Silsesquioxane resin and antireflection composition comprising the same and having Anti-fingerprint properties

Abstract

The present invention relates to a composition comprising a silsesquioxane resin containing specific chemical structural units and fluoroalkyl groups, and a cured product obtained by curing the same. More specifically, it relates to a composition capable of producing a cured product with excellent anti-reflective and water-repellent properties, and a cured product obtained by curing the same.

Description

Technology Field

[0001] The present invention relates to a silsesquioxane resin and a composition containing the same, and more specifically, to a composition having excellent anti-reflective and water-repellent properties simultaneously and a cured product obtained by curing the same. Background Technology

[0002] As display products have recently evolved to larger sizes, it has become important to achieve clearer images while protecting the display surface.

[0003] In addition, as the use of electronic products equipped with small mobile displays, such as touchscreen foldables and rollables, increases rapidly, window covers used to protect displays are being replaced from inflexible tempered glass to flexible plastic.

[0004] As such, anti-fingerprint, anti-scratch, and anti-reflective coatings are becoming important technologies to protect the surface of large-area displays while compensating for the shortcomings of plastic, which has relatively lower transmittance and poorer image clarity compared to glass.

[0005] Conventional anti-reflective coatings primarily utilize a dry process under high-temperature vacuum conditions, which makes large-area coating impossible and results in low productivity due to difficulties in continuous processes. Furthermore, they have the disadvantage of reduced reliability of the anti-reflective coating film due to low physical properties such as scratch resistance and adhesion.

[0006] For example, in Korean Patent Publication KR 2012-0139919 A, an anti-reflective multilayer film is formed by alternately depositing high-refractive index materials such as titanium dioxide (TiO2) or niobium pentoxide (Nb2O5) and low-refractive index materials such as silicon dioxide (SiO2) on a substrate. However, dry coating using such vacuum deposition has the disadvantage that large-area coating is not possible and productivity is low due to the difficulty of continuous processes.

[0007] In addition, the prior art implements anti-reflective and water-repellent functions through individual coating layers by laminating a coating layer with a water-repellent function separately from the anti-reflective coating layer on a substrate, as described in Korean registered patent KR 1395681 B1. However, in this case, the wet coating process is difficult because it requires a process of curing each coating layer and then laminating them, and consequently, there is a disadvantage of reduced processability and productivity. The problem to be solved

[0008] In order to solve the problems of the prior art as described above, the objective of the present invention is to provide a composition capable of forming a cured product that is applicable to a wet coating process advantageous for continuous processes and large-area coating, has excellent productivity, and simultaneously possesses excellent anti-reflective and water-repellent properties.

[0009] Another objective of the present invention is to provide a cured material with excellent anti-reflection of visible light and water-repellent properties, while having a low refractive index. means of solving the problem

[0010] To achieve the above objective, a silsesquioxane resin according to one embodiment of the present invention comprises structural units of the following chemical formulas 1 to 3.

[0011] [Chemical Formula 1]

[0012]

[0013] [Chemical Formula 2]

[0014]

[0015] [Chemical Formula 3]

[0016]

[0017] In the above formulas 1 to 3, R1 is each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, a fluorine-containing organic group having 1 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, or a thiol group, and at least one of R1 is a fluorine-containing organic group having 1 to 30 carbon atoms; R2 is each independently hydrogen, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0018] A composition according to another embodiment of the present invention comprises the silsesquioxane resin, an initiator, and a solvent.

[0019] A cured product according to another embodiment of the present invention is the above composition cured.

[0020] A display device according to another embodiment of the present invention includes the cured material. Effects of the invention

[0021] The composition containing the silsesquioxane resin according to the present invention can be applied to a wet process, thus eliminating the need for expensive vacuum dry deposition equipment, and can form a cured product with excellent processability and productivity. In addition, the composition provides excellent physical properties such as anti-reflective effect, water repellency, fingerprint resistance, stain resistance, and scratch resistance, and has the effect of lowering the refractive index.

[0022] The cured product according to the present invention has excellent water-repellent properties, fingerprint resistance, stain resistance, and chemical resistance, and can serve as a coating layer that is positioned on the outermost layer of electronic products having a touchscreen form to stably protect the display, etc. from fingerprints or scratches. Specific details for implementing the invention

[0023] Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0024] Therefore, the configurations illustrated in the embodiments and manufacturing examples described in this specification are merely one preferred embodiment of the present invention and do not represent all of the technical ideas of the present invention; thus, it should be understood that various equivalents and modifications that can replace them may exist at the time of filing this application.

[0025] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the manufacturing examples and embodiments described herein.

[0026] A silsesquioxane resin according to one embodiment of the present invention comprises all structural units of Chemical Formulas 1 to 3, and when applied to a cured product, it has the effect of providing both anti-reflective and water-repellent properties without a separate additional coating.

[0027] [Chemical Formula 1]

[0028]

[0029] [Chemical Formula 2]

[0030]

[0031] [Chemical Formula 3]

[0032]

[0033] In the above formulas 1 to 3, R1 is each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, a fluorine-containing organic group having 1 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, or a thiol group, and at least one of R1 is a fluorine-containing organic group having 1 to 30 carbon atoms; R2 is each independently hydrogen, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0034] The above-mentioned fluorine-containing organic group may be, for example, a fluoroalkyl group.

[0035] When the structure of Chemical Formula 1 is combined with the structure of Chemical Formula 2 or Chemical Formula 3, it is preferable that two structures of Chemical Formula 1 be combined together at the bonding site of Chemical Formula 2 or Chemical Formula 3, as shown in Chemical Formula 1-1 below.

[0036] [Chemical Formula 1-1]

[0037]

[0038] In the above silsesquioxane resin, the above chemical formula 1 has a form in which two Si groups are not connected to each other, and due to the above structure, pores are formed in the silsesquioxane resin, and are included in a composition according to one embodiment of the present invention to impart anti-reflective properties.

[0039] The above chemical formula 2 includes OR2, and the above silsesquioxane resin is included in the composition according to one embodiment of the present invention to improve adhesion and contribute to forming a stable cured product. In particular, the above OR2 is capable of forming covalent bonds with Si-OH or Si-O, etc., on the glass surface, so when the above composition is used as a coating composition, it imparts characteristics that increase bonding and adhesion to the substrate during coating.

[0040] In addition, the above chemical formula 3 is included in a composition according to one embodiment of the present invention and functions to impart resin properties, impart water repellency, and enable a low refractive index.

[0041] In addition, the above silsesquioxane resin contains a fluorine-containing organic group, specifically, which may be located at the R1 position of Chemical Formulas 1 to 3. As the composition according to the present invention contains the above fluorine-containing organic group, it has the effect of imparting water-repellent properties. Therefore, when the silsesquioxane resin according to the present invention is included in a composition, it can impart anti-reflective effects, water-repellent properties, fingerprint resistance, and low refractive index properties.

[0042] The above-mentioned fluorine-containing organic group preferably has a carbon number of 3 or more. The above-mentioned fluorine-containing organic group may be included in all of the above-mentioned chemical formulas 1 to 3. If the carbon number is less than 3, a problem may arise where the water repellency and anti-reflective effect of the composition are reduced. If the carbon number is greater than 15, the size of the fluorine-containing organic group becomes excessively large, which reduces compatibility, making it difficult to manufacture the composition containing the silsesquioxane resin in the form of a cured product, and a problem of poor haze may occur even after curing. Specifically, it is preferable that the carbon number is 12 or less.

[0043] The above silsesquioxane resin may be copolymerized by independently including 1 to 100,000 of each structural unit represented by Chemical Formulas 1 to 3. If even one type of each structural unit is not included, a problem may arise in that the composition lacks the anti-reflective function, adhesion enhancement function, and water repellency function imparted by the corresponding structure. If more than 100,000 of the structural units are included in the resin, the polymer chains of the resin become excessively long and do not dissolve in a solvent, which may result in a problem where wet coating becomes impossible when applied as a coating composition. More specifically, including 1,000 to 10,000 of each structural unit in the resin effectively maintains the characteristics imparted by each structural unit and has an effect that is advantageous for wet coating.

[0044] The above resin may be a block copolymer, or a random copolymer in which the unit structures of Chemical Formulas 1 to 3 are randomly arranged, but is not limited to the type of copolymer.

[0045] When the structures of Formulas 1 to 3 included in the above silsesquioxane resin are copolymerized at a specific ratio, the anti-reflective function, water repellency, and adhesion of the composition can be maximized. Specifically, the sum of the number of structural units of Formula 1 (hereinafter n) and the number of structural units of Formula 3 (hereinafter k) may be 1 to 50 times the number of structural units of Formula 2 (hereinafter m), i.e., (n+k) / m may be in the range of 1 to 50, and each structural unit may be included in the copolymerization. If the ratio of structural units of Formula 2 is high compared to the above ratio range ((n+k) / m < 1), a problem may arise where the anti-reflective function and water repellency of the composition are reduced. If the ratio of structural units of Formula 2 is low compared to the above ratio ((n+k) / m > 1), the adhesion of the composition is reduced, and when formed as a coating layer, a problem may arise where the coating layer is easily detached from the substrate underneath the coating layer.

[0046] In the above silsesquioxane resin, it is preferable that the number of structural units of Formula 1 be greater than the number of structural units of Formula 3, as this allows the composition to have excellent anti-reflective function and water repellency. Specifically, the ratio (n : k) of the number of structural units of Formula 1 to the number of structural units of Formula 3 is preferably 20 : 1 to 1 : 20. If the ratio of the number of Formula 1 is higher than the above range, there may be a problem with reduced water repellency, and if the ratio of the number of Formula 3 is higher than the above range, there may be a problem with reduced anti-reflective properties.

[0047] The above silsesquioxane resin may be a resin comprising structural units of Chemical Formulas 1 to 3 and represented by Chemical Formula 4 below.

[0048] [Chemical Formula 4]

[0049]

[0050] In the above chemical formula 4, R1 is each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, a fluorine-containing organic group having 1 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, or a thiol group, and at least one of R1 is a fluorine-containing organic group having 1 to 30 carbon atoms; R2 is each independently hydrogen, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; and n, m, and k are each independently integers from 1 to 100,000.

[0051] The fluorine-containing organic group included in the above silsesquioxane resin may specifically be located at the R1 position of Chemical Formula 4. However, in addition to the fluorine-containing organic group, one of a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 aryl group, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, or a thiol group may be located at the R1 position, and it is sufficient for the silsesquioxane resin to have at least one fluorine-containing organic group. However, having a higher proportion of the fluorine-containing organic group at the R1 position compared to the other functional groups is effective for imparting anti-reflective function and water repellency to the composition. Specifically, when 50 to 90 mol%, more specifically 65 to 85 mol%, of the fluorine-containing organic group at R1 of Chemical Formula 4 is included in the composition, anti-reflective function and water repellency can be imparted more effectively. If the above-mentioned fluorine-containing organic group is included in an amount of less than 50 mol% of R1, the anti-reflective and water-repellent effects of the composition containing the silsesquioxane resin may be reduced, and if it is included in an amount greater than 90 mol%, a problem may occur in which the curing of the composition does not proceed easily.

[0052] In the above chemical formula 4, 10 to 30 mol% of R1 is composed of one of an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, and a thiol group, which helps to effectively cure the cured product. If the functional group composed of one of the amino group, (meth)acrylic group, vinyl group, epoxy group, and thiol group is composed of less than 10 mol% of R1, the cured product may not cure well, and a problem may arise where the durability of the cured product is reduced. If it is included in an amount greater than 30 mol%, the relative proportion of the fluorine-containing organic group decreases, and a problem may arise where properties such as anti-reflective function and water repellency are not effectively imparted to the composition.

[0053] R1 of the above chemical formula 4 may be composed of one functional group selected from an alkyl group, a cycloalkyl group, and a phenyl group in an amount of 0 to 20 mol%, i.e., 20 mol% or less. The alkyl group, the cycloalkyl group, and the phenyl group are located in R1 where the amino group, (meth)acrylic group, vinyl group, epoxy group, thiol group, and fluorine-containing organic group are not located, and are included in an amount of 20 mol% or less to ensure that the function of other functional groups is sufficiently exhibited. However, since they are not the main functional groups in the above silsesquioxane resin, it is acceptable if they are not included.

[0054] A composition according to one embodiment of the present invention includes an initiator and a solvent to form a cured product by curing the silsesquioxane resin, which is a binder resin. Depending on the type of R1 of Formulas 1 to 3 included in the silsesquioxane, various initiators may be used. As a specific example, when an unsaturated hydrocarbon is introduced into the above R1, a radical initiator may be used, and the radical initiator may be trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxyl-2-methylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2,4,6-trimethyl benzoyl diphenylphosphine oxide, camphor quinine, 2,2'-azobis(2-methylbutyronitrile), One of the photoradical initiators such as dimethyl-2,2'-azobis(2-methyl butylate), 3,3-dimethyl-4-methoxy-benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenyl ethane-1-one, thermal radical initiators such as t-butylperoxymaleic acid, t-butylhydroperoxide, 2,4-dichlorobenzoyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, N-butyl-4,4'-di(t-butylperoxy)valerate, and various mixtures thereof may be used, but is not limited to the above examples.

[0055] In addition, when the above R1 includes an epoxy, specific examples include, as photopolymerization cation initiators, sulfonium-based initiators such as triphenylsulfonium and diphenyl-4-(phenylthio)phenylsulfonium, iodium initiators such as diphenyliodonium or bis(dodecylphenyl)iodonium, diazonium initiators such as phenyldiazonium, ammonium initiators such as 1-benzyl-2-cyanopyrinium or 1-(naphthylmethyl)-2-cyanopridinium, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate iodonium, bis(4-t-butylphenyl)hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoromethanesulfonate iodonium, triphenylsulfonium tetrafluoroborate, tri-p-toylsulfonium hexafluorophosphate, and tri-p-toylsulfonium Fe cations such as trifluoromethanesulfonate and (2,4-cyclopentadiene-1-yl)[(1-methylethyl)benzene]-Fe and BF4 - , PF6 - , SbF6 - [BQ4] of the etc. - Onium salt combinations may be used, but are not limited to the examples above (where Q is a phenyl group substituted with at least two fluorine or trifluoromethyl groups). Additionally, as heat-activated cationic initiators, cationic or proton acid catalysts such as triphosphates, boron trifluoride ether complexes, boron trifluoride, etc., various onium salts such as ammonium salts, phosphonium salts, and sulfonium salts, and methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide, etc., may be used without limitation but are not limited to the examples above. These initiators may also be added in various mixed forms, and may be mixed with the various radical initiators specified above.

[0056] For every 100 parts by weight of the above silsesquioxane resin, the initiator is preferably included in an amount of 0.1 to 5 parts by weight. If the initiator is included in an amount less than 0.1 parts by weight, the curing may not be initiated properly, which may cause problems in forming a cured product; if it is included in an amount greater than 5 parts by weight, the initiator may be excessively included, resulting in residual initiator components in the cured product and a decrease in the physical properties of the cured product.

[0057] The composition according to the present invention may further include an amine curing agent depending on the type of R1, and may include, for example, one or more of ethylenediamine, triethylenetetramine, tetraethylenepentamine, 1,3-diaminopropane, dipropylentiamine, 3-(2-aminoethyl)amino-propylamine, N,N'-bis(3-aminopropyl)-ethylenediamine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecan-1,13-diamine, hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis(4-animocyclohexyl)methane, norbornendiamine, and 1,2-diaminocyclohexane.

[0058] The composition according to the present invention may further include a curing accelerator to promote the curing action, for example, triazine compounds such as acetoguanamin, benzoguanamine, and 2,4-diamino-6-vinyl-s-triazine; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole; 1,5-diazabicyclo[4.3.0]nonen-5,1,8-diazabicyclo[5.4.0]undecen-7, triphenylphosphine, diphenyl(p-tril)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, One or more of tetrabutylphosphonium acetate, tetrabutylphosphonium hydrogendifluoride, and tetrabutylphosphonium dihydrogentrifluoride may be used.

[0059] In addition, acid anhydride curing agents such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl anhydride, hydrogenated methyl anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, and 2,4-diethylglutaric anhydride can also be widely used.

[0060] The solvent included in the above composition may be used regardless of type as long as it can dissolve the silsesquioxane resin and the initiator. However, if the solvent includes a fluorine-based solvent, the fluorine in the fluorine-based solvent, along with the fluorine-containing organic groups of the silsesquioxane resin dissolved in the solvent, can help effectively impart anti-reflective and water-repellent properties to the composition. Specifically, if the content of the fluorine-based solvent accounts for 80% by weight or more of the solvent, a significant increase in the aforementioned effects due to the use of the fluorine-based solvent can be observed, and the composition is advantageous for forming a uniform cured product. In particular, when the above composition is used as a coating composition, it can be uniformly coated on a substrate and form a flat and even coating layer. For the composition according to the present invention, the solvent may be included in an amount of 80 to 99% by weight, and the silsesquioxane resin may be included in an amount of 0.1 to 15% by weight.

[0061] The above solvent is, for example, a solvent capable of dissolving silsesquioxane resin, and includes not only polar solvents such as ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, perfluorobutyl ethyl ether, perfluorohexyl methyl ether, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, alcohols such as cellosolve-based solvents, lactate-based solvents, ketones such as acetone and methyl(isobutyl)ethyl ketone, glycols such as ethylene glycol, furans such as tetrahydrofuran, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, but also hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, methylene chloride, and octadecylamine, Various solvents such as aniline, dimethyl sulfoxide, and benzyl alcohol may be used, and one or more solvents may be used, but are not limited thereto.

[0062] The composition according to the present invention may further include a fluorinated silane. The fluorinated silane has the effect of further enhancing the anti-fingerprint effect by increasing the slipperiness of the surface of the cured product when additionally included in the composition and cured, but it is not a problem if it is not included.

[0063] The above-mentioned fluorinated silane is, for example, a derivative and polymer of a silane containing a perfluoro(poly)ether group, chlorosilane, dichlorosilane, trichlorosilane, alkylsilane, dialkylsilane, trialkylsilane, alkoxysilane, dialkoxysilane, dialkoxysilane, benzylsilane, dibenzylsilane, tribenzylsilane, cycloalkylsilane, dicycloalkylsilane, tricycloalkylsilane, chloro-dialkylsilane, dichloro-alkylsilane, chloro-dialkoxysilane, dichloro-alkoxysilane, alkyl-dialkoxysilane, dialkyl-alkoxysilane, alkyl-dialkoxysilane, dialkyl-alkoxysilane, derivative and polymer of silane, chlorosilane, dichlorosilane, trichlorosilane, alkylsilane, dialkylsilane, trialkylsilane, alkoxysilane, silane, chlorosilane, dichlorosilane, trichlorosilane, trialkylsilane, alkoxysilane, alkylsilane, dialkylsilane, trialkylsilane, alkoxysilane, benzylsilane, dibenzylsilane, trialkylsilane, alkoxysilane, silane, chlorosilane, dichlorosilane, trichlorosilane, trialkylsilane, alkoxysilane, alkylsilane, dialkylsilane, trialkylsilane, alkoxysilane, benzylsilane, dialkylbenzylsilane, dialkylsilane, trialkylsilane, alkoxysilane, alkylsilane, dialkylsilane, trialkylsilane, alkoxysilane, benz One or more derivatives and polymers of dialkoxysilane, trialkoxysilane, benzylsilane, dibenzylsilane, tribenzylsilane, cycloalkylsilane, dicycloalkylsilane, tricycloalkylsilane, chloro-dialkylsilane, dichloro-alkylsilane, chloro-dialkylsilane, dichloro-alkoxysilane, alkyl-dialkylsilane, and dialkyl-alkoxysilane may be used.

[0064] A composition according to one embodiment of the present invention is a composition comprising the silsesquioxane resin of the present invention, and may be used as a coating composition, a film-forming composition, an injection-molding composition, a membrane-forming composition, etc., but is not limited thereto.

[0065] A cured product according to one embodiment of the present invention is a cured product formed by curing the above composition, and may be a coating layer, a functional film, an injection molded product, a membrane, etc., but is not limited thereto.

[0066] The refractive index of the cured product may be 1.20 to 1.45, and the refractive index of the composition before curing with the cured product may also have a low refractive index of 1.20 to 1.45, which is similar to the refractive index of the cured product.

[0067] Specifically, the cured product may be a coating layer, and the composition may be cured to form a coating layer on a substrate. Since the coating layer has water-repellent and anti-reflective functions simultaneously, it is not necessary to form two separate layers having water-repellent and anti-reflective functions as in the past, and accordingly, the processability and productivity of forming the coating layer are greatly improved.

[0068] When the above-mentioned cured material is a coating layer, it may be coated on a glass or plastic material, a substrate, or on top of a hard coating layer. When coated on top of the hard coating layer, the cured material exhibits excellent adhesion. By coating the composition according to the present invention on top of the hard coating layer, a cured material having a thickness of 30 to 250 nm can be formed. The thickness range can be adjusted according to the wavelength of the irradiated light. As a specific example, a coating layer at a level of 1 / 4 of the visible light wavelength can be formed to cause destructive interference in the coating layer, thereby imparting an anti-reflection effect to the coating layer according to the present invention for visible light; however, the anti-reflection effect is not limited to the visible light region and can also be applied to light such as ultraviolet and infrared rays. Furthermore, within the above thickness range, the coating layer according to the present invention exhibits excellent water-repellent, fingerprint-resistant, stain-resistant, and scratch-resistant properties.

[0069] When the above-mentioned cured material is a coating layer, the composition according to the present invention can be applied in a wet coating method during the process of forming the coating layer. In the case of conventional dry anti-reflective coatings using vacuum deposition, large-area coating was not possible, which made continuous processing difficult. Consequently, there was a problem in that productivity was low and a coating layer with poor physical properties such as scratch resistance and adhesion was formed. However, the composition according to the present invention enables large-area coating and continuous processing through wet coating, thereby having the effect of increasing productivity along with the excellent physical properties of the coating layer.

[0070] A display device according to one embodiment of the present invention is a display device including the cured material, and specifically, the cured material may be applied to a coating layer of the display device. However, the cured material according to one embodiment of the present invention is not limited to use in a display device, and may be applied to devices or products such as eyeglass lenses, camera lenses, architectural windows, display panels, automotive glass, solar cells, etc., and may have the effect of reducing light reflected from the surface and increasing light transmittance when applied to said device or product.

[0071] Hereinafter, preferred embodiments are presented to aid in understanding the present invention; however, the following embodiments are merely illustrative of the invention and the scope of the invention is not limited to the following embodiments.

[0072] [Preparation Example: Preparation of Silsesquioxane Resin]

[0073] [Preparation Example 1]

[0074] In a dry flask equipped with a condenser and a stirrer, 25.6 g of distilled water and 100 g of methanol were mixed and prepared, and 52.32 g (0.2 mol) of 3-(Trichlorosilyl)propyl methacrylate was slowly added dropwise over 10 minutes. During this process, the temperature was maintained at -4°C. After stirring the mixture for 20 minutes, 500 g of toluene was additionally added dropwise, and the temperature was raised to room temperature and stirred for another 10 minutes. Subsequently, 351.21 g (0.75 mol) of (Tridecafluoro-1,1,2,2-tetrahydrooctyl)-1-Trimethoxysilane and 11.78 g (0.05 mol) of (3-methacryloxy)propylmethyl dimethoxysilane were added dropwise simultaneously and stirred for 10 minutes.

[0075] While the above reaction was in progress, a 20 wt% aqueous solution of Na2CO3 was prepared separately, and 20 g of the solution was added dropwise to a flask containing the reaction mixture. Subsequently, the temperature was raised to 100°C and the condensation reaction was carried out for one day. The mixture from which the condensation reaction was carried out underwent purification by separating the layers of water and toluene twice, and after confirming that the pH was neutral, the toluene layer was separated and all the toluene was removed under reduced vacuum pressure to obtain a silsesquioxane resin.

[0076] [Preparation Example 2]

[0077] Silsesquioxane resin was obtained by the same method as in Preparation Example 1, except that 100g of methanol in Preparation Example 1 was replaced with 800g of methanol and mixed.

[0078] [Preparation Example 3]

[0079] Silsesquioxane resin was obtained by the same method as in Preparation Example 1, except that 100g of methanol in Preparation Example 1 was replaced with 30g of methanol and mixed.

[0080] [Preparation Example 4]

[0081] Silsesquioxane resin was obtained by the same method as in Preparation Example 1, except that 100g of methanol in Preparation Example 1 was replaced with 500g of methanol and mixed.

[0082] [Preparation Example 5]

[0083] Silsesquioxane resin was obtained by the same method as in Preparation Example 1, except that the 100g of methanol in Preparation Example 1 was replaced with 50g of methanol and mixed.

[0084] [Preparation Example 6]

[0085] A silsesquioxane resin was obtained using the same method as in Preparation Example 1, except that 104.64 g (0.4 mol) of 3-(Trichlorosilyl)propyl methacrylate, 187.31 g (0.4 mol) of (Tridecafluoro-1,1,2,2-tetrahydrooctyl)-1-Trimethoxysilane, and 47.14 g (0.2 mol) of (3-methacryloxy)propylmethyl dimethoxysilane were used.

[0086] [Preparation Example 7]

[0087] A silsesquioxane resin was obtained using the same method as in Preparation Example 1, except that 10.46 g (0.04 mol) of 3-(Trichlorosilyl)propyl methacrylate, 444.87 g (0.95 mol) of (Tridecafluoro-1,1,2,2-tetrahydrooctyl)-1-Trimethoxysilane, and 2.36 g (0.01 mol) of (3-methacryloxy)propylmethyl dimethoxysilane were used.

[0088] [Preparation Example 8]

[0089] Silsesquioxane resin was obtained by the same method as in Preparation Example 1, except that 78.48 g (0.3 mol) of 3-(Trichlorosilyl)propyl methacrylate, 280.97 g (0.6 mol) of (Tridecafluoro-1,1,2,2-tetrahydrooctyl)-1-Trimethoxysilane, and 23.57 g (0.1 mol) of (3-methacryloxy)propylmethyl dimethoxysilane were used.

[0090] [Preparation Example 9]

[0091] Silsesquioxane resin was obtained by the same method as in Preparation Example 1, except that 26.16 g (0.1 mol) of 3-(Trichlorosilyl)propyl methacrylate, 412.09 g (0.88 mol) of (Tridecafluoro-1,1,2,2-tetrahydrooctyl)-1-Trimethoxysilane, and 4.71 g (0.02 mol) of (3-methacryloxy)propylmethyl dimethoxysilane were used.

[0092] [Comparative Preparation Example 1]

[0093] In a dry flask equipped with a condenser and a stirrer, 25.6 g of distilled water and 100 g of methanol were mixed and 52.32 g (0.2 mol) of 3-(Trichlorosilyl)propyl methacrylate was slowly added dropwise over 10 minutes. During this process, the temperature was maintained at -4°C. After stirring the mixture for 20 minutes, 500 g of toluene was added dropwise, and the temperature was raised to room temperature and stirred for another 10 minutes. Subsequently, 11.82 g (0.05 mol) of 3-Glycidoxypropyl trimethoxysilane and 351.21 g (0.75 mol) of (Tridecafluoro-1,1,2,2-tetrahydrooctyl)-1-Trimethoxysilane were added dropwise simultaneously and stirred for 10 minutes.

[0094] While the above reaction was in progress, a 20 wt% aqueous solution of Na2CO3 was prepared separately, and 20 g of the solution was added dropwise to a flask containing the reaction mixture. Subsequently, the temperature was raised to 100°C and the condensation reaction was carried out for one day. The mixture from which the condensation reaction was carried out underwent purification by separating the water and toluene layers twice, and after confirming that the pH was neutral, the toluene layer was separated and all the toluene was removed under reduced vacuum pressure to obtain a silsesquioxane resin.

[0095] [Comparative Preparation Example 2]

[0096] Silsesquioxane resin was obtained by the same method as in Comparative Example 1, except that 209.29 g (0.8 mol) of 3-(Trichlorosilyl)propyl methacrylate, 23.63 g (0.1 mol) of 3-Glycidoxypropyl trimethoxysilane, and 46.83 g (0.1 mol) of (Tridecafluoro-1,1,2,2-tetrahydrooctyl)-1-Trimethoxysilane were used.

[0097] Table 1 below shows the number of carbon atoms of the F-alkyl (fluorine-containing organic group) of the resin obtained according to the above manufacturing example and comparative manufacturing example, the (n+k) / m ratio according to Chemical Formula 4, and the F-alkyl ratio (mol%) in R1 according to Chemical Formula 4.

[0098] F-alkyl carbon number (n+k) / m R1-alkyl ratio (mol%) Preparation Example 1 8 15 75 Preparation Example 2 8 0.5 75 Preparation Example 3 8 55 75 Preparation Example 4 8 5 75 Preparation Example 5 8 40 75 Preparation Example 6 8 15 40 Preparation Example 7 8 15 95 Preparation Example 8 8 15 60 Preparation Example 9 8 15 88 Comparative Manufacturing Example 1 8 No n group 75 Comparative Manufacturing Example 2 8 No n group 10

[0099] [Example: Preparation of a composition containing silsesquioxane resin]

[0100] [Example 1]

[0101] 2.0 g of the silsesquioxane resin obtained in Preparation Example 1 above was dissolved in a fluorine-based solvent (3M FC-3283) to prepare 100 g of a composition containing 2.0 wt% of silsesquioxane resin. For every 100 parts by weight of the composition, 0.1 parts by weight of a fluorine-based silane (DAIKIN OPTOOL UD509) and 0.1 parts by weight of a radical thermal initiator (Wako V65) were added to the 100 g of the composition and stirred for 10 minutes to prepare a water-repellent coating composition.

[0102] [Examples 2 to 5]

[0103] A water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Preparation Examples 2 to 5 was used.

[0104] [Example 6]

[0105] A water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Preparation Example 6 was used and 0.2 parts by weight of a radical thermal initiator (Wako V65) was used.

[0106] [Example 7]

[0107] A water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Preparation Example 7 was used and 0.02 parts by weight of a radical thermal initiator (Wako V65) was used.

[0108] [Example 8]

[0109] A water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Preparation Example 8 was used and 0.15 parts by weight of a radical thermal initiator (Wako V65) was used.

[0110] [Example 9]

[0111] A water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Preparation Example 9 was used and 0.05 parts by weight of a radical thermal initiator (Wako V65) was used.

[0112] [Example 10]

[0113] A water-repellent coating composition was prepared in the same manner as in Example 1, except that a mixed solvent was used in which a fluorine-based solvent (3M FC-3283) and methyl ethyl ketone were mixed in a ratio of 7:3 by weight.

[0114] [Example 11]

[0115] A water-repellent coating composition was prepared in the same manner as in Example 6, except that methyl ethyl ketone was used as the solvent.

[0116] [Comparative Example 1]

[0117] A water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Comparative Preparation Example 1 was used.

[0118] [Comparative Example 2]

[0119] A water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Comparative Preparation Example 2 was used and 0.4 parts by weight of a radical thermal initiator (Wako V65) was used.

[0120] [Comparative Example 3]

[0121] A water-repellent coating composition was prepared in the same manner as in Example 1, except that a commercial silsesquioxane compound represented by the following chemical formula a [Hybrid plastics FL0578 (Trifluoropropyl POSS Cage Mixture)] was used instead of the silsesquioxane resin of the present invention.

[0122] [Chemical formula a]

[0123]

[0124] [Comparative Example 4]

[0125] A water-repellent coating composition was prepared in the same manner as in Example 1, except that a siloxane-based compound represented by the following chemical formula b (Trifluoropropylmethylsiloxane) was used instead of the silsesquioxane resin of the present invention.

[0126] [Chemical formula b]

[0127]

[0128] [Experimental Example: Evaluation of Cured Product Containing Silsesquioxane Resin]

[0129] The composition prepared in the above examples and comparative examples was applied to an LCD glass substrate (SM-TECH, 75×75×0.5), and UV curing (A-line 1J) and 150 After curing for 30 minutes, the transmittance, haze, refractive index, scratch resistance, eraser abrasion resistance test, and eraser chemical resistance test were evaluated, and the results are shown in Table 2 below.

[0130] o Transmittance, Haze: Measured using COH-400 (Nippon Denshoku) in accordance with ISO 14782. Five measurements were taken per sample, and the average value was recorded.

[0131] o Refractive index: Measured using a prism coupler, with 5 measurements taken per sample and the average value recorded.

[0132] o Scratch resistance: In accordance with JIS K5600-5-9, #0000 steel wool was used and tested with a load of 1 kgf. At this time, the number of reciprocating cycles was 10,000 under harsh conditions, and the presence or absence of scratches was checked using an optical microscope and indicated as O / X.

[0133] o Eraser wear resistance test: Conducted in accordance with KS B ISO 9211-4. A dedicated eraser for wear resistance testing was used, and the test was performed 5,000 times back and forth with a load of 1 kgf, and the contact angle values ​​of the substrate surface were measured before and after the test.

[0134] o Eraser chemical resistance test: An eraser specifically designed for abrasion resistance testing was used, and the test was conducted 10,000 times back and forth with a load of 1 kgf. During this process, ethanol was dripped between the eraser and the sample to prevent it from drying out during the test. The contact angle values ​​of the substrate surface were measured before and after the test.

[0135] Transmittance (%) Haze Refractive index My Scratch (O / X) Eraser wear resistance(°) Eraser chemical resistance(°) jeon after jeon after Example 1 95.55 0.08 1.36 O 118 113 118 112 Example 2 95.04 0.06 1.39 O 112 97 112 109 Example 3 95.71 0.14 1.32 O 120 115 120 96 Example 4 95.27 0.07 1.37 O 115 103 115 110 Example 5 95.63 0.12 1.33 O 119 114 119 101 Example 6 94.42 0.07 1.38 O 113 108 113 105 Example 7 96.18 0.24 1.31 O 121 96 121 98 Example 8 94.96 0.08 1.37 O 117 110 117 107 Example 9 95.92 0.19 1.33 O 119 98 119 99 Example 10 94.82 0.34 1.39 O 116 107 116 105 Example 11 94.06 0.46 1.40 O 111 98 111 95 Comparative Example 1 93.45 0.51 1.40 O 112 106 112 102 Comparative Example 2 92.92 0.68 1.48 X 98 69 98 65 Comparative Example 3 93.11 0.11 1.38 X 117 65 117 69 Comparative Example 4 93.05 0.12 1.46 X 116 66 116 70 Reference Example 1 92.34 0.07 1.52 O 91 - 91 -

[0136] * Reference Example 1: Evaluation results of LCD glass prior to coating with the composition

[0137] As shown in Table 2 above, in the case of the embodiment of the present invention, the transmittance was 94.00 or higher, the haze was 0.5 or lower, and the refractive index was 1.40 or lower. In addition, no scratches occurred in the scratch test, and after the eraser wear resistance and eraser chemical resistance tests, the contact angle was 95° or higher, and it can be seen that the wear resistance and chemical resistance are excellent as the change in contact angle is small compared to before the test.

[0138] (Effect according to the ratio of structural units of Chemical Formulas 1 to 3)

[0139] The values ​​of Examples 1 to 5 are represented by expressing the ratio of structural units of Chemical Formulas 1 to 3 as (n+k) / m values ​​as described above, as shown in Table 3 below.

[0140] Example 1 Example 2 Example 3 Example 4 Example 5 (n+k) / m 10~30 Less than 1 Over 50 1~10 30~50

[0141] Referring to Tables 2 and 3 above, the transmittance and contact angle after wear resistance of Example 1 are shown to be higher values ​​compared to Examples 2 and 4, and transmittance and wear resistance become more excellent as the (n+k) / m value increases. However, the contact angle after the chemical resistance test of Examples 5 and 3 is lower than that of Example 1, and a phenomenon of decreased chemical resistance occurs when the (n+k) / m value exceeds 30. Therefore, considering transmittance, eraser wear resistance, and chemical resistance, Example 1, with an (n+k) / m value of 10 to 30, exhibits the most superior effect among the examples.

[0142] (In the structure of Chemical Formula 4, the total R 1 Effects according to the ratio of fluorinated organic groups)

[0143] Examples 1 and 6 to 9 are shown in Table 4 below based on the molar ratio of the total R1 fluorine-containing organic group in the structure of Formula 4.

[0144] Example 1 Example 6 Example 7 Example 8 Example 9 Molar ratio of fluorinated organic groups in R1 (mol%) 65~85 Less than 50 Over 90 50~65 85~90

[0145] Referring to Tables 2 and 4 above, the transmittance of Example 1 is higher than that of Examples 6 and 8, and the transmittance improves as the molar ratio of the fluorine-containing organic group increases. However, the contact angle of the eraser wear resistance and chemical resistance tests of Example 1 is lower compared to Examples 7 and 9, and a phenomenon in which wear resistance and chemical resistance decrease occurs when the molar ratio of the fluorine-containing organic group exceeds a certain molar ratio. Therefore, considering transmittance, wear resistance, and chemical resistance, Example 1, in which the molar ratio (mol%) of the fluorine-containing organic group of R1 is 65 to 85, exhibits the best effect.

[0146] (Effects of using fluorinated solvents)

[0147] The values ​​of Examples 1 and 10 to 11 based on the weight % of the fluorine-based solvent among the above solvents are shown in Table 5 below.

[0148] Example 1 Example 10 Example 11 Proportion of fluorinated solvent in the solvent (weight%) 100 10~80 Excluded

[0149] Referring to Tables 2 and 5 above, Example 1, which contains less than 80 wt% of a fluorinated solvent in the solvent, shows superior performance in all aspects compared to Example 10, and Example 6, which uses only a fluorinated solvent, shows superior performance in all aspects compared to Example 11, which does not contain a fluorinated solvent (using the silsesquioxane resin of Synthesis Example 6). This indicates that overall performance improves as the content of the fluorinated solvent increases.

[0150] Although embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and it will be obvious to those skilled in the art that various modifications and variations are possible within the scope of the technical concept of the present invention as described in the claims.

Claims

Claim 1 Silsesquioxane resin comprising structural units of the following chemical formulas 1 to 3: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the above formulas 1 to 3, R1 is each independently an unsubstituted alkyl group having 1 to 30 carbon atoms, an unsubstituted cycloalkyl group having 1 to 30 carbon atoms, an unsubstituted aryl group having 1 to 30 carbon atoms, a fluorine-containing organic group having 1 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, or a thiol group, and at least one of R1 is a fluorine-containing organic group having 1 to 30 carbon atoms; R2 is each independently hydrogen or an unsubstituted alkyl group having 1 to 10 carbon atoms. Claim 2 In claim 1, the fluorine-containing organic group having 1 to 30 carbon atoms is a silsesquioxane resin having 3 to 15 carbon atoms and a fluoroalkyl group. Claim 3 A silsesquioxane resin according to claim 1, comprising 1 to 100,000 structural units of each of the above chemical formulas 1 to 3 independently. Claim 4 A silsesquioxane resin according to claim 1, wherein the sum of the number of structural units of Chemical Formula 1 and the number of structural units of Chemical Formula 3 is 1 to 50 times the number of structural units of Chemical Formula 2. Claim 5 A silsesquioxane resin according to claim 1, wherein the ratio of the number of structural units of Chemical Formula 1 to the number of structural units of Chemical Formula 3 is 20:1 to 1:

20. Claim 6 In claim 1, a silsesquioxane resin having the structure of the following chemical formula 4: [Chemical Formula 4] In the above formula 4, R1 is each independently an unsubstituted alkyl group having 1 to 30 carbon atoms, an unsubstituted cycloalkyl group having 1 to 30 carbon atoms, an unsubstituted aryl group having 1 to 30 carbon atoms, a fluorine-containing organic group having 1 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, or a thiol group, and at least one of R1 is a fluorine-containing organic group having 1 to 30 carbon atoms; R2 is each independently hydrogen or an unsubstituted alkyl group having 1 to 10 carbon atoms; and n, m, and k are each independently integers from 1 to 100,000. Claim 7 In claim 6, 50 to 90 mol% of the total R1 in the structure of Chemical Formula 4 is a silsesquioxane resin containing a fluorine-containing organic group. Claim 8 In claim 6, 10 to 30 mol% of R1 of the above chemical formula 4 is a silsesquioxane resin selected from one or more of an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, and a thiol group. Claim 9 A composition comprising a silsesquioxane resin according to any one of claims 1 to 8; an initiator; and a solvent. Claim 10 A composition according to claim 9, wherein the initiator is included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the silsesquioxane resin. Claim 11 In claim 9, the solvent is a composition comprising a fluorine-based solvent. Claim 12 A cured product obtained by curing the composition according to paragraph 9. Claim 13 In paragraph 12, a hardened material having a refractive index of 1.20 to 1.

45. Claim 14 In claim 12, a cured product having a thickness of 30 to 250 nm. Claim 15 A display device containing a cured material according to Paragraph 12.

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