Low-refractive-index compound, preparation method therefor, and low-refractive-index optical film and display device, which comprise same

Abstract

The present invention relates to a low-refractive-index compound, a preparation method therefor, and a low-refractive-index optical film and a display device, which comprise same. The low-refractive-index compound of the present invention satisfies physical properties of both low refractive index and high viscosity, and thus can be effectively applied to the production of a low-refractive-index layer or a low-refractive-index optical film, which has low reflectance, and to a mold patterning technique. Therefore, a low-refractive-index optical film with ensured quality uniformity can be cost-effectively manufactured, and is applied such that a high-quality display device with improved light efficiency can be provided.

Description

Low refractive index compound, method for manufacturing the same, low refractive index optical film including the same, and display device

[0001] The present invention relates to a low-refractive index compound, a method for manufacturing the same, a low-refractive index optical film comprising the same, and a display device.

[0002] UV resin patterning technology plays a crucial role in improving product performance by forming fine patterns in various fields such as displays, optics, and biosensors, and recently, with the advancement of UV resin patterning technology, its applications into new fields are continuously expanding.

[0003] Among these, mold patterning technology is a technique capable of forming fine structures using molds, and it is widely utilized in various fields such as displays and lighting to increase light efficiency and improve quality. Mold patterning technology is suitable for high-resolution displays as it can precisely form fine structures at the nanometer level; it also offers the advantages of freely realizing desired patterns using molds and rapidly producing large quantities of films while ensuring quality uniformity.

[0004] Accordingly, research is ongoing to manufacture light extraction films capable of maximizing light extraction efficiency by controlling light scattering and refraction through the application of mold patterning technology. These light extraction films contain low-refractive index compounds to reduce total internal reflection of incident light. Currently commercialized fluorine-based low-refractive index compounds have low refractive indices suitable for light extraction films, but they exhibit low viscosity properties of about 1 to 10 cP, which causes problems such as failure to maintain the mold pattern or insufficient mechanical strength when applied to mold patterning technology.

[0005] Therefore, there is a need to develop a new low-refractive index compound that can simultaneously satisfy high viscosity properties applicable to mold patterning technology while exhibiting low refractive index properties applicable to light extraction films, etc.

[0006] In order to solve the aforementioned problems, the present invention aims to provide a new low-refractive index compound that satisfies both low refractive index and high viscosity properties, and a method for manufacturing the same.

[0007] In addition, the present invention aims to provide a low-refractive index optical film and a display device comprising the above-mentioned low-refractive index compound.

[0008] However, the problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned problems will be clearly understood by a person skilled in the art from the description below.

[0009] To achieve the above objective, the present invention provides a low-refractive index compound represented by the following chemical formula 1.

[0010] [Chemical Formula 1]

[0011]

[0012] (In the above chemical formula 1,

[0013] Z 1 To Z 3 Each is independently -NH- or -O-, and

[0014] L 1 to L 3 Each is independently a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms, and

[0015] R 1 to R 3 Each is independently a reactive group or a fluorine (F) containing group, wherein R 1 to R 3 There are no cases where all of these are reactive groups or all of them are fluorine-containing groups,

[0016] l is an integer from 1 to 100, wherein l is an integer from 2 to 100, a plurality are identical or different from each other,

[0017] The above reactive group is an acrylic group or a methacrylate group, and

[0018] The above fluorine-containing group is -(CF2) x -CHF2 or -(CF2) y -CH2OH and,

[0019] x and y are each independently integers from 1 to 10.

[0020] In the above low-refractive index compound, the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 2 below.

[0021] [Chemical Formula 2]

[0022]

[0023] (In the above chemical formula 2,

[0024] Z 11 To Z 13 Each is independently -NH- or -O-, and

[0025] L 11 to L 13 Each is independently a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms, and

[0026] R 11 to R 13 Each is independently a reactive group or a fluorine (F) containing group, wherein R 11 to R 13 There are no cases where all of these are reactive groups or all of them are fluorine-containing groups,

[0027] The above reactive group is an acrylic group or a methacrylate group, and

[0028] The above fluorine-containing group is -(CF2) x -CHF2 or -(CF2) y -CH2OH and,

[0029] x and y are each independently integers from 1 to 10.

[0030] In the above low-refractive index compound, the compound represented by Chemical Formula 1 may be a copolymer represented by Chemical Formula 3 below.

[0031] [Chemical Formula 3]

[0032]

[0033] (In the above chemical formula 3,

[0034] Z 21 To Z 26 Each is independently -NH- or -O-, and

[0035] L 21 to L 25 Each is independently a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms, and

[0036] R 21 to R 24 Each is independently a reactive group or a fluorine (F) containing group, wherein R 21 to R 24 There are no cases where all are reactive groups or all are fluorine-containing groups,

[0037] o and p are each independently integers from 1 to 20, and

[0038] The above reactive group is an acrylic group or a methacrylate group, and

[0039] The above fluorine-containing group is -(CF2) x -CHF2 or -(CF2) y -CH2OH and,

[0040] x and y are each independently integers from 1 to 10.

[0041] In the above low-refractive index compound, the compound represented by Chemical Formula 1 may be a copolymer represented by Chemical Formula 4 below.

[0042] [Chemical Formula 4]

[0043]

[0044] (In the above chemical formula 4,

[0045] Z 31 To Z 39 are, independently, -NH- or -O-, and

[0046] L 31 to L 37 Each is independently a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms, and

[0047] R 31 to R 35 Each is independently a reactive group or a fluorine (F) containing group, wherein R 31 to R 35 There are no cases where all are reactive groups or all are fluorine-containing groups,

[0048] q, r, and s are each independently integers from 1 to 20, and

[0049] The above reactive group is an acrylic group or a methacrylate group, and

[0050] The above fluorine-containing group is -(CF2) x -CHF2 or -(CF2) y -CH2OH and,

[0051] x and y are each independently integers from 1 to 10.

[0052] In the above low-refractive index compound, the low-refractive index compound may have a refractive index of 1.34 to 1.41.

[0053] In the above low-refractive index compound, the low-refractive index compound may have a viscosity of 50 cP or more.

[0054] In addition, the present invention comprises: (a) a step of synthesizing a low-refractive index compound using a phosphoryl halide, a compound having a reactive group, and a compound having a fluorine-containing group; and (b) a step of purifying the synthesized low-refractive index compound; wherein the compound having a reactive group is a compound represented by the following chemical formula 5, and the compound having a fluorine-containing group is HO-(CF2) x -CHF2 or HOCH2-(CF2) y A method for preparing a low-refractive index compound is provided, wherein -CH2OH, and x and y are each independently integers from 1 to 10.

[0055] [Chemical Formula 5]

[0056]

[0057] (In the above chemical formula 5,

[0058] R a is a hydrogen atom or a methyl group, and

[0059] R b is a hydrocarbon group having 1 to 12 carbon atoms having an -OH group at the terminal end, and

[0060] t is an integer from 1 to 3.

[0061] In the method for manufacturing the low-refractive index compound above, step (a) may involve synthesizing the low-refractive index compound by further including a compound represented by the following chemical formula 6.

[0062] [Chemical Formula 6]

[0063]

[0064] (In the above chemical formula 6,

[0065] Z a and Z b Each is independently -NH2 or -OH, and

[0066] L a ...is a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms.)

[0067] In the method for preparing the low-refractive index compound above, the low-refractive index compound may be a compound represented by the chemical formula 1 above.

[0068] In addition, the present invention provides a low-refractive index optical film comprising a low-refractive index compound.

[0069] In addition, the present invention provides a display device comprising the low-refractive index optical film.

[0070] The low-refractive index compound according to the present invention has a phosphine-based compound as a backbone and includes a reactive group for photocuring and a fluorine (F) containing group for low refractive index, thereby providing the effect of satisfying both low refractive index and high viscosity properties.

[0071] In addition, the low-refractive index compound according to the present invention exhibits low-refractive index characteristics and can be effectively applied to the manufacture of a low-refractive index layer or a low-refractive index optical film having a low reflectance, thereby providing the effect of improving the light efficiency of display devices, etc.

[0072] In addition, the low-refractive index compound according to the present invention satisfies low-refractive index characteristics while exhibiting high viscosity properties, so it can be effectively applied to mold patterning technology capable of precisely forming microstructures, thereby providing the effect of economically manufacturing high-quality low-refractive index optical films with ensured quality uniformity.

[0073] In addition, the present invention provides a method for manufacturing a low-refractive index compound that satisfies both low refractive index and high viscosity properties.

[0074] All terms used in this specification (including technical and scientific terms) may be used in a meaning commonly understood by those skilled in the art to which the present invention pertains, unless otherwise defined. Additionally, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless explicitly and specifically defined otherwise.

[0075] Additionally, as used herein, "comprising" and / or "comprising" are used in the sense that they do not exclude the presence or addition of one or more other components and / or steps other than the mentioned components and / or steps.

[0076] Additionally, as used in this specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acryl" means acryl and methacryl, and "(meth)acryloyl" means acryloyl and methacryloyl.

[0077] < Low-refractive index compounds >

[0078] The low-refractive index compound of the present invention is a compound represented by the following chemical formula 1.

[0079] [Chemical Formula 1]

[0080]

[0081] In the above chemical formula 1, Z 1 To Z 3 Each can be -NH- or -O- independently.

[0082] In the above chemical formula 1, L 1 to L 3 Each can be a hydrocarbon group having 1 to 12 carbon atoms, independently.

[0083] The above hydrocarbon group having 1 to 12 carbon atoms may be a hydrocarbon group having 2 to 4 carbon atoms.

[0084] Examples of the above divalent hydrocarbon groups include straight-chain alkanedyl groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, and dodecylene; branched-chain alkanedyl groups such as isopropylene, isobutylene, isopentylene, neopentylene, 2-ethylhexylene, sec-butylene, 1,3-dimethylbutylene, and 2-ethylbutylene; and alicyclic alkanedyl groups such as cyclopropylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and tricyclodecylene.

[0085] Examples of the above trivalent hydrocarbon groups include methanetriyl, ethanetriyl, propanetriyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl, octanetriyl, nonantriyl, decantriyl, dodecanetriyl, etc.

[0086] Examples of the above tetravalent hydrocarbon groups include methane tetrayl group, ethane tetrayl group, propane tetrayl group, butane tetrayl group, pentane tetrayl group, hexane tetrayl group, heptane tetrayl group, octane tetrayl group, nonane tetrayl group, decane tetrayl group, dodecane tetrayl group, etc.

[0087] In the above chemical formula 1, L 1 to L 3 If this is a trivalent or tetravalent hydrocarbon group, R 1 to R 3 Each can exist in multiple numbers. For example, L 1 to L 3 In the case of this trivalent hydrocarbon group, R 1 to R 3 There are 2 of each, and L 1 to L 3 In the case of this tetravalent hydrocarbon group, R 1 to R 3 There can be 3 of each.

[0088] The hydrogen included in the above hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms.

[0089] Examples of the above alkyl groups having 1 to 10 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, sec-butyl, 1,3-dimethylbutyl, and 2-ethylbutyl groups; and alicyclic alkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups.

[0090] Examples of the above alkanol groups having 1 to 10 carbon atoms include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, isopropanol, isobutanol, isopentanol, neopentanol, 2-ethylhexanol, sec-butanol, 1,3-dimethylbutanol, 2-ethylbutanol, cyclopropanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, tricyclodecanol, etc.

[0091] In the above chemical formula 1, R 1 to R 3 Each may independently be a reactive group or a fluorine (F) containing group. provided that R 1 to R 3 There are no cases where all of these are reactive, and R 1 to R 3 There are no cases where all of these are fluorine-containing groups. That is, R 1 to R 3 At least one of them is a reactive group, and R 1 to R 3 At least one of them is a fluorine-containing group.

[0092] The above reactive group is introduced for photocuring and may be an acrylic group or a methacrylate group.

[0093] The above fluorine-containing group is introduced to lower the refractive index of the compound, -(CF2) x -CHF2 or -(CF2) y -CH2OH may be used, and x and y may each be independent integers from 1 to 10.

[0094] In the above Chemical Formula 1, l may be an integer from 1 to 100. However, if l is an integer from 2 to 100, a plurality They may be the same or different from each other.

[0095] Conventional fluorine-containing acrylate compounds have been used to reduce the overall refractive index of a composition, but conversely, the surface energy is reduced, resulting in lower viscosity. Consequently, there was a problem in that the hardness and scratch resistance of a film formed using a composition containing such compounds were compromised.

[0096] In contrast, the low-refractive index compound represented by Chemical Formula 1 of the present invention is characterized by having a phosphine-based compound as a backbone and including at least one reactive group and at least one fluorine-containing group within the molecule. Unlike conventional fluorine-containing acrylate-based compounds, the low-refractive index compound of the present invention is believed to be able to simultaneously satisfy low refractive index characteristics and high viscosity characteristics even though a fluorine-containing group is present within the molecule, by introducing a phosphine-based compound as a backbone structure.

[0097] In one embodiment of the present invention, the compound represented by Chemical Formula 1 may further include other structural units to the extent that it does not impede the effect intended by the present invention.

[0098] The above low-refractive index compound may have a refractive index of 1.34 to 1.41, preferably 1.35 to 1.40, and more preferably 1.36 to 1.395.

[0099] In addition, the low refractive index compound may have a viscosity of 50 cP or more, preferably 80 cP or more, and more preferably 100 cP or more. Since the mechanical strength and scratch resistance of the optical film formed using the low refractive index compound can be improved as the viscosity increases, the upper limit of the viscosity is not particularly limited, but, for example, it may be 500,000 cP or less, or 300,000 cP or less.

[0100] In addition, the low refractive index compound may have a weight average molecular weight (Mw) of 800 to 10,000, and preferably 1,000 to 5,000.

[0101] In one embodiment of the present invention, the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 2 below.

[0102] [Chemical Formula 2]

[0103]

[0104] In the above chemical formula 2, Z 11 To Z 13 Each can be -NH- or -O- independently.

[0105] In the above chemical formula 2, L 11 to L 13 Each may independently be a hydrocarbon group having 1 to 12 carbon atoms, and the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms.

[0106] The above hydrocarbon group having 1 to 12 carbon atoms, the alkyl group having 1 to 10 carbon atoms, and the alkanol group having 1 to 10 carbon atoms are as described above.

[0107] In the above chemical formula 2, R 11 to R 13 Each may independently be a reactive group or a fluorine-containing group. provided that R 11 to R 13 There are no cases where all of these are reactive, and R 11 to R 13 There are no cases where all of these are fluorine-containing groups. That is, R 11 to R 13 At least one of them is a reactive group, and R 11 to R 13 At least one of them is a fluorine-containing group.

[0108] The above-mentioned reactive group and fluorine-containing group are as described above.

[0109] In one embodiment of the present invention, the compound represented by Chemical Formula 1 may be a copolymer represented by Chemical Formula 3 below.

[0110] [Chemical Formula 3]

[0111]

[0112] In the above chemical formula 3, Z 21 To Z 26 Each can be -NH- or -O- independently.

[0113] In the above chemical formula 3, L 21 to L 25 Each may independently be a hydrocarbon group having 1 to 12 carbon atoms, and the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms.

[0114] The above hydrocarbon group having 1 to 12 carbon atoms, the alkyl group having 1 to 10 carbon atoms, and the alkanol group having 1 to 10 carbon atoms are as described above.

[0115] In the above chemical formula 3, R 21 to R 24Each may independently be a reactive group or a fluorine-containing group. provided that R 21 to R 24 There are no cases where all are reactive groups, and R 21 to R 24 There is no case where all are fluorine-containing groups. That is, R 21 to R 24 At least one of them is a reactive group, and R 21 to R 24 At least one of them is a fluorine-containing group.

[0116] The above-mentioned reactive group and fluorine-containing group are as described above.

[0117] In the above chemical formula 3, o and p can each independently be integers from 1 to 20.

[0118] In one embodiment of the present invention, the compound represented by Chemical Formula 1 may be a copolymer represented by Chemical Formula 4 below.

[0119] [Chemical Formula 4]

[0120]

[0121] In the above chemical formula 4, Z 31 To Z 39 Each can be -NH- or -O- independently.

[0122] In the above chemical formula 4, L 31 to L 37 Each may independently be a hydrocarbon group having 1 to 12 carbon atoms, and the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms.

[0123] The above hydrocarbon group having 1 to 12 carbon atoms, the alkyl group having 1 to 10 carbon atoms, and the alkanol group having 1 to 10 carbon atoms are as described above.

[0124] In the above chemical formula 4, R 31 to R 35Each may independently be a reactive group or a fluorine-containing group. provided that R 31 to R 35 There are no cases where all are reactive groups, and R 31 to R 35 There is no case where all are fluorine-containing groups. That is, R 31 to R 35 At least one of them is a reactive group, and R 31 to R 35 At least one of them is a fluorine-containing group.

[0125] The above-mentioned reactive group and fluorine-containing group are as described above.

[0126] In the above chemical formula 4, q, r, and s can each independently be integers from 1 to 20.

[0127] Method for preparing low-refractive index compounds >

[0128] The method for preparing a low-refractive index compound of the present invention comprises: (a) a step of synthesizing a low-refractive index compound using a phosphoryl halide, a compound having a reactive group, and a compound having a fluorine-containing group; and (b) a step of purifying the synthesized low-refractive index compound.

[0129] The above step (a) is a step of synthesizing a low-refractive index compound from starting materials.

[0130] First, a diluted solution is prepared by diluting each of the starting materials—phosphoryl halide, a compound having a reactive group, and a compound having a fluorine-containing group—in a solvent. At this time, since an exothermic reaction occurs in which the starting materials dissolve in the solvent to form a salt, it is preferable to perform the step of preparing the diluted solution at a low temperature to suppress the exothermic reaction. The preparation of the diluted solution can be performed at a temperature of -20 to 15°C, preferably -10 to 10°C, and more preferably -5 to 5°C.

[0131] The above halogenated phosphoryl may be one or more selected from the group consisting of trifluoride phosphoryl, trichloride phosphoryl, tribromide phosphoryl, and triiodide phosphoryl, and preferably may be trichloride phosphoryl.

[0132] The compound having the above-mentioned reactive group may be a compound represented by the following chemical formula 5.

[0133] [Chemical Formula 5]

[0134]

[0135] In the above chemical formula 5, R a It can be a hydrogen atom or a methyl group.

[0136] In the above chemical formula 5, R b It may be a hydrocarbon group having 1 to 12 carbon atoms having an -OH group at the terminal end.

[0137] The above hydrocarbon group having 1 to 12 carbon atoms may be a hydrocarbon group having 2 to 4 carbon atoms.

[0138] The above divalent hydrocarbon group, trivalent hydrocarbon group, and tetravalent hydrocarbon group are as described above.

[0139] In the above Chemical Formula 5, t is an integer from 1 to 3. However, if t is 2 or 3, a plurality They may be the same or different from each other.

[0140] The compound having the above fluorine-containing group is HO-(CF2) x -CHF2 or HOCH2-(CF2) y -CH2OH may be used, and x and y may each be independent integers from 1 to 10.

[0141] The above solvent is not particularly limited as long as it is capable of dissolving the phosphoryl halide, the compound having a reactive group, and the compound having a fluorine-containing group, but examples include polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrolidone, dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone; polar protic solvents such as triethylamine, methanol, ethanol, propanol derivatives (PrOH, iso-PrOH), butanol derivatives (n-BuOH, tert-BuOH); and non-polar solvents such as benzene, toluene, xylene, mesitylene, tetrahydrofuran, dioxane, and dichloromethane.

[0142] In one embodiment of the present invention, step (a) may involve synthesizing a low-refractive index compound by further including a compound represented by the following chemical formula 6.

[0143] [Chemical Formula 6]

[0144]

[0145] In the above chemical formula 6, Z a and Z b Each can be independently -NH2 or -OH.

[0146] In the above chemical formula 6, L a The hydrocarbon group may be a hydrocarbon group having 1 to 12 carbon atoms, and the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms. For example, the -CH2- included in the hydrocarbon group may be replaced with -CF2- in which all hydrogen is substituted with fluorine.

[0147] The above hydrocarbon group having 1 to 12 carbon atoms, the alkyl group having 1 to 10 carbon atoms, and the alkanol group having 1 to 10 carbon atoms are as described above.

[0148] Next, a synthesis reaction is carried out by sequentially adding a diluted solution of a compound having a reactive group and a diluted solution of a compound having a fluorine-containing group to a diluted solution of phosphoryl halide. At this time, the order of adding the diluted solution of the compound having a reactive group and the diluted solution of the compound having a fluorine-containing group may be appropriately changed depending on the structure of the target compound, etc. It is preferable that the diluted solution of the compound having a reactive group and the diluted solution of the compound having a fluorine-containing group be added slowly, and if the diluted solution is added all at once or at a rapid rate, the synthesis yield may decrease and the proportion of by-products may increase.

[0149] The addition of a diluted solution of a compound having the above-mentioned reactive group or a diluted solution of a compound having a fluorine-containing group may be carried out at a temperature of -20 to 15°C, preferably -10 to 10°C, more preferably -5 to 5°C to suppress exothermic reaction.

[0150] In addition, the synthesis reaction may be carried out at a temperature of 10 to 40°C, preferably 15 to 35°C, more preferably 20 to 30°C, for 6 to 72 hours, preferably 12 to 48 hours.

[0151] The above step (b) is a step of purifying only the low-refractive index compound of the present invention from the materials produced through step (a), and may include a first filtration step, a neutralization step, a washing step, a drying step, and a second filtration step.

[0152] The above first filtration step is a step of separating an organic layer containing a low-refractive index compound from a reaction mixture in which the reaction is completed, for example, the organic layer can be separated by filtering the reaction mixture under reduced pressure.

[0153] The above neutralization step is a step of neutralizing the filtrate containing the organic layer, and by sequentially adding an acidic solution and a basic solution to neutralize the filtrate, unnecessary side reactions can be prevented.

[0154] Once the above neutralization step is completed, it is desirable to perform a washing step to remove any by-products that were not completely removed from the filtrate. Additionally, once the washing step is completed, the organic layer formed in the filtrate is dried.

[0155] The above second filtration step is a step of separating the final product by filtering the dried organic layer and then drying it under reduced pressure, and when the second filtration step is completed, a liquid low-refractive index compound can be obtained.

[0156] < Low-refractive index optical film and display device >

[0157] The present invention provides a low-refractive index optical film comprising the low-refractive index compound. The low-refractive index optical film may be manufactured by a step of applying the aforementioned low-refractive index compound onto a substrate and exposing and developing it into a predetermined pattern; and a step of curing the pattern.

[0158] The above substrate is not limited and may use, for example, a flat-surfaced substrate such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an Al substrate, or a GaAs substrate. The above substrate may undergo pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, vapor phase reaction treatment, or vacuum deposition treatment. Additionally, the above substrate may have a barrier matrix formed thereon.

[0159] The above-mentioned low-refractive index optical film may be a light extraction film, and the light extraction film may be manufactured by applying mold patterning technology. Since the method for manufacturing a light extraction film by applying mold patterning technology is well known in the relevant technical field, a detailed description is omitted.

[0160] In addition, the present invention provides a display device comprising the low-refractive index optical film. Examples of the display device include, but are not limited to, a liquid crystal display (LCD), an electroluminescent display (EL), a plasma display (PDP), a field emission display (FED), and an organic light-emitting diode (OLED). The display device of the present invention may further include a blue light source together with the low-refractive index optical film, and may include configurations known in the art as necessary.

[0161] The present invention will be explained in more detail below through examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to these examples.

[0162] <Example>

[0163] Example 1

[0164] 60 g (391.3 mmol) of trichloride phosphoryl was diluted in 600 g of toluene and stirred. A solution of 186 g (802.3 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 87 g (861.1 mmol) of triethylamine diluted in 60 g of toluene was added dropwise to the reaction mixture at 0°C for 1.5 hours, followed by stirring at room temperature for 1 hour. Then, a solution of 116.7 g (391.4 mmol) of pentaerythritol triacrylate and 43.6 g (430.5 mmol) of triethylamine diluted in 60 g of toluene was added dropwise to the reaction mixture at 0°C for 30 minutes, followed by stirring at room temperature for 18 hours. After the reaction was completed, byproducts were removed by vacuum filtration. Then, the filtrate was diluted with 400 mL of ethyl acetate, neutralized once with 500 mL of 1N aqueous hydrogen chloride solution, neutralized once with 500 mL of sodium bicarbonate solution, and the organic layer was washed once with 500 mL of sodium chloride solution. Subsequently, the organic layer was dried with magnesium sulfate, filtered, and the filtrate dried under reduced pressure to obtain 130 g of a liquid compound represented by the chemical formula 1-1 below. The refractive index measured by an Abbe refractometer was 1.379, and the viscosity measured by a rheometer was 103 cP.

[0165] 1 H NMR (400 MHz, CDCl3) δ 6.44 - 6.38 (m, 3H), 6.19 - 6.04 (m, 5H), 5.93 - 5.84 (m, 3H), 4.59 - 4.51 (m, 6H), 4.30 - 4.14 (m, 6H).

[0166] [Chemical Formula 1-1]

[0167]

[0168] Example 2

[0169] 60 g (391.3 mmol) of trichloride phosphoryl was diluted in 600 g of toluene and stirred. A solution of 50 g (430.4 mmol) of 2-hydroxyethyl acrylate and 47.6 g (469.6 mmol) of triethylamine diluted in 60 g of toluene was added dropwise to the reaction mixture at 0°C for 2 hours, and then stirred at room temperature for 17 hours. Then, a solution of 100 g (430.4 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 47.6 g (469.6 mmol) of triethylamine diluted in 60 g of toluene was added dropwise to the reaction mixture at 0°C for 2 hours, and then stirred at room temperature for 6 hours. Subsequently, a solution of 11.8 g (195.7 mmol) of ethylenediamine and 23.8 g (234.8 mmol) of triethylamine diluted in 30 g of toluene was added dropwise to the reaction mixture at 0°C for 30 minutes, followed by stirring at room temperature for 18 hours. After the reaction was complete, the mixture was neutralized once with 500 mL of 1N aqueous hydrogen chloride solution, then neutralized once with 500 mL of sodium bicarbonate solution, and finally washed once with 500 mL of sodium chloride solution. Subsequently, the organic layer was dried with magnesium sulfate, filtered, and the filtrate dried under reduced pressure to obtain 145 g of a liquid compound represented by the following chemical formula 1-2.

[0170] 1 H NMR (400 MHz, CDCl3) δ 6.45 - 6.41 (m, 2H), 6.17 - 6.14 (m, 2H), 5.91 - 5.88 (m, 2H), 4.58 - 4.45 (m, 8H), 4.40 - 4.37 (m, 8H), 4.25 - 4.20 (m, 2H).

[0171] [Chemical Formula 1-2]

[0172]

[0173] Example 3

[0174] 60 g (391.3 mmol) of trichloride phosphoryl was diluted in 600 g of dichloromethane and stirred. A solution of 46.3 g (399.1 mmol) of 2-hydroxyethyl acrylate and 43.6 g (430.4 mmol) of triethylamine diluted in 60 g of dichloromethane was added dropwise to the reaction mixture at 0°C for 1 hour, and then stirred at room temperature for 3 hours. Then, 84.5 g (182.8 mmol) of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol and 39.6 g (391.3 mmol) of triethylamine were added to the reaction mixture at 0°C, and then stirred at room temperature for 2 hours. Subsequently, a solution of 27.2 g (117.4 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 15.8 g (156.5 mmol) of triethylamine diluted in 60 g of dichloromethane was added to the reaction mixture at 0°C and stirred at room temperature for 18 hours. After the reaction was completed, byproducts were removed by vacuum filtration. The filtrate was then diluted in 400 mL of ethyl acetate, neutralized once with 500 mL of 1N aqueous hydrogen chloride solution, neutralized once with 500 mL of sodium bicarbonate solution, and the organic layer was washed once with 500 mL of sodium chloride solution. Afterward, the organic layer was dried with magnesium sulfate, filtered, and the filtrate was vacuum dried to obtain 135 g of a liquid compound represented by the chemical formula 1-3 below.

[0175] [Chemical Formula 1-3]

[0176]

[0177] Example 4

[0178] 19.8 g (129.2 mmol) of trichlorphosphoryl was diluted in 200 g of dichloromethane and stirred. A solution of 15.4 g (132.6 mmol) of 2-hydroxyethyl acrylate and 14.2 g (140.3 mmol) of triethylamine diluted in 20 g of dichloromethane was added dropwise to the reaction mixture at 0°C for 30 minutes, and then stirred at room temperature for 2 hours to prepare Reactant A. 39.6 g (258.3 mmol) of trichlorphosphoryl was diluted in 400 g of dichloromethane and stirred. Reactant B was prepared by adding dropwise a solution of 60.8 g (262.0 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 28.9 g (285.6 mmol) of triethylamine diluted in 40 g of dichloromethane to the reaction mixture at 0°C for 1 hour, and then stirring at room temperature for 2 hours.

[0179] The above reactants A and B were filtered under reduced pressure to remove byproducts. Subsequently, a solution of 12.2 g (195.7 mmol) of ethylene glycol and 39.6 g (391.3 mmol) of triethylamine diluted in 60 g of dichloromethane was added to the filtrate at 0°C and stirred at room temperature for 2 hours. Then, a solution of 27.2 g (117.2 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 15.8 g (156.1 mmol) of triethylamine diluted in 60 g of dichloromethane was added to the reaction mixture at 0°C and stirred at room temperature for 18 hours. After the reaction was completed, byproducts were removed by filtering under reduced pressure. Then, the filtrate was diluted with 400 mL of ethyl acetate and neutralized once with 500 mL of 1N aqueous hydrogen chloride solution, and after neutralization once with 500 mL of sodium bicarbonate solution, the organic layer was washed once with 500 mL of sodium chloride solution. Subsequently, the organic layer was dried with magnesium sulfate and filtered, and the filtrate was dried under reduced pressure to obtain 82.6 g of a liquid compound represented by the following chemical formula 1-4 (m:n = 1:2).

[0180] [Chemical Formula 1-4]

[0181]

[0182] Example 5

[0183] 60 g (391.3 mmol) of trichloride phosphoryl was diluted in 700 ml of toluene and cooled in an ice container. Then, 47.5 g (469.56 mmol) of triethylamine and 50 g (430.43 mmol) of 2-hydroxyethyl acrylate were diluted in 110 ml of toluene, slowly added dropwise over 1 hour, and stirred at room temperature for 15 hours. After the first reaction was completed, the mixture was cooled in an ice container, and 317.8 g (1369.60 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 145.19 g (1434.82 mmol) of triethylamine were diluted in 70 ml of toluene and slowly added dropwise over 1 hour, followed by stirring the reaction mixture at room temperature for 3 hours. After the second reaction was completed, the resulting amine salt was removed by vacuum filtration. The filtrate of the reactants was washed once with a 1M aqueous hydrochloric acid solution, once with a sodium bicarbonate solution, and once with distilled water in that order. The organic layer was then dried with magnesium sulfate, filtered, and the filtrate dried under reduced pressure to obtain 240g of a liquid compound represented by the chemical formula 1-5 below. The refractive index measured by an Abbe refractometer was 1.368, and the viscosity measured by a rheometer was 70 cP.

[0184] 1 H NMR (400 MHz, CDCl3) δ 6.50 - 6.43 (m, 1H), 6.17 - 6.09 (m, 1H), 6.20 - 5.86 (m, 2H), 5.94 - 5.87 (m, 1H), 4.52 (m, 4H), 4.43 - 4.34 (m, 4H).

[0185] [Chemical Formula 1-5]

[0186]

[0187] Example 6

[0188] 60 g (391.3 mmol) of trichloride phosphoryl was diluted in 700 ml of toluene and cooled in an ice container. Then, 43.5 g (430.4 mmol) of triethylamine and 46.35 g (399.13 mmol) of 2-hydroxyethyl acrylate were diluted in 110 ml of toluene, slowly added dropwise over 1 hour, and stirred at room temperature for 15 hours. After the first reaction was completed, the mixture was cooled in an ice container, and 92.6 g (399.13 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 47.5 g (469.56 mmol) of triethylamine were diluted in 70 ml of toluene and slowly added dropwise over 1 hour, and the reaction mixture was stirred at room temperature for 15 hours. 26.2 g (195.65 mmol) of 2-ethyl-2-(hydroxymethyl)propane-1,3-diol and 43.6 g (430.43 mmol) of triethylamine were dissolved in 70 ml of toluene by heating. The reaction mixture was then slowly added dropwise and stirred at room temperature for 30 minutes. After the reaction was complete, the generated amine salt was removed by vacuum filtration, and the reaction filtrate was washed once with 1 M aqueous hydrochloric acid, once with sodium bicarbonate, and once with distilled water. Subsequently, the organic layer was dried with magnesium sulfate and filtered, and the filtrate was dried under reduced pressure to obtain 240 g of the compound represented by the chemical formula 1-6 below. The refractive index measured by an Abbe refractometer was 1.394, and the viscosity measured by a rheometer was 206 cP.

[0189] 1 H NMR (400 MHz, DMSO) δ 7.22 - 6.83 (m, 8H), 6.39 - 6.28 (m, 3H), 6.24 - 6.10 (m, 3H), 6.02 - 5.87 (m, 3H), 4.94 - 4.55 (m, 12H), 4.39 - 4.20 (m, 9H), 4.13 - 3.89 (m, 13H), 3.89 - 3.76 (m, 5H), 1.76 - 1.48 (m, 16H), 1.44 - 1.22 (m, 15H)

[0190] [Chemical Formula 1-6]

[0191]

[0192] Example 7

[0193] 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 300 ml of toluene and cooled in an ice container. Then, 24 g (234.8 mmol) of triethylamine and 25 g (215.2 mmol) of 2-hydroxyethyl acrylate were diluted in 50 ml of toluene and slowly added dropwise over 1 hour, followed by stirring at room temperature for 15 hours. After the first reaction was completed, the mixture was cooled in an ice container, and then 48.6 g (209.63 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 23.76 g (234.8 mmol) of triethylamine were diluted in 30 ml of toluene and slowly added dropwise over 1 hour, followed by stirring the reaction mixture at room temperature for 3 hours. After the second reaction was completed, 45.2 g (97.82 mmol) of 1H,1H,10H,10H-perfluorodecane-1,10-diol and 23.76 g (234.79 mmol) of triethylamine were dissolved in 30 ml of toluene and slowly added dropwise over 1 hour. The reaction mixture was then stirred at room temperature for 15 hours, after which the resulting amine salt was removed by filtration. The reaction filtrate was washed once with 1 M aqueous hydrochloric acid, once with sodium bicarbonate, and once with distilled water. Subsequently, the organic layer was dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure. The obtained compound was diluted in 300 ml of chloroform and stirred for 1 hour using 9 g of activated carbon. Afterward, the mixture was filtered with diatomaceous earth and concentrated under reduced pressure to obtain 90 g of the liquid compound represented by the chemical formula 1-7 below. The refractive index measured by an Abbe refractometer was 1.371, and the viscosity measured by a rheometer was 2452 cP.

[0194] 1H NMR (400 MHz, CDCl3) δ 6.46 (ddd, J = 17.4, 1.3, 0.7 Hz, 2H), 6.19 - 6.09 (m, 2), 5.93 - 5.88 (m, 2H), 6.19-5.90(m, 2H) 4.61 - 4.45 (m, 8H), 4.45 - 4.27 (m, 9H), 4.09 (m, 1H)

[0195] [Chemical Formula 1-7]

[0196]

[0197] Example 8

[0198] 60 g (391.3 mmol) of trichloride phosphoryl was diluted in 450 ml of dichloromethane and cooled in an ice container. Then, 43.55 g (430.43 mmol) of triethylamine and 92.6 g (399.14 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 45 ml of dichloromethane, slowly added dropwise over 1 hour in an ice container, and stirred at room temperature for 3 hours. After the first reaction was completed, 11.76 g (195.65 mmol) of ethylenediamine and 39.60 g (391.3 mmol) of triethylamine were dissolved in 45 ml of dichloromethane and slowly added dropwise over 30 minutes. The reaction mixture was then stirred at 40°C for 2 hours, and the internal temperature was lowered to room temperature. After the second reaction was completed, 13.6 g (117.39 mmol) of 2-hydroxyethyl acrylate and 15.84 g (156.52 mmol) of triethylamine were diluted in 45 ml of dichloromethane and added. Subsequently, the reaction mixture was stirred at room temperature for 15 hours, after which the resulting amine salt was removed by filtration. The reaction filtrate was washed once with 1 M aqueous hydrochloric acid, once with sodium bicarbonate, and once with distilled water. The organic layer was then dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to obtain 75 g of the liquid compound represented by the chemical formula 1-8 below. The refractive index measured by an Abbe refractometer was 1.393, and the viscosity measured by a rheometer was 52146 cP.

[0199] [Chemical Formula 1-8]

[0200]

[0201] Example 9

[0202] 60 g (391.3 mmol) of trichloride phosphoryl was diluted in 450 ml of dichloromethane and cooled in an ice container. Then, 43.55 g (430.43 mmol) of triethylamine and 92.6 g (399.14 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 45 ml of dichloromethane, slowly added dropwise over 1 hour in an ice container, and stirred at room temperature for 3 hours. After the first reaction was completed, 12.14 g (195.65 mmol) of ethylene glycol and 39.60 g (391.3 mmol) of triethylamine were dissolved in 45 ml of dichloromethane and slowly added dropwise over 30 minutes. The reaction mixture was then stirred at 40°C for 2 hours, and the internal temperature was lowered to room temperature. After the second reaction was completed, 13.6 g (117.39 mmol) of 2-hydroxyethyl acrylate and 15.84 g (156.52 mmol) of triethylamine were diluted in 45 ml of dichloromethane and added. Subsequently, the reaction mixture was stirred at room temperature for 15 hours, after which the resulting amine salt was removed by filtration. The reaction filtrate was concentrated under reduced pressure, extracted with ethyl acetate, and washed once with 1 M aqueous hydrochloric acid, once with sodium bicarbonate, and once with distilled water. The organic layer was then dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to obtain 92 g of the liquid compound represented by the chemical formula 1-9 below. The refractive index measured by an Abbe refractometer was 1.377, and the viscosity measured by a rheometer was 124 cP.

[0203] [Chemical Formula 1-9]

[0204]

[0205] Example 10

[0206] 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 230 ml of dichloromethane in a round-bottom flask and cooled in an ice container. Then, 21.8 g (215.23 mmol) of triethylamine and 46.31 g (199.57 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 20 ml of dichloromethane, slowly added dropwise over 1 hour, and stirred at room temperature for 3 hours. In another round-bottom flask, 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 230 ml of dichloromethane and cooled in an ice container. Then, 23.17 g (199.57 mmol) of 2-hydroxyethyl acrylate and 21.78 g (215.23 mmol) of triethylamine were diluted in 20 ml of dichloromethane and slowly added dropwise over 1 hour, after which the reaction mixture was stirred at room temperature for 3 hours. After the first reaction was completed, the mixture was filtered to remove the generated amine salt, and the two filtrates were collected in a single 4-neck round-bottom flask. 11.76 g (195.65 mmol) of ethylenediamine and 43.56 g (430.46 mmol) of triethylamine were dissolved in 45 ml of dichloromethane and slowly added dropwise over 30 minutes, after which the reaction mixture was stirred at 40°C for 2 hours, and then the internal temperature was lowered to room temperature. After the second reaction was completed, 15.84 g (156.53 mmol) of triethylamine and 27.24 g (117.4 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 45 ml of dichloromethane and added. Subsequently, the reaction mixture was stirred at room temperature for 15 hours, after which the resulting amine salt was removed by filtration. The reaction filtrate was concentrated under reduced pressure and extracted with ethyl acetate, and washed once with 1 M aqueous hydrochloric acid, once with an aqueous sodium bicarbonate, and once with distilled water. The organic layer was then dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to obtain 80 g of the liquid compound represented by the chemical formula 1-10 below.The refractive index measured by an Abbe refractometer was 1.403, and the viscosity measured by a rheometer was 3284 cP.

[0207] [Chemical Formula 1-10]

[0208]

[0209] Example 11

[0210] 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 230 ml of dichloromethane in a round-bottom flask and cooled in an ice container. Then, 21.8 g (215.23 mmol) of triethylamine and 46.31 g (199.57 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 20 ml of dichloromethane, slowly added dropwise over 1 hour, and stirred at room temperature for 3 hours. In another round-bottom flask, 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 230 ml of dichloromethane and cooled in an ice container. Then, 23.17 g (199.57 mmol) of 2-hydroxyethyl acrylate and 21.78 g (215.23 mmol) of triethylamine were diluted in 20 ml of dichloromethane and slowly added dropwise over 1 hour, after which the reaction mixture was stirred at room temperature for 3 hours. After the first reaction was completed, the mixture was filtered to remove the generated amine salt, and the two filtrates were collected in a single 4-neck round-bottom flask. 12.14 g (195.65 mmol) of ethylene glycol and 43.56 g (430.46 mmol) of triethylamine were dissolved in 45 ml of dichloromethane and slowly added dropwise over 30 minutes, after which the reaction mixture was stirred at 40°C for 2 hours, and then the internal temperature was lowered to room temperature. After the second reaction was completed, 15.84 g (156.53 mmol) of triethylamine and 27.24 g (117.4 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 45 ml of dichloromethane and added. Subsequently, the reaction mixture was stirred at room temperature for 15 hours, after which the resulting amine salt was removed by filtration. The reaction filtrate was concentrated under reduced pressure, extracted with ethyl acetate, and washed once with 1 M aqueous hydrochloric acid, once with an aqueous sodium bicarbonate, and once with distilled water. The organic layer was then dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to obtain 72 g of the liquid compound represented by the chemical formula 1-11 below (m:n = 1:1). The refractive index measured by an Abbe refractometer was 1.It was 369, and the viscosity measured by a rheometer was 153 cP.

[0211] [Chemical Formula 1-11]

[0212]

[0213] Example 12

[0214] 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 230 ml of dichloromethane in a round-bottom flask and cooled in an ice container. Then, 21.8 g (215.23 mmol) of triethylamine and 46.31 g (199.57 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 20 ml of dichloromethane, slowly added dropwise over 1 hour, and stirred at room temperature for 3 hours. In another round-bottom flask, 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 230 ml of dichloromethane and cooled in an ice container. Then, 23.17 g (199.57 mmol) of 2-hydroxyethyl acrylate and 21.78 g (215.23 mmol) of triethylamine were diluted in 20 ml of dichloromethane and slowly added dropwise over 1 hour, after which the reaction mixture was stirred at room temperature for 3 hours. After the first reaction was completed, the mixture was filtered to remove the generated amine salt, and the two filtrates were collected in a single 4-neck round-bottom flask. 12.14 g (195.65 mmol) of ethylene glycol and 43.56 g (430.46 mmol) of triethylamine were dissolved in 45 ml of dichloromethane and slowly added dropwise over 30 minutes, after which the reaction mixture was stirred at 40°C for 2 hours, and then the internal temperature was lowered to room temperature. After the second reaction was completed, 15.84 g (156.53 mmol) of triethylamine and 27.24 g (117.4 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 45 ml of dichloromethane and added. Subsequently, the reaction mixture was stirred at room temperature for 15 hours, after which the resulting amine salt was removed by filtration. The reaction filtrate was concentrated under reduced pressure, extracted with ethyl acetate, and washed once with 1 M aqueous hydrochloric acid, once with an aqueous sodium bicarbonate, and once with distilled water. The organic layer was then dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to obtain 82 g of the liquid compound represented by the chemical formula 1-12 below (m:n = 1:3). The refractive index measured by an Abbe refractometer was 1.It was 361, and the viscosity measured by a rheometer was 586 cP.

[0215] [Chemical Formula 1-12]

[0216]

[0217] Example 13

[0218] 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 230 ml of dichloromethane in a round-bottom flask and cooled in an ice container. Then, 30.4 g (300.12 mmol) of triethylamine and 69.46 g (299.35 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 20 ml of dichloromethane, slowly added dropwise over 1 hour, and stirred at room temperature for 3 hours. In another round-bottom flask, 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 230 ml of dichloromethane and cooled in an ice container. Then, 11.58 g (99.78 mmol) of 2-hydroxyethyl acrylate and 15.18 g (100.23 mmol) of triethylamine were diluted in 20 ml of dichloromethane and slowly added dropwise over 1 hour, after which the reaction mixture was stirred at room temperature for 3 hours. After the first reaction was completed, the mixture was filtered to remove the generated amine salt, and the two filtrates were collected in a single 4-neck round-bottom flask. 11.76 g (195.65 mmol) of ethylene diamine and 43.56 g (430.46 mmol) of triethylamine were dissolved in 45 ml of dichloromethane and slowly added dropwise over 30 minutes, after which the reaction mixture was stirred at 40°C for 2 hours, and then the internal temperature was lowered to room temperature. After the second reaction was completed, 15.84 g (156.53 mmol) of triethylamine and 27.24 g (117.4 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 45 ml of dichloromethane and added. Subsequently, the reaction mixture was stirred at room temperature for 15 hours, after which the resulting amine salt was removed by filtration. The reaction filtrate was concentrated under reduced pressure, extracted with ethyl acetate, and washed once with 1 M aqueous hydrochloric acid, once with sodium bicarbonate, and once with distilled water. The organic layer was then dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to obtain 95 g of the liquid compound represented by the chemical formula 1-13 below. The refractive index measured by an Abbe refractometer was 1.It was 385, and the viscosity measured by a rheometer was 104808 cP.

[0219] [Chemical Formula 1-13]

[0220]

[0221] Example 14

[0222] 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 230 ml of dichloromethane in a round-bottom flask and cooled in an ice container. Then, 21.8 g (215.23 mmol) of triethylamine and 46.31 g (199.57 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 20 ml of dichloromethane, slowly added dropwise over 1 hour, and stirred at room temperature for 3 hours. In another round-bottom flask, 30 g (195.66 mmol) of trichloride phosphoryl was diluted in 230 ml of dichloromethane and cooled in an ice container. Then, 23.17 g (199.57 mmol) of 2-hydroxyethyl acrylate and 21.78 g (215.23 mmol) of triethylamine were diluted in 20 ml of dichloromethane and slowly added dropwise over 1 hour, after which the reaction mixture was stirred at room temperature for 3 hours. After the first reaction was completed, the mixture was filtered to remove the generated amine salt, and the two filtrates were collected in a single 4-neck round-bottom flask. 23.12 g (195.66 mmol) of 1,6-hexanediol and 41.58 g (418.89 mmol) of triethylamine were dissolved in 45 ml of dichloromethane and slowly added dropwise over 30 minutes, after which the reaction mixture was stirred at 40°C for 2 hours, and then the internal temperature was lowered to room temperature. After the second reaction was completed, 15.84 g (156.53 mmol) of triethylamine and 27.24 g (117.4 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were diluted in 45 ml of dichloromethane and added. Subsequently, the reaction mixture was stirred at room temperature for 15 hours, after which the resulting amine salt was removed by filtration. The reaction filtrate was concentrated under reduced pressure, extracted with ethyl acetate, and washed once with 1 M aqueous hydrochloric acid, once with sodium bicarbonate, and once with distilled water. The organic layer was then dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to obtain 105 g of the liquid compound represented by the chemical formula 1-14 below. The refractive index measured by an Abbe refractometer was 1.It is 399, and the viscosity measured by a rheometer is 1923 cP.

[0223] [Chemical Formula 1-14]

[0224]

[0225] Comparative Examples 1 and 2

[0226] Compounds represented by the following chemical formula 7 (V-3F, Shin-Nakamura Co., Ltd.) and compound represented by the following chemical formula 8 (DA-FO, Shin-Nakamura Co., Ltd.) were used as Comparative Examples 1 and 2, respectively.

[0227] [Chemical Formula 7]

[0228]

[0229] [Chemical Formula 8]

[0230]

[0231] <Experimental Example>

[0232] 1. Measurement of Refractive Index

[0233] The refractive index of each compound according to the above examples and comparative examples was measured using an Abbe refractometer (NAR 1T, ATAGO), and the results are shown in Table 1 below.

[0234] 2. Viscosity measurement

[0235] The viscosity of each compound according to the above examples and comparative examples was measured using a rheometer (MCR 702 TwinDrive, Anton Paar), and the results are shown in Table 1 below.

[0236] Refractive Index Viscosity (cP) Example 1 1.379 103 Example 2 1.39 2372 Example 3 1.38 68 263 Example 4 1.36 6495 Example 5 1.36 870 Example 6 1.39 4206 Example 7 1.37 12452 Example 8 1.39 35 2146 Example 9 1.37 7124 Example 10 1.40 33284 Example 1 1.36 9153 Example 12 1.36 1586 Example 13 1.38 5104808 Example 14 1.39 91923 Comparative Example 1 1.34 81.1 Comparative Example 2 1.38 10

[0237] Referring to Table 1, it can be confirmed that the low-refractive index compounds of Examples 1 to 14 of the present invention are all compounds within the range of compounds represented by Formula 1 of the present invention, exhibiting low-refractive index characteristics with a refractive index of 1.41 or less, while simultaneously satisfying high viscosity characteristics of at least 70 cP. Accordingly, it can be seen that an optical film formed using the low-refractive index compounds of the present invention exhibits superior mechanical strength and scratch resistance, and can be effectively applied to mold patterning technology capable of precisely forming microstructures, thereby enabling the economical production of a high-quality low-refractive index optical film with ensured quality uniformity.

[0238] In contrast, the low-refractive index compounds according to Comparative Examples 1 and 2 are compounds that do not include phosphine-based compounds in the backbone and exhibit low-refractive index characteristics with a refractive index of 1.41 or less, but it can be confirmed that they do not satisfy high viscosity characteristics with a viscosity of 10 cP or less, and it can be seen that due to the low viscosity properties, the mechanical strength and scratch resistance of the optical film are insufficient and it will be difficult to apply them to mold patterning technology.

[0239] 3. Measurement of molecular weight

[0240] The number average molecular weight, weight average molecular weight, and dispersion of the low-refractive index compounds synthesized in each example were measured using GPC analysis (Waters 2414 Refractive Index Detector / 1515 Isocratic HPLC Pump), and the results are shown in Table 2 below.

[0241] Number Average Molecular Weight (Mn) Weight Average Molecular Weight (Mw) Degree of Dispersion (PDI = Mw / Mn) Example 3 1 2 3 2 4 5 2 3 2.32 Example 4 7 5 2 2 1 4 2 2.03 Example 8 1 1 2 4 3 8 6 5 1.86 Example 9 6 8 5 1 8 6 5 2.23 Example 10 9 8 6 3 5 6 8 1.96 Example 11 5 6 9 2 3 5 3 2.18 Example 12 4 5 9 1 9 3 2 1.99 Example 13 1 3 6 5 5 6 2 2.33 Example 14 1 2 1 3 9 6 6 2.31

Claims

1. A low-refractive index compound represented by the following chemical formula 1. [Chemical Formula 1] (In the above chemical formula 1, Z 1 To Z 3 Each is independently -NH- or -O-, and L 1 to L 3 Each is independently a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms, and R 1 to R 3 Each is independently a reactive group or a fluorine (F) containing group, wherein R 1 to R 3 There are no cases where all of these are reactive groups or all of them are fluorine-containing groups, l is an integer from 1 to 100, wherein l is an integer from 2 to 100, a plurality are identical or different from each other, The above reactive group is an acrylic group or a methacrylate group, and The above fluorine-containing group is -(CF2) x -CHF2 or -(CF2) y -CH2OH and, x and y are each independently integers from 1 to 10.

2. In Claim 1, The compound represented by the above chemical formula 1 is a low-refractive index compound represented by the following chemical formula 2. [Chemical Formula 2] (In the above chemical formula 2, Z 11 To Z 13 Each is independently -NH- or -O-, and L 11 to L 13 Each is independently a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms, and R 11 to R 13 Each is independently a reactive group or a fluorine-containing group, wherein R 11 to R 13 There are no cases where all of these are reactive groups or all of them are fluorine-containing groups, The above reactive group is an acrylic group or a methacrylate group, and The above fluorine-containing group is -(CF2) x -CHF2 or -(CF2) y -CH2OH and, x and y are each independently integers from 1 to 10.

3. In Claim 1, A low-refractive index compound, wherein the compound represented by the above chemical formula 1 is a copolymer represented by the following chemical formula 3. [Chemical Formula 3] (In the above chemical formula 3, Z 21 To Z 26 Each is independently -NH- or -O-, and L 21 to L 25 Each is independently a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms, and R 21 to R 24 is, each independently, a reactive group or a fluorine-containing group, wherein R 21 to R 24 There are no cases where all are reactive groups or all are fluorine-containing groups, o and p are each independently integers from 1 to 20, and The above reactive group is an acrylic group or a methacrylate group, and The above fluorine-containing group is -(CF2) x -CHF2 or -(CF2) y -CH2OH and, x and y are each independently integers from 1 to 10.

4. In Claim 1, A low-refractive index compound, wherein the compound represented by the above chemical formula 1 is a copolymer represented by the following chemical formula 4. [Chemical Formula 4] (In the above chemical formula 4, Z 31 To Z 39 are, independently, -NH- or -O-, and L 31 to L 37 Each is independently a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms, and R 31 to R 35 is, each independently, a reactive group or a fluorine-containing group, wherein R 31 to R 35 There are no cases where all are reactive groups or all are fluorine-containing groups, q, r, and s are each independently integers from 1 to 20, and The above reactive group is an acrylic group or a methacrylate group, and The above fluorine-containing group is -(CF2) x -CHF2 or -(CF2) y -CH2OH and, x and y are each independently integers from 1 to 10.

5. In Claim 1, A low-refractive index compound having a refractive index of 1.34 to 1.

41.

6. In Claim 1, A low-refractive index compound with a viscosity of 50 cP or higher.

7. (a) a step of synthesizing a low-refractive index compound using a phosphoryl halide, a compound having a reactive group, and a compound having a fluorine-containing group; and (b) a step of purifying the synthesized low-refractive index compound; comprising, The compound having the above-mentioned reactive group is a compound represented by the following chemical formula 5, and The compound having the above fluorine-containing group is HO-(CF2) x -CHF2 or HOCH2-(CF2) y A method for preparing a low-refractive index compound, wherein -CH2OH, and x and y are each independently integers from 1 to 10. [Chemical Formula 5] (In the above chemical formula 5, R a is a hydrogen atom or a methyl group, and R b is a hydrocarbon group having 1 to 12 carbon atoms having an -OH group at the terminal end, and t is an integer from 1 to 3.

8. In Claim 7, The above step (a) is a method for preparing a low-refractive index compound, wherein the low-refractive index compound is synthesized by further including a compound represented by the following chemical formula 6. [Chemical Formula 6] (In the above chemical formula 6, Z a and Z b Each is independently -NH2 or -OH, and L a ...is a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms.) 9. In Claim 7, A method for preparing a low-refractive index compound, wherein the low-refractive index compound is a compound represented by the following chemical formula 1. [Chemical Formula 1] (In the above chemical formula 1, Z 1 To Z 3 Each is independently -NH- or -O-, and L 1 to L 3 Each is independently a hydrocarbon group having 1 to 12 carbon atoms, wherein the hydrogen included in the hydrocarbon group may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkanol group having 1 to 10 carbon atoms, and R 1 to R 3 Each is independently a reactive group or a fluorine (F) containing group, wherein R 1 to R 3 There are no cases where all of these are reactive groups or all of them are fluorine-containing groups, l is an integer from 1 to 100, wherein l is an integer from 2 to 100, a plurality are identical or different from each other, The above reactive group is an acrylic group or a methacrylate group, and The above fluorine-containing group is -(CF2) x -CHF2 or -(CF2) y -CH2OH and, x and y are each independently integers from 1 to 10.

10. A low-refractive index optical film comprising a low-refractive index compound of any one of claims 1 to 6.

11. A display device comprising the low-refractive index optical film of claim 10.

Images