer composite. If the solvent is less than 49% by weight of the particle composite and the oligomer composite, particle dispersion stability may decrease, which may reduce the formation of a uniform coating film. If the solvent is more than 70% by weight, it is difficult to adjust the thickness of the film, curing time is delayed, and drying occurs. Staining may occur and cause appearance defects. When the solvent is included within the above content range in the particle composite and the oligomer composite, appropriate viscosity and fluidity for coating on the substrate of the hard coating composition can be secured and a hard coating composition having excellent hardness and flexibility can be provided.

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

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

According to one embodiment, the particle composite may include an acidic catalyst, and the oligomer composite 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 It contains at least one selected from the group consisting of citric acid, and the basic catalyst is sodium hydroxide, potassium hydroxide, ammonia, n-butylamine, di-n-butylamine, tri-n-butylamine, imidazole, and perchloric acid. It may contain at least one selected from the group consisting of ammonium and barium hydroxide.

According to one embodiment, the acidic catalyst may be 0.1% to 1% by weight of the particle composite. If the acid catalyst is less than 0.1% by weight of the particle composite, there may be a problem of particle formation, and if it is more than 1% by weight, large-sized particles may be formed and haze may occur during coating. there is.

According to one embodiment, each of the acidic catalyst and the basic catalyst may be 0.1% to 1% by weight of the oligomer composite. If each of the acidic catalyst and the basic catalyst is less than 0.1% by weight in the oligomer composite, there may be a problem of slowing down the sol-gel (SOL-GEL) reaction and difficulty forming oligomers, and if it is more than 1% by weight, sol-gel There may be gelation problems due to increased reaction speed 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. In other words, an acidic catalyst can increase the reaction rate of the sol-gel reaction and cause polymerization. The basic catalyst may be one that controls the gelation reaction in addition to the acid catalyst.

According to one embodiment, the 6-unit monomer is dipentaerythritol hexa acrylate, dipentaerythritol hexamethacrylate, aliphatic polyurethane hexaacrylate, and silicone hexaacrylate. It may include at least one selected from the group consisting of acrylate (silocone hexaacrylate), polyester hexaacrylate, and polyethylene glycol hexaacrylate.

According to one embodiment, the 6-unit monomer may be 40% to 93% by weight of the hard coating composition. If the amount of the 6-unit monomer is less than 40% by weight in the hard coating composition, there is a risk that photocuring may not be sufficiently achieved, and a problem of reduced hardness may occur. If the content exceeds 93% by weight, curls and cracks may occur in the hard coating film manufactured with 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 compounds, diazonium salt-based compounds, sulfonium salt-based compounds, and imidazole-based compounds. For example, the photocationic initiator is diphenyliodonium, 4-methoxydiphenyliodonium, bis(4-methylphenyl)iodonium, bis(4-methylphenyl)iodonium, (4-tert-butylphenyl)iodonium (bis(4-tert-butylphenyl)iodonium), bis(dodecylphenyl)iodonium), (4-methylphenyl)[(4-(2- Diaryliodonium, triphenylsulfonium, diphenyl-4-thiophenylphenylsulfonium, such as methylpropyl)phenyl)iodonium (4-methylphenyl) [(4-(2-methylpropyl)phenyl)iodonium] (diphenyl-4-thiophenylphenylsulfonium), triarylsulfonium such as diphenyl-4-thiophenoxyphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide ( Cations such as bis[4-(diphenylsulfonio)phenyl]sulfide) and hexafluorophosphate (PF ₆ ^- ), tetrafluoroborate (BF ₄ ^- ), hexafluoroantimonate (SbF ₆ ^- ), and hexafluoro It is an onium salt containing anions such as arsenate (AsF ₆ ^- ) and hexachloroantimonate (SbCl ₆ ^- ), and includes triaryl sulfonium perfluoroalkyl sulfonate, triaryl sulfonium triflate, and triaryl sulfonate. It may be phonium nonaflate, diaryliodonium nonaflate, succinimidyl triflate, 2,6-dinitrobenzyl sulfonate, etc., but is not limited thereto.

According to one embodiment, a photocationic initiator; and thioxanthone-based, phosphorus-based, triazine-based, benzophenone-based, benzoin-based, oxime-based, propanone-based, amino ketone-based, ketone-based, benzoin ether acetophenone-based, anthraquinone-based and aromatic phosphine oxide-based compounds. It may include at least one selected from the group. For example, the radical photoinitiator is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylanino 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-khnoloacetophenone, 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-morpholine propanone- 1, diphenyl ketone benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylatetophenone, 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 etc., but is not limited thereto.

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 above mixing ratio, it absorbs various wavelengths and promotes reactivity to increase curing speed, and can improve light transmittance and curl characteristics after curing of the hard coating composition.

According to one embodiment, the photoinitiator may be 2% to 5% by weight of the hard coating composition. If the photoinitiator is less than 2% by weight of the hard coating composition, the hard coating composition is not sufficiently cured, making it difficult to secure appropriate hardness, and if it exceeds 5% by weight, cracks and hard coating layer occur after curing of the hard coating composition due to 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, an ultraviolet stabilizer, and a heat stabilizer, but is not limited thereto. , may further include additives commonly used in the technical field.

According to one embodiment, the leveling agent may be added to provide smoothness and coating properties to the coating film when coating the hard coating composition. The leveling agent may be a commercially available silicone type leveling agent, a fluorine type leveling agent, an acrylic polymer type leveling agent, etc., for example, BYK Chemistry's 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 in Daegu 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's KY-1203, etc. can be used, but are not limited to these. No.

According to one embodiment, the UV stabilizer may be added for the purpose of protecting the coating film by blocking or absorbing such UV rays because the surface of the cured coating film decomposes due to continuous exposure to UV rays, causing discoloration and brittleness. The UV stabilizers are classified into absorbers, quenchers, and hindered amine light stabilizers (HALS) depending on their mechanism of action. Also, depending on the chemical structure, it can be divided into Phenyl Salicylates (absorbent), Benzophenone (absorbent), Benzotriazole (absorbent), Nickel Derivative (quencher), and Radical Scavenger. You can. In the present invention, there is no particular limitation as long as the UV stabilizer does not significantly change the initial color of the coating film.

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

Another aspect of the invention includes preparing a particle composite; Preparing an oligomeric composite; a composite comprising the particle composite, the oligomer composite, or both; 6-unit monomer; and a photoinitiator; preparing a hard coating composition by mixing; and photocuring the hard coating composition. It provides a method for producing a hard coating film, including a step.

1 is a flowchart showing the manufacturing process of the hard coating film of the present invention. Referring to Figure 1, the manufacturing process of the hard coating film of the present invention includes a composite manufacturing step (110), a hard coating composition manufacturing step (120), and a hard coating composition photocuring step (130).

According to one embodiment, the composite preparation step 110 includes preparing a particulate composite, an oligomeric composite, or a composite comprising both.

According to one embodiment, the particle composite manufacturing step involves manufacturing a particle composite, wherein the particle composite includes: a silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; and an acidic catalyst. Since the specific types of each composition are described above, detailed description is omitted.

According to one embodiment, the particle composite is manufactured by a sol-gel reaction, and the sol-gel reaction may be carried out at a temperature of 0 ° C to 90 ° C and for 1 hour to 72 hours. For example, silica precursors; A reaction mixture is prepared by mixing or dissolving a monomer containing an epoxy group, a (meth)acrylate group, or both in a solvent, heating the reaction mixture to 30° C. to 90° C., and adding the mixture to the heated reaction mixture. A particle composite may be produced by adding an acid catalyst to proceed with a sol-gel reaction.

According to one embodiment, the step of preparing an oligomer composite is to prepare an oligomer composite, wherein the oligomer composite includes: a silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; acid catalyst; and a basic catalyst. Since the specific types of each composition are described above, detailed description is omitted.

According to one embodiment, the step of preparing the oligomer composite includes: a silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; and an acidic catalyst; and then mixing the basic catalyst. For example, silica precursors; A reaction mixture is prepared by mixing or dissolving a monomer containing an epoxy group, a (meth)acrylate group, or both in a solvent, heating the reaction mixture to 30° C. to 90° C., and adding the mixture to the heated reaction mixture. An oligomer composite may be prepared by adding an acid catalyst and then sequentially adding a basic catalyst. The basic catalyst may be added to control the gelation reaction.

According to one embodiment, the hard coating composition manufacturing step 120 may involve mixing the particle composite, the oligomer composite, a 6-unit monomer, and a photoinitiator.

According to one embodiment, the step 130 of photocuring the hard coating composition is performed by using an ultraviolet lamp, a metal halide lamp, a mercury ultraviolet lamp, a high-pressure mercury lamp, a mercury short arc lamp, a nitrogen laser, or a transfer line. It may be hardened 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 the integrated exposure amount at an ultraviolet ray wavelength of about 365 nm, and may be 50 mJ/cm ² to 5000 mJ/cm ² . If the irradiation amount is less than 50 mJ/cm ² , hardness of the hard coating layer may decrease due to insufficient curing, and if it exceeds 5000 mJ/cm ² , the hard coating layer may be colored and transparency may be reduced.

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

The hard coating film according to an embodiment of the present invention may be one in which a coating layer containing the cured product of the hard coating composition described above is formed on one or both sides of a transparent substrate. Any transparent polymer film can 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, specifically 80% to 100%. In addition, cases where the entire area is not transparent and the aperture ratio is 60% or more may be included.

According to one embodiment, the polymer film can be manufactured by a film forming method or an extrusion method depending on the molecular weight and film manufacturing method, and any commercially available transparent polymer film can be used, for example, triacetyl cellulose, Acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, or polyester, polystyrene, polyamide, polyetherimide, polyacrylic, polyimide, polyether sulfone, Polysulfone, polyethylene, polypropylene, polymethyl pentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terelate. Various transparent polymer substrates include phthalate, polybutylene terephthalate, polyethylene naphthalate, and polycarbonate.

According to one embodiment, when applied to a crystalline polymer substrate, an engineering plastic substrate, or a polymer substrate whose surface has become hydrophilic due to hydrolysis or saponification, where it is difficult to provide adhesion after coating, the adhesion can be increased without deteriorating mechanical properties, and the polymer substrate If the hard coating composition of the present invention is coated by plasma or corona treatment, the adhesion can be further increased.

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

The hard coating film according to one embodiment of the present invention can be manufactured by applying the hard coating composition of the present invention to one or both sides of a transparent substrate and curing it to form a coating layer.

The hard coating composition according to one embodiment of the present invention is coated on a transparent substrate using known methods such as die coater, air knife, reverse roll, spray, blade, casting, gravure, micro gravure, and spin coating. ) is possible.

According to one embodiment, after applying the hard coating composition to the transparent substrate, the volatiles are evaporated and dried at a temperature of 30 ℃ to 150 ℃ for 10 seconds to 1 hour, more specifically for 30 seconds to 10 minutes. Then, irradiated with a light source irradiated by at least one selected from the group consisting of 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 beam accelerator, and a radioactive element. Harden. The irradiation amount of the light source may specifically be 50 mJ/cm ² to 5000 mJ/cm ² .

According to one embodiment, the thickness of the coating layer formed may be specifically 3 ㎛ to 200 ㎛, specifically 5 ㎛ to 100 ㎛, and more specifically 10 ㎛ to 30 ㎛. When the thickness of the coating layer is within the above range, it is possible to manufacture a hard coating film that has excellent hardness and flexible properties, can be thinned, and rarely causes curling.

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

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

According to one embodiment, the hard coating film may have a haze of 3% or less.

The hard coating film of the present invention is flexible by introducing silane with an epoxy functional group that shrinks less when cured, has high hardness with little curl, and is excellent in durability.

Another aspect of the present invention provides a flexible display equipped with the hard coating film. The hard coating film has excellent hardness and flexibility and high light transmittance, so it can be applied to flexible displays.

In addition to flexible displays, the hard coating of the present invention can also be used by attaching it to polarizers, touch sensors, etc.

The hard coating film according to an embodiment of the present invention can be used in LCDs of various driving types such as reflective, transmissive, and transflective LCDs, or TN type, STN type, OCB type, HAN type, VA type, and IPS type. Additionally, the hard coating film according to one 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, and electronic papers.

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

Preparation of particle composites

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

Preparation of oligomeric composites

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

Preparation of hard coating composition

0-10% by weight of the prepared particle composite, 5-48% by weight of oligomer, 40-93% by weight of dipentaerythol hexaacrylate as a 6-unit monomer, and 5% by weight of Omnicat-250 as a cationic initiator were combined for 1 hour. A photo-curable hard coating composition was prepared by stirring.

Manufacturing of hard coating film

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

[Comparative Example, Examples 1 to 5]

Comparative Examples: The hard coating films of Examples 1 to 5 were prepared containing 6 monomers, oligomer compounds, and curing agents in the values shown in Table 1 below.

[Examples 6 to 10]

The hard coating films of Examples 6 to 10 were manufactured containing 6 monomers, oligomer composites, and particle composites in the values shown in Table 2 below.

6 units
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 units
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

Physical property evaluation

The pencil hardness and film curl of the hard coating films prepared in Examples and Comparative Examples were evaluated and are shown in Table 1.

(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, surface hardness was confirmed when a standard pencil was scratched at a speed of 50 mm/min under a constant load (750 g) while tilted at 45°. This was done 5 times per pencil hardness.

(2) Film curl

A test piece was produced by cutting the hard coating film into 10 cm × 10 cm sizes. After being left at 25°C48 RH% for 24 hours, the average height of the four corners from the floor was measured. The rise length (mm) of the test piece from the glass plate was measured at the four corners. The average value of these measured values was used as an index for curl evaluation.

Referring to Table 1, it can be seen that the hardness is maintained and curl is improved even when the hard coating films of Examples 1 to 5 are manufactured by adding only the oligocomposition without adding the particle composite. However, as in the comparative example, it can be seen that when the mixing ratio of the 6-unit monomer and oligomer composite is 50%:50%, the hardness decreases and a lot of curls occur.

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

Figure 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 confirmed that particles were formed in the hard coating film. The particles prevent the hard coating film from curling and improve hardness.

Although the embodiments have been described with limited drawings as described above, 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 than the described method, or are replaced or substituted by other components or equivalents. Adequate results can be achieved.

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

Claims (28)

oligomeric composite;
6-unit monomer; and
photoinitiator;
Including,
may further include particle composites,
The weight ratio of the 6-unit monomer:oligomer composite is 8:2 to 6:4,
The content of the particle composite is 0% to 7% based on the combined weight of the 6-unit monomer and oligomer composite,
Hard coating composition.
According to paragraph 1,
Each of the particle composites and oligomeric composites,
silica precursor;
A monomer containing an epoxy group, a (meth)acrylate group, or both;
solvent; and
catalyst;
which includes,
Hard coating composition.
According to paragraph 2,
The silica precursor is tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TETRAETHYL ORTHOSILICATE; TEOS), and tetrapropyl orthosilicate (TPOS). ), Tetrabutyl orthosilicate (TBOS), tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri Propoxysilane, dimethyldimethoxysilane, dimethyldi ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane ), diphenyldiethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, ethyltri ethoxysilane, propyltrimethoxysilane, vinyltri Methoxysilane (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-acryloxy-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-acryloxypropylmethylbis(trimethoxy)silane), 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyl Tripropoxysilane (3-acryloxypropyl tripropoxysilane), 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane (3-(meth) )acryloxypropyltriethoxysilane), 3-(meth)acryloxy propyltripropoxysilane), N-(2-aminoethic)-3-aminopropyl trimethoxysilane (N-(2 -aminoethyl)-3-aminopropylt rimethoxysilane), N-(2-aminoethyl)-3-aminopropyltriethoxysilane (N-(2-aminoethyl)-3-aminopropyltriethox ysilane), 3-aminopropyltrimethoxysilane (3-aminopropyltriethoxysilane), a group consisting of 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, and cyltrimethoxysilane Containing at least one selected from,
Hard coating composition.
According to paragraph 2,
The silica precursor is 20% to 30% by weight of the particle composite,
The silica precursor is 0.5% to 3% by weight of the oligomer composite,
Hard coating composition.
According to paragraph 2,
The monomer containing the epoxy group is,
(3-glycidyloxypropyl)trimethoxysilane (GPTMS), (3-glycidyloxypropyl)triethoxysilane (GPTES), 3- 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane (2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane) and 2-(3, Containing at least one selected from the group consisting of 4-epoxycyclohexyl)-ethyltriethoxysilane (2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane),
Hard coating composition.
According to paragraph 2,
The monomer containing the (meth)acrylate group is,
Trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, trimethoxysilylpropyl acrylate and triethoxysilylpropyl acrylate, dipentaerythol hexa(meth)acrylate, penta Erythol tetra(meth)acrylate, pentaerythol tri(meth)acrylate, trimethylene propyl tri(meth)acrylate, ethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, ethyl (meth)acrylate ) 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 Containing at least one selected from the group consisting of isononyl (meth)acrylate,
Hard coating composition.
According to paragraph 1,
The monomer containing an epoxy group, a (meth)acrylate group, or both is 10% to 20% by weight of the particle composite,
The monomer containing an epoxy group, a (meth)acrylate group, or both is 0.5% by weight to 3% by weight of the oligomer composite,
Hard coating composition.
According to paragraph 2,
The solvent includes water, an organic solvent, or both,
The organic solvents include ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), isopropyl alcohol (IPA), isopropyl alcohol propanol, isobutyl alcohol, hexanol, cyclohexanol, and dimethyl acetate. Amide (DMAC), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), 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 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 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-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, xylene, cyclohexanone, ethylene glycol, diethylene glycol, tetrahydrofuran, 1,4- Containing at least one selected from the group consisting of dioxane and glycerin,
Hard coating composition.
According to paragraph 2,
The solvent is 49% to 70% by weight of the particle composite,
The solvent is 93% to 99% by weight of the oligomer composite,
Hard coating composition.
delete According to paragraph 2,
The particle composite includes an acidic catalyst,
The oligomer composite includes an acidic catalyst and a basic catalyst,
Hard coating composition.
According to clause 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. Contains at least one of the
The basic catalyst is 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, and barium hydroxide. which includes,
Hard coating composition.
According to clause 11,
The acidic catalyst is 0.1% to 1% by weight of the particle composite,
The acidic catalyst and the basic catalyst, each in an amount of 0.1% to 1% by weight in the oligomer composite,
Hard coating composition.
According to paragraph 1,
The 6-unit monomer is dipentaerythritol hexa acrylate, dipentaerythritol hexamethacrylate, aliphatic polyurethane hexaacrylate, and silicone hexaacrylate. , containing at least one selected from the group consisting of polyester hexaacrylate and polyethylene glycol hexaacrylate,
Hard coating composition.
delete According to paragraph 1,
The photoinitiator is,
A photocationic initiator selected from onium salts, diazonium salts, sulfonium salts, and imidazoles; and
thioxanthone-based, phosphorus-based, triazine-based, benzophenone-based, benzoin-based, oxime-based, propanone-based, amino ketone-based, ketone-based, benzoin ether acetophenone-based, anthraquinone-based and aromatic phosphine oxide-based compounds selected from radical photoinitiator;
Containing at least one selected from the group consisting of,
Hard coating composition.
According to clause 16,
The mass ratio of the photocationic initiator to the radical photoinitiator is mixed at 99:0.1 to 0.1:99,
Hard coating composition.
According to paragraph 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 9, 11 to 14, and 16 to 18.
According to clause 19,
The pencil hardness of the hard coating film is 4H or more,
Hard coating film.
According to clause 19,
The curl due to curing shrinkage of the hard coating film is 40 mm or less,
Hard coating film.
According to clause 19,
The haze of the hard coating film is 3% or less,
Hard coating film.
particle composite; or preparing a composite comprising a particle composite and an oligomer composite;
the particle composite; or a composite comprising the particle composite and the oligomer composite;
6-unit monomer; and
Preparing the hard coating composition of any one of claims 1 to 9, 11 to 14, and 16 to 18 by mixing a photoinitiator; and
photocuring the hard coating composition;
Including,
Manufacturing method of hard coating film.
According to clause 23,
The step of preparing the particle composite is prepared by a sol-gel reaction,
The sol-gel reaction is carried out at a temperature of 0 ℃ to 90 ℃ and for 1 hour to 72 hours,
Manufacturing method of hard coating film.
According to clause 23,
The particle composite includes a silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; and an acidic catalyst;
The oligomeric composite includes a silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; acid catalyst; And a basic catalyst;
Manufacturing method of hard coating film.
According to clause 23,
The step of preparing the oligomer composite is,
silica precursor; A monomer containing an epoxy group, a (meth)acrylate group, or both; solvent; and an acidic catalyst; and then mixing the basic catalyst;
Manufacturing method of hard coating film.
According to clause 23,
The step of photocuring the hard coating composition is,
The hard coating composition is irradiated by a light source irradiated by at least one selected from the group consisting of 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 beam accelerator, and a radioactive element. which is hardened by
Manufacturing method of hard coating film.
A flexible display provided with the hard coating film according to claim 19.