Modified inorganic particles, hard coating composition comprising same, and coating film thereof

Abstract

The present invention relates to: modified inorganic particles which comprise a silsesquioxane having an open structure and inorganic particles bonded to the silsesquioxane, and have a refractive index of 1.3 or more; a hard coating composition comprising same; and a coating film thereof.

Description

Modified inorganic particles, hard coating composition containing the same, and coating film thereof

[0001] The present invention relates to modified inorganic particles, a hard coating composition comprising the same, and a coating film thereof.

[0002]

[0003] The display market has recently undergone a rapid transformation toward thinner, more flexible, and larger displays, and products are now entering the realization phase. This shift is also driving a shift in display coating processes, shifting from conventional dry processes to wet processes, which offer lower costs and enable continuous processing. Research is actively underway to enhance functional properties within the coating film, thereby enhancing various optical effects and addressing product shortcomings. Furthermore, research is being conducted to achieve thinner, more flexible, and larger displays.

[0004] In particular, the thick glass materials used on the outermost surfaces of displays are being replaced by thinner or plastic materials. Consequently, the importance of coating materials that overcome the thinning of glass and the surface properties of plastic materials, while controlling refractive index to produce clearer images, is also emerging.

[0005]

[0006] An object of the present invention is to provide surface-modified inorganic particles for improving the dispersion stability of a hard coating composition.

[0007] In addition, the present invention provides a hard coating composition having excellent refractive index and physical properties of a coating film by including the inorganic particles, which not only improves the dispersion stability of the composition, but also further includes high-refractive-index inorganic particles and a silicon-based binder.

[0008] In addition, the present invention provides a coating film having excellent refractive index and physical properties formed from the hard coating composition.

[0009]

[0010] The problems to be solved by the present invention are not limited to the problem(s) mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0011]

[0012] To achieve the above object, the present invention provides a modified inorganic particle comprising silsesquioxane having an open structure; and inorganic particles combined with the silsesquioxane, and having a refractive index of 1.3 or higher.

[0013] The above silsesquioxane may include at least one of the repeating units represented by the following chemical formulas 1 and 2.

[0014] [Chemical Formula 1]

[0015]

[0016] [Chemical Formula 2]

[0017]

[0018] In the above chemical formulas 1 and 2,

[0019] R1 is, each independently, a halogen group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, a thiol group, a glycidyl ether-substituted alkyl group having 1 to 10 carbon atoms, or an alicyclic epoxy-substituted alkyl group having 1 to 10 carbon atoms,

[0020] R2 is, each independently, hydrogen or a straight-chain or branched alkyl group having 1 to 10 carbon atoms,

[0021] n and m are, each independently, integers between 1 and 100,000,

[0022] However, n or m only means the number contained in one silsesquioxane molecule, and when including both repeating units represented by Chemical Formula 1 and Chemical Formula 2, the connection order of the n structural units and the m structural units is not limited and can be connected in a random order.

[0023] The above silsesquioxane may include a repeating unit represented by the above chemical formula 1 and a repeating unit represented by the above chemical formula 2.

[0024] The molecular weight of the above silsesquioxane may be 1,000 g / mol to 200,000 g / mol.

[0025] The above inorganic particles may be at least one selected from the group consisting of zirconia, titania and barium titanate.

[0026] The above modified inorganic particles may include silane on the surface of the inorganic particles, and the silsesquioxane may be bonded to the inorganic particles through the silane.

[0027] The weight ratio of the above-mentioned inorganic particles: the above-mentioned silane: the above-mentioned silsesquioxane may be 40 to 75:10 to 30:15 to 35.

[0028] In addition, the present invention provides a hard coating composition comprising the modified inorganic particles; high refractive index inorganic particles; and a silicon-based binder.

[0029] The above silicone-based binder may be a silsesquioxane containing at least one of the repeating units represented by the following chemical formulas 1 and 2.

[0030] [Chemical Formula 1]

[0031]

[0032] [Chemical Formula 2]

[0033]

[0034] In the above chemical formulas 1 and 2,

[0035] R1 is, each independently, a halogen group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, a thiol group, a glycidyl ether-substituted alkyl group having 1 to 10 carbon atoms, or an alicyclic epoxy-substituted alkyl group having 1 to 10 carbon atoms,

[0036] R2 is, each independently, hydrogen or a straight-chain or branched alkyl group having 1 to 10 carbon atoms,

[0037] n and m are, each independently, integers between 1 and 100,000,

[0038] However, n or m only means the number contained in one silsesquioxane molecule, and when including both repeating units represented by Chemical Formula 1 and Chemical Formula 2, the connection order of the n structural units and the m structural units is not limited and can be connected in a random order.

[0039] The above silsesquioxane may include a repeating unit represented by the above chemical formula 1 and a repeating unit represented by the above chemical formula 2.

[0040] The above silicone-based binder may have SiOH of 1 wt% or less.

[0041] The above high refractive index inorganic particles may include silane on the surface of the inorganic particles.

[0042] The inorganic particles of the above modified inorganic particles or high refractive inorganic particles may be at least one selected from the group consisting of zirconia, titania, and barium titanate.

[0043] The weight ratio of the above modified inorganic particles: high refractive index inorganic particles may be 1: 0.25 to 3.

[0044] In addition, the present invention provides a coating film comprising the modified inorganic particles; high refractive index inorganic particles; and a silicon-based binder.

[0045] The refractive index of the above coating film may be 1.3 or higher, and the hardness may be H or higher.

[0046]

[0047] The modified inorganic particles of the present invention can improve the dispersion stability of a hard coating composition by surface-treating silsesquioxane on high-refractive inorganic particles.

[0048] In addition, the hard coating composition of the present invention not only has excellent dispersion stability by including high-refractive inorganic particles surface-treated with the silsesquioxane, but also provides a coating film having high refractive index and excellent physical properties without lowering dispersion stability by further including high-refractive inorganic particles and a silicone-based binder.

[0049] In addition, the hard coating composition of the present invention has excellent dispersion stability and can be applied to a large-area wet coating process, and the viscosity can be easily controlled depending on the solvent content, so that it can be easily applied to various coating processes.

[0050]

[0051] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the composition of the invention described in the claims.

[0052]

[0053] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention. The present invention is defined solely by the scope of the claims set forth below.

[0054]

[0055] In this specification, unless otherwise defined, the term “substituted” includes a case where the term is substituted with a substituent selected from the group consisting of hydrogen, deuterium, halogen atoms, hydroxyl groups, C1~C30 alkyl groups, C3~C50 cycloalkyl groups, C2~C30 alkenyl groups, C3~C50 cycloalkenyl groups, C2~C30 alkynyl groups, C5~C50 cycloalkynyl groups, cyano groups, silyl groups, C1~C20 alkoxy groups, C5~C60 aryl groups, C1~C60 heteroaryl groups, and C6~C60 arylalkyl groups, and combinations thereof.

[0056] In this specification, “*” means a part that is connected to the same or different atoms or chemical formulas.

[0057]

[0058] In one embodiment of the present invention, a modified inorganic particle comprising silsesquioxane having an open structure and an inorganic particle combined with the silsesquioxane, and having a refractive index of 1.3 or more is provided.

[0059] In one embodiment, the silsesquioxane may include at least one of repeating units represented by the following chemical formulas 1 and 2.

[0060] [Chemical Formula 1]

[0061]

[0062] [Chemical Formula 2]

[0063]

[0064] In the above chemical formulas 1 and 2,

[0065] R1 is, each independently, a halogen group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, a thiol group, a glycidyl ether-substituted alkyl group having 1 to 10 carbon atoms, or an alicyclic epoxy-substituted alkyl group having 1 to 10 carbon atoms,

[0066] R2 is, each independently, hydrogen or a straight-chain or branched alkyl group having 1 to 10 carbon atoms,

[0067] n and m are, each independently, integers between 1 and 100,000.

[0068] However, n or m only means the number contained in one molecule of the silsesquioxane, and when including both repeating units represented by Chemical Formula 1 and Chemical Formula 2, the connection order of the n number of structural units and the m number of structural units is not limited and can be connected in a random order.

[0069] In one embodiment, the n / m may be 1 to 50. The adhesion properties with the substrate can be controlled by the ratio of the n / m, and the smaller the ratio of the n / m, the better the adhesion with the substrate.

[0070] In one embodiment, among the repeating unit represented by the above chemical formula 1 and the repeating unit represented by the chemical formula 2, R1 may be a (meth)acrylic group or an epoxy group.

[0071] In one embodiment, R2 among the repeating units represented by the above chemical formula 2 may be hydrogen or a C1 to C12 alkyl group.

[0072] When the above silsesquioxane includes a repeating unit represented by the above chemical formula 2, by introducing an -OR2 group including R2 in the above chemical formula 2, the bonding and adhesive strength between the substrate and the composition can be improved. In particular, covalent bonding with Si-OH and Si-O of the glass surface in the organic substrate is possible, thereby increasing the bonding and adhesive strength with the substrate during coating.

[0073] In the present invention, the modified inorganic particle may mean an inorganic particle having silsesquioxane containing at least one of the repeating units represented by the chemical formulas 1 and 2 bonded to the surface of the inorganic particle.

[0074] In one embodiment, when the silsesquioxane includes both a repeating unit represented by the chemical formula 1 and a repeating unit represented by the chemical formula 2, it may be represented by the following chemical formula 3.

[0075] [Chemical Formula 3]

[0076]

[0077] In the above chemical formula 3, R1 and R2 are as defined in the above chemical formulas 1 and 2.

[0078] However, n or m only means the number contained in one silsesquioxane molecule, and the connection order of the n structural units and the m structural units is not limited and can be connected in a random order.

[0079] According to one embodiment, the silsesquioxane may include an open cage type silsesquioxane. According to another embodiment, the silsesquioxane may include an open cage type silsesquioxane repeating unit and a ladder type silsesquioxane repeating unit.

[0080] In the present invention, the open cage type may mean an open structure.

[0081] According to one embodiment, the proportion of ladder-type silsesquioxane in the silsesquioxane may be 15 mol% or more, for example, 19 mol% or more, of the total silsesquioxane. As the ladder-type silsesquioxane structure increases, the physical properties (e.g., film strength) of the coating film formed after coating may be improved. However, if the ladder-type silsesquioxane structure is too much, the coating film may become brittle or break easily. In addition, as the open cage-type silsesquioxane structure increases, the adhesive strength increases and the compatibility with aliphatic urethane acrylate oligomers increases, but the strength may be weakened.

[0082] In one embodiment, the molecular weight of the silsesquioxane may be 600 g / mol to 1,000,000 g / mol, specifically 1,000 g / mol to 200,000 g / mol, and when the silsesquioxane having the above molecular weight range is included in the hard coating composition as an inorganic particle bonded to the surface, the dispersion stability of the hard coating composition is better, and the hardness of the coating film manufactured by including the same is H, specifically 2H or higher.

[0083] In one embodiment, the modified inorganic particles may include silane on the surface of the inorganic particles, and the silsesquioxane may be bonded to the inorganic particles through the silane. That is, the modified inorganic particles may be inorganic particles surface-treated with silane, in which the silsesquioxane is bonded to the surface. At this time, the weight ratio of the inorganic particles: silane: silsesquioxane may be 40 to 75:10 to 30:15 to 35, and when the inorganic particles, silane, and silsesquioxane are included in the above weight ratio range, the hardness and refractive index of the coating film and the dispersion stability of the hard coating composition may be better.

[0084] In the present invention, the inorganic particles surface-treated with silane may mean high-refractive-index inorganic particles.

[0085] In one embodiment, the inorganic particles surface-treated with the silane may be inorganic particles surface-treated with a silane coupling agent. The silane coupling agent may be an alkoxy silane having a reactive group, and specifically, may be 2-(3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-Glycidoxypropyl methyldimethoxysilane, 3-Glycidoxypropyl trimethoxysilane, 3-Glycidoxypropyl methyldiethoxysilane, 3-Glycidoxypropyl triethoxysilane, 3-Methacryloxypropyl methyldimethoxysilane, 3-Methacryloxypropyl trimethoxysilane, 3-Methacryloxypropyl methyldiethoxysilane, 3-Methacryloxypropyl triethoxysilane, 3-Acryloxypropyl trimethoxysilane, etc.

[0086] In one embodiment, the refractive index of the inorganic particle having the silsesquioxane bonded to the surface of the inorganic particle treated with silane may be 1.3 or more, specifically, 1.5 or more.

[0087] In one embodiment, the inorganic particles may be at least one selected from the group consisting of zirconia, titania, silica and barium titanate.

[0088] In the present invention, the silica may mean silica other than hollow silica.

[0089]

[0090] In one embodiment of the present invention, a hard coating composition is provided, comprising the above-described modified inorganic particles; high-refractive inorganic particles; and a silicon-based binder.

[0091] The modified inorganic particles included in the above hard coating composition are the same as the modified inorganic particles described above, and any content overlapping with that described in the above modified inorganic particles will not be described again.

[0092] The hard coating composition may contain 5 to 60 wt%, specifically 10 to 30 wt%, of modified inorganic particles based on the total weight of the hard coating composition. When the hard coating composition contains the modified inorganic particles in the above range, the hard coating composition may have a more excellent dispersion stability effect.

[0093] In one embodiment, the high refractive index inorganic particles may be inorganic particles surface-treated with silane, and specifically, may be inorganic particles surface-treated with a silane coupling agent.

[0094] The hard coating composition may contain 5 to 80 wt%, specifically 10 to 40 wt%, of high-refractive inorganic particles based on the total weight of the hard coating composition. When the hard coating composition contains the high-refractive inorganic particles in the above range, the refractive index of the coating film may have a more excellent effect.

[0095] In one embodiment, the silicone-based binder may be a silsesquioxane comprising at least one of repeating units represented by the following chemical formulas 1 and 2.

[0096] [Chemical Formula 1]

[0097]

[0098] [Chemical Formula 2]

[0099]

[0100] In the above chemical formulas 1 and 2,

[0101] R1 is, each independently, a halogen group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, a thiol group, a glycidyl ether-substituted alkyl group having 1 to 10 carbon atoms, or an alicyclic epoxy-substituted alkyl group having 1 to 10 carbon atoms,

[0102] R2 is, each independently, hydrogen or a straight-chain or branched alkyl group having 1 to 10 carbon atoms,

[0103] n and m are, each independently, integers between 1 and 100,000.

[0104] However, n or m only means the number contained in one silsesquioxane molecule, and when including both repeating units represented by Chemical Formula 1 and Chemical Formula 2, the connection order of the n structural units and the m structural units is not limited and can be connected in a random order.

[0105] In one embodiment, the n / m may be 1 to 50. The adhesion properties with the substrate can be controlled by the ratio of the n / m, and the smaller the ratio of the n / m, the better the adhesion with the substrate.

[0106] In one embodiment, among the repeating unit represented by the above chemical formula 1 and the repeating unit represented by the chemical formula 2, R1 may be a (meth)acrylic group or an epoxy group.

[0107] In one embodiment, R2 among the repeating units represented by the above chemical formula 2 may be hydrogen or a C1 to C12 alkyl group.

[0108] By introducing the -OR2 group including the above R2, the bonding and adhesion between the substrate and the composition can be improved. In particular, covalent bonding with Si-OH and Si-O of the glass surface is possible in the organic substrate, thereby increasing the bonding and adhesion with the substrate during coating.

[0109] In one embodiment, when the silsesquioxane includes both a repeating unit represented by the chemical formula 1 and a repeating unit represented by the chemical formula 2, it may be represented by the following chemical formula 3.

[0110] [Chemical Formula 3]

[0111]

[0112] In the above chemical formula 3, R1 and R2 are as defined in the above chemical formulas 1 and 2.

[0113] However, n or m only means the number contained in one silsesquioxane molecule, and the connection order of the n structural units and the m structural units is not limited and can be connected in a random order.

[0114] According to one embodiment, the silsesquioxane may include an open cage type silsesquioxane. According to another embodiment, the silsesquioxane may include an open cage type silsesquioxane repeating unit and a ladder type silsesquioxane repeating unit.

[0115] According to one embodiment, the proportion of ladder-type silsesquioxane in the silsesquioxane may be 15 mol% or more, for example, 19 mol% or more, of the total silsesquioxane. As the ladder-type silsesquioxane structure increases, the physical properties (e.g., film strength) of the coating film formed after coating may be improved. However, if the ladder-type silsesquioxane structure is too much, the coating film may become brittle or break easily. In addition, as the open cage-type silsesquioxane structure increases, the adhesive strength increases and the compatibility with the aliphatic urethane acrylate oligomer increases, but the strength may be weakened.

[0116] The above silsesquioxane may have SiOH of 1 wt% or less, specifically 0.5 wt% or less, and if the SiOH of the silsesquioxane is equal to or more than the above value, the stability of the silsesquioxane may be impaired.

[0117] In the present invention, the silsesquioxane bound to the modified inorganic particles and the silsesquioxane used as a silicone binder may be the same or different from each other.

[0118] In one embodiment, the weight ratio of the modified inorganic particles: high-refractive inorganic particles may be 1:0.25 to 3, and when the weight ratio of the modified inorganic particles: high-refractive inorganic particles is included in the above weight ratio range, the hardness and refractive index of the coating film and the dispersion stability of the hard coating composition may be better.

[0119] The hard coating composition may contain 5 to 60 wt%, specifically 10 to 30 wt%, of the silicone-based binder based on the total weight of the hard coating composition. When the hard coating composition contains the silicone-based binder in the above range, the hardness of the coating film may be more effectively improved.

[0120] In one embodiment, the hard coating composition may further include a remainder of a dispersing additive, a surface additive, an initiator, or a solvent in addition to the inorganic particles combined with silsesquioxane, the high-refractive inorganic particles, and the silicone-based binder.

[0121] The above hard coating composition may further include a cationic photopolymerization initiator, a radical initiator, or both as an initiator.

[0122] The hard coating composition may contain 0.1 to 10 wt%, specifically 1 to 5 wt%, of an initiator based on the total weight of the hard coating composition. When the hard coating composition contains the initiator in the above range, the coating film may have a more excellent permeability effect.

[0123] The cationic photopolymerization initiator is, for example, a sulfonium type such as triphenylsulfonium, diphenyl-4-(phenylthio)phenylsulfonium, iodonium such as diphenyliodonium or bis(dodecylphenyl)iodonium, diazonium such as phenyldiazonium, ammonium such as 1-benzyl-2-cyanopyrrinium or 1-(naphthylmethyl)-2-cyanopyrrinium, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate iodonium, bis(4-t-butylphenyl)hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoromethanesulfonate iodonium, triphenylsulfonium tetrafluoroborate, tri-p-toylsulfoniumhexafluorophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and Fe cations such as (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe and BF 4- , PF 6- , SbF 6- [BQ4] of the back - Examples thereof include onium salts (wherein Q is a phenyl group substituted with at least two fluorine or trifluoromethyl groups), and at least one or more of these may be used, and, without limitation, known compounds known as cationic photopolymerization initiators may be used.

[0124] The radical initiator, for example, hydroxyketone series such as 1-hydroxy cyclohexylphenyl ketone (Irgacure 184), aminoketone series such as 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone (Irgacure 369), α-aminoacetophenone (Irgacure 907), benzyldimethyl ketal series such as benzyldimethyl ketal (Irgacure-651), phenyl bis(2,4,6-trimethyl benzoyl), Examples include bis-acyl phosphine series such as Irgacure 819, and mono-acyl phosphine series such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and at least one of these can be used, but is not limited thereto, and known compounds known as radical initiators can be used.

[0125] The above hard coating composition may further include a silicone-based surface additive, an acrylic-based surface additive, or both as a surface additive.

[0126] The hard coating composition may contain 0.1 to 5 wt%, specifically 0.5 to 3 wt%, of a surface additive based on the total weight of the hard coating composition. When the hard coating composition contains the surface additive in the above range, the flatness of the coating film surface can be further improved.

[0127] The above silicone-based surface additives include, for example, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc., and at least one of these can be used, but is not limited thereto, and a known material known as a silicone-based surface additive can be used.

[0128] Examples of the acrylic surface additive include, for example, BYK-340, BYK-350, BYK-352, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-359, BYK-361N, BYK-380N, BYK-381, BYK-388, BYK-390, BYK-392, BYK-394, etc., and at least one of these can be used, and the present invention is not limited thereto, and a known material known as an acrylic surface additive can be used.

[0129] The above hard coating composition may further include a dispersing additive.

[0130] The hard coating composition may contain 0.1 to 10 wt%, specifically 1 to 5 wt%, of a dispersing additive based on the total weight of the hard coating composition. When the hard coating composition contains the dispersing additive in the above range, the miscibility of the hard coating composition and the dispersibility and dispersion stability of the inorganic particles can be further improved.

[0131] The dispersing additives include, for example, ANTI-TERRA-203, ANTI-TERRA-204, ANTI-TERRA-U, BYK-220S, BYK-9076, BYK-9077, DISPERBYK-103, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-118, DISPERBYK-130, DISPERBYK-140, DISPERBYK-145, DISPERBYK-160, BYK-161, DISPERBYK-166, DISPERBYK-168, DISPERBYK-170, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, Examples include DISPERBYK-2008, DISPERBYK-2013, DISPERBYK-2055, DISPERBYK-2059, DISPERBYK-2117, DISPERBYK-2118, DISPERBYK-2150, DISPERBYK-2151, DISPERBYK-2152, DISPERBYK-2200, ANTI-TERRA-250, BYK-154, DISPERBYK-180, DISPERBYK-185, DISPERBYK-192, DISPERBYK-194N DISPERBYK-2013, DISPERBYK-2015, DISPERBYK-2060, DISPERBYK-2061, BYKJET-9132, BYKJET-9142, BYKJET-9151, and at least one of these may be used, but are not limited thereto. , and known substances known as dispersing additives can be used.

[0132] The above hard coating composition may further contain a solvent.

[0133] The hard coating composition may contain 5 to 95 wt%, specifically 30 to 70 wt%, of the solvent based on the total weight of the hard coating composition. When the hard coating composition contains the solvent in the above range, it facilitates coating by imparting and controlling the flowability of the hard coating composition, and helps uniform mixing of the entire composition and dispersibility of inorganic particles.

[0134] The solvent may be, for example, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and cellosolve; ketones such as lactate, acetone, and methyl (isobutyl) ethyl ketone; glycols such as ethylene glycol; furans such as tetrahydrofuran; polar solvents such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; and various solvents such as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, and benzyl alcohol, but is not limited thereto.

[0135]

[0136] In one embodiment of the present invention, a coating film formed from the hard coating composition described above is provided. The hard coating composition is as described above, and any overlapping details will not be described again.

[0137] The above-mentioned hard coating composition not only has excellent dispersion stability by including high-refractive inorganic particles surface-treated with the above-mentioned silsesquioxane, but also has the effect of having high refractive index and excellent physical properties without lowering dispersion stability by further including high-refractive inorganic particles and a silicone-based binder.

[0138] In one embodiment, the refractive index of the coating film may be 1.3 or greater, specifically 1.45 or greater, and more specifically 1.6 or greater.

[0139] In one embodiment, the hardness of the coating film may be H, specifically 2H or greater.

[0140] According to one embodiment, the coating film may be for a flexible display.

[0141]

[0142] The above description has explained the technical idea of ​​the present invention using one embodiment. Those skilled in the art will appreciate that various modifications and variations can be made without departing from the essential characteristics of the present invention. Therefore, the embodiments described in the present invention are not intended to limit the technical idea of ​​the present invention, but rather to explain it, and the scope of the technical idea of ​​the present invention is not limited by these embodiments. The scope of protection of the present invention should be interpreted by the claims, and all technical ideas within a scope equivalent thereto should be interpreted as being included within the scope of the rights of the present invention.

[0143]

[0144] [Preparation Example 1A]

[0145] (1) Manufacturing of polymerization catalyst

[0146] To control the basicity, a catalyst was prepared by mixing a 10% potassium hydroxide aqueous solution with a 25 wt% tetramethylammonium hydroxide aqueous solution.

[0147] (2) Synthesis of silsesquioxane 1A

[0148] In a dried flask equipped with a condenser and a stirrer, 20 g of distilled water and 300 g of methanol were mixed to prepare a mixture, and 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane and 24.84 g (0.1 mol) of 3-Methacryloxypropyl trimethoxysilane were added dropwise and stirred for 30 minutes. Afterwards, 4 g of 0.36 wt% HCl aqueous solution was very slowly added dropwise to the reaction solution to adjust the pH to acidic, and the mixture was stirred for 1 hour to promote hydrolysis. At this time, the temperature was maintained at -4℃.

[0149] Afterwards, 40 g of a separately manufactured catalyst was added dropwise to adjust the pH to be alkaline, and the temperature was raised to 50°C to carry out a condensation reaction for 12 hours.

[0150] The catalyst and impurities were extracted from the mixture of the silsesquioxane structure and solvent obtained in the above reaction using distilled water, and after confirming that the pH was neutral, all the solvent was removed by vacuum decompression to obtain silsesquioxane (weight average molecular weight 2,600; n / m=9 in chemical formulas 1 and 2) containing 0.5 wt% SiOH.

[0151]

[0152] [Preparation Example 1B]

[0153] In the above Preparation Example 1A, except that 47.26 g (0.2 mol) of 3-Glycidoxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane and 24.84 g (0.1 mol) of 3-Methacryloxypropyl trimethoxysilane, a silsesquioxane (weight average molecular weight 2,600; n / m=9 in chemical formulas 1 and 2) having 0.5 wt% SiOH was obtained under the same conditions and method as in the above Preparation Example 1A.

[0154]

[0155] [Preparation Example 1C]

[0156] In the above Preparation Example 1A, except that 49.68 g (0.2 mol) of 3-Methacryloxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane and 24.84 g (0.1 mol) of 3-Methacryloxypropyl trimethoxysilane, a silsesquioxane (weight average molecular weight 2,600; n / m=9 in chemical formulas 1 and 2) having 0.5 wt% SiOH was obtained under the same conditions and method as in the above Preparation Example 1A.

[0157]

[0158] [Preparation Example 1D]

[0159] In the above Preparation Example 1A, except that 1500 g of methanol was used instead of 300 g, silsesquioxane (weight average molecular weight 800; n / m=2 in chemical formulas 1 and 2) containing 0.5 wt% SiOH was obtained under the same conditions and method as in the above Preparation Example 1A.

[0160]

[0161] [Preparation Example 1E]

[0162] In the above Preparation Example 1A, except that 25 g of methanol was used instead of 300 g and the condensation reaction was performed for 48 hours instead of 12 hours, a silsesquioxane (weight average molecular weight 250,000; n / m=50 in chemical formulas 1 and 2) containing 0.5 wt% SiOH was obtained under the same conditions and method as in the above Preparation Example 1A.

[0163]

[0164] [Preparation Example 1F]

[0165] In the above Preparation Example 1A, 50 g was used instead of 20 g of distilled water, 600 g was used instead of 300 g of methanol, 49.68 g (0.2 mol) of 3-Methacryloxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane and 24.84 g (0.1 mol) of 3-Methacryloxypropyl trimethoxysilane, 8 g was used instead of 4 g of aqueous HCl solution, and 35 g was used instead of 40 g of catalyst, thereby obtaining a silsesquioxane (weight average molecular weight 1,600; n / m=2 in chemical formulas 1 and 2) having a SiOH content of 3 wt% under the same conditions and method as in the above Preparation Example 1A.

[0166]

[0167] [Preparation Example 1G]

[0168] Glycidyl Methacryl POSS (HC0407.11) from Hybrid Plastics Co. was purchased and used (weight average molecular weight 1,362).

[0169]

[0170] [Preparation Example 1H]

[0171] Methacryl POSS (MA0735) from Hybrid Plastics Co. was purchased and used (weight average molecular weight 1,434).

[0172]

[0173] [Preparation Example 1I]

[0174] In the above Preparation Example 1A, except that 1,200 g of methanol was used instead of 300 g, silsesquioxane (weight average molecular weight 1,000; n / m=2 in chemical formulas 1 and 2) containing 0.5 wt% SiOH was obtained under the same conditions and method as in the above Preparation Example 1A.

[0175]

[0176] [Preparation Example 1J]

[0177] In the above Preparation Example 1A, except that 60 g of methanol was used instead of 300 g and that the condensation reaction was performed for 48 hours instead of 12 hours, a silsesquioxane (weight average molecular weight 100,000; n / m=40 in chemical formulas 1 and 2) containing 0.5 wt% SiOH was obtained under the same conditions and method as in the above Preparation Example 1A.

[0178]

[0179] [Preparation Example 1K]

[0180] In the above Preparation Example 1A, except that 35 g of methanol was used instead of 300 g, and the condensation reaction was performed for 48 hours instead of 12 hours, a silsesquioxane (weight average molecular weight 200,000; n / m=45 in chemical formulas 1 and 2) containing 0.5 wt% SiOH was obtained under the same conditions and method as in the above Preparation Example 1A.

[0181]

[0182] [Preparation Example 1L]

[0183] In the above Preparation Example 1A, 33 g was used instead of 20 g of distilled water, 600 g was used instead of 300 g of methanol, 49.68 g (0.2 mol) of 3-Methacryloxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane and 24.84 g (0.1 mol) of 3-Methacryloxypropyl trimethoxysilane, 8 g was used instead of 4 g of aqueous HCl solution, and 35 g was used instead of 40 g of catalyst, thereby obtaining silsesquioxane (weight average molecular weight 1,600; n / m=2 in chemical formulas 1 and 2) having a SiOH content of 1.1 wt% under the same conditions and method as in the above Preparation Example 1A.

[0184]

[0185] [Preparation Example 1M]

[0186] In the above Preparation Example 1A, 30 g was used instead of 20 g of distilled water, 600 g was used instead of 300 g of methanol, 49.68 g (0.2 mol) of 3-Methacryloxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane and 24.84 g (0.1 mol) of 3-Methacryloxypropyl trimethoxysilane, 8 g was used instead of 4 g of aqueous HCl solution, and 35 g was used instead of 40 g of catalyst, thereby obtaining silsesquioxane (weight average molecular weight 1,600; n / m=2 in chemical formulas 1 and 2) having a SiOH content of 1.0 wt% under the same conditions and method as in the above Preparation Example 1A.

[0187]

[0188] [Preparation Example 1N]

[0189] In the above Preparation Example 1A, except that 10 g of distilled water was used instead of 20 g, and 49.68 g (0.2 mol) of 3-Methacryloxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane and 24.84 g (0.1 mol) of 3-Methacryloxypropyl trimethoxysilane, a silsesquioxane (weight average molecular weight 2,600; n / m=9 in chemical formulas 1 and 2) having 0.1 wt% SiOH was obtained under the same conditions and method as in the above Preparation Example 1A.

[0190]

[0191] (3) Synthesis of high refractive index inorganic particles 2A

[0192] [Preparation Example 2A]

[0193] In a dried flask equipped with a condenser and a stirrer, 10 g of distilled water and 500 g of methanol were mixed to prepare a mixture, and 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane was added dropwise and stirred for 30 minutes. Then, 1 g of 0.36 wt% HCl aqueous solution was very slowly added dropwise to the reaction solution to adjust the pH to be acidic, and the mixture was stirred for 1 hour to promote hydrolysis. Thereafter, 50 g of zirconia (ZrO2) nanoparticles with a particle size of 50 nm were slowly added dropwise and stirred for an additional 30 minutes. During this time, the temperature was maintained at -4℃.

[0194] Thereafter, in order to promote a condensation reaction between zirconia nanoparticles and silane, 20 g of the separately prepared catalyst of Preparation Example 1A was added dropwise, and the pH was adjusted to be alkaline. The temperature was raised to 50°C, and the condensation reaction was performed for 12 hours.

[0195] The above reaction product, after completing the condensation reaction, was precipitated using a centrifuge, and then thoroughly washed with water and ethanol to extract the catalyst and impurities. After confirming that the pH was neutral, the product was dried in an oven at 60°C for 6 hours to remove all solvent, and zirconia nanoparticles surface-treated with silane were obtained.

[0196]

[0197] [Preparation Example 2B]

[0198] In the above Preparation Example 2A, except that 24.84 g (0.1 mol) of Methacryloxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane, zirconia nanoparticles surface-treated with silane were obtained under the same conditions and method as in the above Preparation Example 2A.

[0199]

[0200] [Preparation Example 2C-1]

[0201] In the above Preparation Example 2A, titania nanoparticles surface-treated with silane were obtained under the same conditions and method as in the above Preparation Example 2A, except that titania nanoparticles having a size of 50 nm were used instead of zirconia nanoparticles having a size of 50 nm.

[0202]

[0203] [Preparation Example 2C-2]

[0204] In Preparation Example 2A, 24.84 g (0.1 mol) of Methacryloxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane, and 50 nm titania nanoparticles were used instead of 50 nm zirconia nanoparticles, and titania nanoparticles surface-treated with silane were obtained under the same conditions and method as in Preparation Example 2A.

[0205]

[0206] [Preparation Example 2D-1]

[0207] In the above Preparation Example 2A, silica nanoparticles surface-treated with silane were obtained under the same conditions and method as in the above Preparation Example 2A, except that silica nanoparticles having a size of 50 nm were used instead of zirconia nanoparticles having a size of 50 nm.

[0208]

[0209] [Preparation Example 2D-2]

[0210] Silica nanoparticles surface-treated with silane were obtained under the same conditions and method as in Preparation Example 2A, except that 24.84 g (0.1 mol) of Methacryloxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane, and 50 nm silica nanoparticles were used instead of 50 nm zirconia nanoparticles.

[0211]

[0212] [Preparation Example 2E]

[0213] In the above Preparation Example 2A, 35.45 g (0.15 mol) of 3-Glycidoxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane, 1.5 g of HCl aqueous solution was used instead of 1 g, and 30 g of zirconia nanoparticles was used instead of 50 g, except that zirconia nanoparticles surface-treated with silane were obtained under the same conditions and method as in the above Preparation Example 2A.

[0214]

[0215] [Preparation Example 2F]

[0216] In the above Preparation Example 2A, hollow silica nanoparticles surface-treated with silane were obtained under the same conditions and method as in the above Preparation Example 2A, except that 50 nm hollow silica was used instead of zirconia nanoparticles.

[0217]

[0218] [Preparation Example 2G]

[0219] In Preparation Example 2A, hollow silica nanoparticles surface-treated with silane were obtained under the same conditions and method as in Preparation Example 2A, except that 24.84 g (0.1 mol) of Methacryloxypropyl trimethoxysilane was used instead of 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane, and hollow silica surface-treated with hydroxyl groups was used instead of zirconia nanoparticles.

[0220]

[0221] [Example 1]

[0222] 30 g of silsesquioxane obtained in Preparation Example 1A and 200 g of Tetrahydrofuran (THF) were mixed and stirred for 30 minutes. After stirring, 70 g of silane-surface-treated zirconia nanoparticles obtained in Preparation Example 2A were slowly added dropwise and mixed for another 30 minutes. 10 g of N-benzylpyrazinium hexafluoroantimonate was added dropwise to the prepared mixed solution and stirred for 30 minutes. After completely sealing the reactor, the temperature was increased to 100°C and stirring was continued for 1 day to carry out the reaction. After 1 day of reaction, the reactor was cooled to room temperature, and 200 g of propylene glycol methyl ether (PGME) was added dropwise and stirred for 30 minutes. After that, THF was removed using a vacuum decompression device, and zirconia (ZrO2) nanoparticles re-surface-treated with silsesquioxane dispersed in PGME were obtained. At this time, the content of zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane in PGME was 50 wt%.

[0223]

[0224] [Example 2]

[0225] 30 g of silsesquioxane obtained in Preparation Example 1A and 200 g of acetonitrile (ACN) were mixed and stirred for 30 minutes. After stirring, 70 g of silane-surface-treated zirconia nanoparticles obtained in Preparation Example 2B were slowly added dropwise and mixed for another 30 minutes. After refluxing the reactor under a nitrogen atmosphere, 20 g of azobisisobutyronitrile (AIBN) was added dropwise to the prepared mixed solution and stirred for 30 minutes. After completely sealing the reactor and increasing the temperature to 100°C, stirring was continued for 10 hours to perform the reaction. After 10 hours of reaction, the reactor was cooled to room temperature, and 200 g of propylene glycol methyl ether (PGME) was added dropwise and stirred for 30 minutes. After that, ACN was removed using a vacuum decompression device, and zirconia (ZrO2) nanoparticles re-surface-treated with silsesquioxane dispersed in PGME were obtained. At this time, the content of zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane in PGME was 50 wt%.

[0226]

[0227] [Example 3]

[0228] In the above Example 1, except that the silane-surface-treated titania nanoparticles obtained in Preparation Example 2C-1 were used instead of Preparation Example 2A, titania nanoparticles resurface-treated with silsesquioxane dispersed in PGME were obtained under the same conditions and method as in Example 1. At this time, the content of the silsesquioxane-surface-treated titania nanoparticles in PGME was 50 wt%.

[0229]

[0230] [Example 4]

[0231] In the above Example 1, except that the silica nanoparticles surface-treated with silane obtained in Preparation Example 2D-1 were used instead of Preparation Example 2A, silica nanoparticles re-surface-treated with silsesquioxane dispersed in PGME were obtained under the same conditions and method as in Example 1. At this time, the content of the silica nanoparticles re-surface-treated with silsesquioxane in PGME was 50 wt%.

[0232]

[0233] [Example 5]

[0234] In the above Example 1, except that the silsesquioxane obtained in Preparation Example 1D was used instead of Preparation Example 1A, zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane dispersed in PGME were obtained under the same conditions and method as in Example 1. At this time, the content of zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane in PGME was 50 wt%.

[0235]

[0236] [Example 6]

[0237] In the above Example 1, except that the silsesquioxane obtained in Preparation Example 1E was used instead of Preparation Example 1A, zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane dispersed in PGME were obtained under the same conditions and method as in Example 1. At this time, the content of zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane in PGME was 50 wt%.

[0238]

[0239] [Example 7]

[0240] In the above Example 1, except that 40 g of silsesquioxane obtained in Preparation Example 1A was used instead of 30 g, and 60 g of silane-surface-treated zirconia nanoparticles obtained in Preparation Example 2E were used instead of 70 g of silane-surface-treated zirconia nanoparticles obtained in Preparation Example 2A, zirconia (ZrO2) nanoparticles re-surface-treated with silsesquioxane dispersed in PGME were obtained under the same conditions and by the same method as in Example 1. At this time, the content of silsesquioxane-surface-treated zirconia (ZrO2) nanoparticles in PGME was 50 wt%.

[0241]

[0242] [Example 8]

[0243] In the above Example 1, except that the silsesquioxane obtained in Preparation Example 1I was used instead of Preparation Example 1A, zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane dispersed in PGME were obtained under the same conditions and method as in Example 1. At this time, the content of zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane in PGME was 50 wt%.

[0244]

[0245] [Example 9]

[0246] In the above Example 1, except that the silsesquioxane obtained in Preparation Example 1J was used instead of Preparation Example 1A, zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane dispersed in PGME were obtained under the same conditions and method as in Example 1. At this time, the content of zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane in PGME was 50 wt%.

[0247]

[0248] [Example 10]

[0249] In the above Example 1, except that the silsesquioxane obtained in Preparation Example 1K was used instead of Preparation Example 1A, zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane dispersed in PGME were obtained under the same conditions and method as in Example 1. At this time, the content of zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane in PGME was 50 wt%.

[0250]

[0251] [Comparative Example 1]

[0252] In the above Example 1, except that the cage-structured silsesquioxane of Preparation Example 1G was used instead of Preparation Example 1A, zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane dispersed in PGME were obtained under the same conditions and method as in Example 1. At this time, the content of zirconia (ZrO2) nanoparticles resurfaced with silsesquioxane in PGME was 50 wt%.

[0253]

[0254] [Comparative Example 2]

[0255] In the above Example 1, hollow silica nanoparticles surface-treated with silane obtained in Preparation Example 2F were used instead of 2A, and hollow silica nanoparticles re-surface-treated with silsesquioxane dispersed in PGME were obtained under the same conditions and method as in Example 1. At this time, the content of hollow silica nanoparticles re-surface-treated with silsesquioxane in PGME was 50 wt%.

[0256]

[0257] [Manufacturing Example 1: Composition for hard coating and coating film thereof]

[0258] 12 g of silsesquioxane obtained in the above Preparation Example 1B, 18 g of inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2A, and 24 g of a dispersion of nanoparticles treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in the above Example 2 were stirred, and then 46 g of PGME was additionally added and mixed to prepare a 100 g composition. Thereafter, based on 100 parts by weight of the prepared composition, 4 parts by weight of an ionic UV initiator irgacure-250, 3 parts by weight of a dispersing additive DISPERBYK-180, and 1 part by weight of a silicone-based surface additive BYK-302 were added, and stirred for 10 minutes to prepare a composition for hard coating.

[0259] The manufactured hard coating composition was applied on a 250um PET film from SKC, and the solvent was evaporated in an 85 degree drying oven, and then irradiated using UV equipment at 1 J / cm 2 The resultant 10㎛ film was obtained by irradiating it with UV.

[0260]

[0261] [Manufacturing Example 2: Composition for hard coating and coating film thereof]

[0262] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1C was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, except that a hard coating composition and a coating film thereof were produced under the same conditions and by the same method as in the above Preparation Example 1.

[0263]

[0264] [Manufacturing Example 3: Composition for hard coating and coating film thereof]

[0265] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1C was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of titania obtained in the above Preparation Example 2C-2 were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of titania dispersed in PGME obtained in the above Example 3 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0266]

[0267] [Manufacturing Example 4: Composition for hard coating and coating film thereof]

[0268] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1C was used instead of the Preparation Example 1B, the inorganic particles on the surface of the silica obtained in the above Preparation Example 2D-2 were used instead of the Preparation Example 2A, the nanoparticle dispersion on the surface of the silica dispersed in PGME obtained in the above Example 4 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, except that a hard coating composition and a coating film thereof were produced under the same conditions and by the same method as in the above Preparation Example 1.

[0269]

[0270] [Manufacturing Example 5: Composition for hard coating and coating film thereof]

[0271] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1C was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 5 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0272]

[0273] [Manufacturing Example 6: Composition for hard coating and coating film thereof]

[0274] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1C was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 6 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0275]

[0276] [Manufacturing Example 7: Composition for hard coating and coating film thereof]

[0277] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1C was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 7 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0278]

[0279] [Manufacturing Example 8: Composition for hard coating and coating film thereof]

[0280] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1F was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, except that a hard coating composition and a coating film thereof were produced under the same conditions and by the same method as in the above Preparation Example 1.

[0281]

[0282] [Manufacturing Example 9: Composition for hard coating and coating film thereof]

[0283] In the above Preparation Example 1, 12 g of silsesquioxane obtained in the above Preparation Example 1C was used instead of Preparation Example 1B, 32 g of inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B was used instead of Preparation Example 2A, 12 g of a dispersion of nanoparticles treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of Example 2, and a radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, except that a hard coating composition and a coating film thereof were manufactured under the same conditions and by the same method as in Preparation Example 1.

[0284]

[0285] [Manufacturing Example 10: Composition for hard coating and coating film thereof]

[0286] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1C was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 8 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0287]

[0288] [Manufacturing Example 11: Composition for hard coating and coating film thereof]

[0289] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1C was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 9 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0290]

[0291] [Manufacturing Example 12: Composition for hard coating and coating film thereof]

[0292] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1C was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 10 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0293]

[0294] [Manufacturing Example 13: Composition for hard coating and coating film thereof]

[0295] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1L was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were manufactured under the same conditions and method as in the above Preparation Example 1.

[0296]

[0297] [Manufacturing Example 14: Composition for hard coating and coating film thereof]

[0298] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1M was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0299]

[0300] [Manufacturing Example 15: Composition for hard coating and coating film thereof]

[0301] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1N was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were manufactured under the same conditions and method as in the above Preparation Example 1.

[0302]

[0303] [Manufacturing Example 16: Composition for hard coating and coating film thereof]

[0304] In the above Preparation Example 1, 12 g of silsesquioxane obtained in the above Preparation Example 1C was used instead of Preparation Example 1B, 43 g of inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B was used instead of Preparation Example 2A, 22 g of a dispersion of nanoparticles treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of Example 2, and a radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0305]

[0306] [Manufacturing Example 17: Composition for hard coating and coating film thereof]

[0307] In the above Preparation Example 1, 12 g of silsesquioxane obtained in the above Preparation Example 1C was used instead of Preparation Example 1B, 11 g of inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B was used instead of Preparation Example 2A, 32 g of a nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of Example 2, and a radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0308]

[0309] [Manufacturing Example 18: Composition for hard coating and coating film thereof]

[0310] In the above Preparation Example 1, 12 g of silsesquioxane obtained in the above Preparation Example 1C was used instead of Preparation Example 1B, 11 g of inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B was used instead of Preparation Example 2A, 64 g of a dispersion of nanoparticles treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of Example 2, and a radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0311]

[0312] [Manufacturing Example 19: Composition for hard coating and coating film thereof]

[0313] In the above Preparation Example 1, 12 g of silsesquioxane obtained in the above Preparation Example 1C was used instead of Preparation Example 1B, 6 g of inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B was used instead of Preparation Example 2A, 42 g of a nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of Example 2, and a radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0314]

[0315] [Comparative Manufacturing Example 1: Composition for hard coating and coating film thereof]

[0316] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1H was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in the above Preparation Example 2B were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane in a cage structure on the surface of zirconia (ZrO2) dispersed in PGME obtained in Comparative Example 1 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0317]

[0318] [Comparative Manufacturing Example 2: Composition for hard coating and coating film thereof]

[0319] In the above Preparation Example 1, the silsesquioxane obtained in the above Preparation Example 1C was used instead of the Preparation Example 1B, the inorganic particles treated with silane on the surface of the hollow silica obtained in the above Preparation Example 2G were used instead of the Preparation Example 2A, the nanoparticle dispersion treated with silsesquioxane on the surface of the hollow silica dispersed in PGME obtained in Comparative Example 2 was used instead of the above Example 2, and the radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0320]

[0321] [Comparative Manufacturing Example 3: Composition for hard coating and coating film thereof]

[0322] In the above Preparation Example 1, Trimethylolpropane triacrylate was used instead of Preparation Example 1B, inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in Preparation Example 2B were used instead of Preparation Example 2A, a nanoparticle dispersion treated with silsesquioxane on the surface of zirconia (ZrO2) dispersed in PGME obtained in Example 1 was used instead of Example 2, and a radical UV initiator micure CP-4 was used instead of the ionic UV initiator irgacure-250, except that a hard coating composition and a coating film thereof were produced under the same conditions and by the same method as in Preparation Example 1.

[0323]

[0324] [Comparative Manufacturing Example 4: Composition for hard coating and coating film thereof]

[0325] In the above Preparation Example 1, 18 g was used instead of 12 g of silsesquioxane obtained in Preparation Example 1B, 27 g was used instead of 18 g of inorganic particles treated with silane on the surface of zirconia (ZrO2) obtained in Preparation Example 2A, and 55 g was added instead of 46 g of PGME to prepare a 100 g composition, and a hard coating composition and a coating film thereof were prepared under the same conditions and method as in Preparation Example 1.

[0326]

[0327]

[0328] [Comparative Manufacturing Example 5: Composition for hard coating and coating film thereof]

[0329] In the above Preparation Example 1, the silsesquioxane obtained in Preparation Example 1B was not used, 58 g of PGME was added instead of 46 g and mixed to prepare a 100 g composition, and 4 parts by weight of the ionic UV initiator irgacure-250 was used, except that a hard coating composition and a coating film thereof were prepared under the same conditions and method as in the above Preparation Example 1.

[0330]

[0331] [Experimental Example]

[0332] The dispersion stability of the hard coating compositions of the above Manufacturing Examples and Comparative Manufacturing Examples and the adhesion, pencil hardness, refractive index, transmittance and haze of the coating films prepared by curing the hard coating compositions of the above Manufacturing Examples and Comparative Manufacturing Examples were measured and are shown in Table 1 below. In addition, the refractive index of the modified inorganic particles according to some of the above Examples and Comparative Examples was measured and is shown in Table 2 below.

[0333]

[0334] - Dispersion stability: The manufactured composition was stored in an oven at 25℃, and the stability over time was visually confirmed for 6 months.

[0335]

[0336] - Adhesion evaluation: 100 scratches were made in a grid pattern at 1 mm intervals using a cutter blade according to JIS K5600-5-6, and adhesive tape was attached on top of them and then 90 0 The coating layer surface was visually inspected to see if it adhered to the adhesive tape and came off by peeling it off in the direction of the peel. The number that did not come off was indicated as the number out of 100 (e.g., the number that did not come off was indicated as number of pieces / 100, and if 100 pieces did not come off, it was indicated as 100 / 100).

[0337]

[0338] - Pencil hardness: Tested under a 750 g load according to JIS 5600-5-4. Mitsubishi pencils were used, and each pencil was tested five times. If two or more scratches occurred, it was judged as defective. The measured hardness and the number of times no scratches occurred / the number of tests were expressed.

[0339] * Pencil hardness: 9B~3B → 2B → 1B → HB → F → H → 2H → 3H~9H

[0340]

[0341] - Transmittance and haze: Measured using COH-400 (Nippon Denshoku) according to ISO 14782. Measurements were performed five times per sample, and the average value was reported.

[0342]

[0343] - Refractive index: Apply the composition on LCD glass, evaporate the solvent in an 85 degree drying oven, and then use UV equipment at 1 J / cm 2 The resultant 10㎛ film was obtained by irradiating UV, and the refractive index of the film at 632.8 nm was measured using a prism coupler (SPA-4000). The measurement was performed 5 times per sample, and the average value was reported.

[0344]

[0345] - SiOH content analysis:

[0346] 1. The presence or absence of OH was confirmed by measuring IR using the ATR mode of the Perkin-Elmer FT-IR system Spectrum-GX.

[0347] 2. The thermal stability of the manufactured structure was confirmed using a thermal gravimetric analyzer (TGA). Measurements were performed using TGA at a scan rate of 10 ℃ / min from 50 to 800 ℃ under nitrogen. The content was measured by confirming the amount of Si-OH decomposition that occurred between 100 and 200 ℃.

[0348]

[0349] Coating thickness (㎛)Coating adhesion Pencil hardness Transmittance (%)Refractive index (632.8 nm)Dispersion stabilityPET film--9B or less89.35--Manufacturing example 110Pass(100 / 100)3H(4 / 5)90.251.636 months or more Stable Manufacturing example 210Pass(100 / 100)2H(4 / 5)90.191.636 months or more Stable Manufacturing example 310Pass(100 / 100)2H(5 / 5)90.041.656 months or more Stable Manufacturing example 410Pass(100 / 100)2H(4 / 5)90.561.526 months or more Stable Manufacturing example 510Pass(100 / 100)H(4 / 5)90.151.626 months or more Stable Manufacturing example 610Pass(100 / 100)3H(5 / 5)90.021.576 months or more stable manufacturing example 710Pass(100 / 100)2H(5 / 5)90.211.583 months after, sediment is formed manufacturing example 810Pass(100 / 100)2H(5 / 5)90.211.623 months after, sediment is formed manufacturing example 910Pass(100 / 100)H(5 / 5)90.081.663 months after, sediment is formed manufacturing example 1010Pass(100 / 100)2H(4 / 5)90.201.636 months or more stable manufacturing example 1110Pass(100 / 100)2H(5 / 5)90.171.636 months or more stable manufacturing example 1210Pass(100 / 100)2H(5 / 5)90.151.626 months or more stable manufacturing example 1310Pass(100 / 100)2H(4 / 5)90.161.62 After 3 months, sediment is formed manufacturing example 1410Pass(100 / 100)2H(4 / 5)90.181.636 months or more stable manufacturing example 1510Pass(100 / 100)2H(4 / 5)90.221.636 months or more stable manufacturing example 1610Pass(100 / 100)2H(4 / 5)90.121.646 months or more stable manufacturing example 1710Pass(100 / 100)2H(4 / 5)90.171.616 months or more stable manufacturing example 1810Pass(100 / 100)2H(5 / 5)90.201.606 months or more stable manufacturing example 1910Pass(100 / 100)2H(5 / 5)90.221.After 563 months, sediment was formed. Comparative manufacturing example 110. Failure---After 7 days, sediment was formed. Comparative manufacturing example 210. Pass(100 / 100)5B91.071.25. Stable for more than 6 months. Comparative manufacturing example 310. Pass(100 / 100)B90.081.57. After 24 hours, sediment was formed. Comparative manufacturing example 410. Pass(100 / 100)B(3 / 5)82.62. Unmeasurable. After 24 hours, sediment was formed. Comparative manufacturing example 5. Uncured-.

[0350] Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 2 Refractive index (632.8 nm) 1.56 1.59 1.52 1.57 1.53 1.53 1.55 1.54 1.53 1.27

[0351]

[0352] Although the present invention has been described with reference to embodiments and manufacturing examples, it is to be understood that the present invention is not limited to the embodiments disclosed herein, and that various modifications may be made by those skilled in the art within the scope of the technical spirit of the present invention. Furthermore, even if the operational effects of the configuration of the present invention have not been explicitly described and explained while describing the embodiments of the present invention, it is natural that the effects predictable by the configuration should also be acknowledged.

Claims

1. Silsesquioxane comprising an open structure; and Containing inorganic particles combined with the above silsesquioxane, Modified inorganic particles having a refractive index of 1.3 or higher.

2. In paragraph 1, The above silsesquioxane is a modified inorganic particle comprising at least one of the repeating units represented by the following chemical formulas 1 and 2: [Chemical Formula 1] [Chemical formula 2] In the above chemical formulas 1 and 2, R1 is, each independently, a halogen group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, a thiol group, a glycidyl ether-substituted alkyl group having 1 to 10 carbon atoms, or an alicyclic epoxy group-substituted alkyl group having 1 to 10 carbon atoms, R2 is, each independently, hydrogen or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, n and m are, each independently, integers between 1 and 100,000, However, n or m only means the number contained in one silsesquioxane molecule, and when including both repeating units represented by Chemical Formula 1 and Chemical Formula 2, the connection order of the n number of structural units and the m number of structural units is not limited and can be connected in a random order.

3. In paragraph 1, The above silsesquioxane is a modified inorganic particle comprising a repeating unit represented by the chemical formula 1 and a repeating unit represented by the chemical formula 2: [Chemical Formula 1] [Chemical formula 2] In the above chemical formulas 1 and 2, R1 is, each independently, a halogen group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, a thiol group, a glycidyl ether-substituted alkyl group having 1 to 10 carbon atoms, or an alicyclic epoxy group-substituted alkyl group having 1 to 10 carbon atoms, R2 is, each independently, hydrogen or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, n and m are, each independently, integers between 1 and 100,000, However, n or m only means the number contained in one silsesquioxane molecule, and when including both repeating units represented by Chemical Formula 1 and Chemical Formula 2, the connection order of the n number of structural units and the m number of structural units is not limited and can be connected in a random order.

4. In paragraph 1, Modified inorganic particles, wherein the molecular weight of the above silsesquioxane is 1,000 g / mol to 200,000 g / mol.

5. In paragraph 1, The above-mentioned inorganic particles are modified inorganic particles, wherein the inorganic particles are at least one selected from the group consisting of zirconia, titania and barium titanate.

6. In paragraph 1, A modified inorganic particle, wherein the modified inorganic particle comprises silane on the surface of the modified inorganic particle, and the silsesquioxane is bonded to the modified inorganic particle through the silane.

7. In paragraph 6, A modified inorganic particle, wherein the weight ratio of the above inorganic particle: the silane: the silsesquioxane is 40 to 75:10 to 30:15 to 35.

8. Modified inorganic particles according to any one of clauses 1 to 7; High refractive inorganic particles; and A hard coating composition comprising a silicone-based binder.

9. In paragraph 8, A hard coating composition wherein the silicone-based binder is a silsesquioxane containing at least one of the repeating units represented by the following chemical formulas 1 and 2: [Chemical Formula 1] [Chemical formula 2] In the above chemical formulas 1 and 2, R1 is, each independently, a halogen group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, a thiol group, a glycidyl ether-substituted alkyl group having 1 to 10 carbon atoms, or an alicyclic epoxy group-substituted alkyl group having 1 to 10 carbon atoms, R2 is, each independently, hydrogen or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, n and m are, each independently, integers between 1 and 100,000, However, n or m only means the number contained in one silsesquioxane molecule, and when including both repeating units represented by Chemical Formula 1 and Chemical Formula 2, the connection order of the n number of structural units and the m number of structural units is not limited and can be connected in a random order.

10. In paragraph 9, A hard coating composition, wherein the silsesquioxane comprises a repeating unit represented by the chemical formula 1 and a repeating unit represented by the chemical formula 2.

11. In paragraph 8, A hard coating composition, wherein the silicone-based binder contains SiOH in an amount of 1 wt% or less.

12. In paragraph 8, A hard coating composition, wherein the high refractive index inorganic particles contain silane on the surface of the inorganic particles.

13. In paragraph 8, A hard coating composition, wherein the inorganic particles of the modified inorganic particles or the high refractive index inorganic particles are at least one selected from the group consisting of zirconia, titania and barium titanate.

14. In paragraph 8, A composition for hard coating, wherein the weight ratio of the modified inorganic particles to the high refractive inorganic particles is 1:0.25 to 3.

15. Modified inorganic particles according to Articles 1 to 7; High refractive index inorganic particles; A coating film comprising a silicon-based binder.

16. In paragraph 15, The refractive index of the above coating film is 1.3 or higher, A coating film with a hardness of H or higher.

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