Polymerizable composition, cured film thereof, and optical member and display device comprising same

Abstract

The present invention provides a high-refractive-index polymerizable composition comprising: a first monomer having at least one polymerizable group; and a binder comprising a repeating unit represented by chemical formula 1. [Chemical formula 1]

Description

Polymerizable composition, cured film thereof, and optical member and display device including the same

[0001] The present invention relates to a polymerizable composition, a cured film thereof, and an optical member and a display device comprising the same.

[0002] In the case of a light-transmitting optical film having a structured prism, the rate of increase in luminance varies depending on the refractive index of the resin forming the prism structure. Generally, as the refractive index of the resin constituting the prism increases, the rate of increase in luminance increases. Therefore, regarding the above-mentioned light-transmitting optical film, research and development is being conducted in the direction of increasing the refractive index of the resin forming the prism structure.

[0003] However, the resin that generally forms a prism is composed of organic compounds, and the theoretical upper limit of the refractive index range adjustable by such organic compounds is known to be approximately 1.65, which is a narrower range compared to inorganic compounds.

[0004] Furthermore, when attempting to increase the refractive index of a resin formed from organic compounds, the viscosity of the monomer composition increases, leading to problems such as reduced processability or decreased UV stability, which presents many technical limitations.

[0005] Furthermore, when forming the resin and optical film using a polymerizable composition containing conventional monomers, surface curing often fails to occur sufficiently during the photocuring process due to the influence of oxygen in the air. As a result, the resin and optical film exhibit increased haze and problems such as reduced light transmittance (e.g., UV transmittance) and visibility. To address this, methods to conduct the curing process under an inert gas atmosphere, such as nitrogen, have been considered, but this can lead to a significant increase in manufacturing costs.

[0006] Meanwhile, materials with a structure containing sulfur are used to achieve a high refractive index, but there is a problem in that sulfur causes yellowing, thereby reducing the reliability of the device.

[0007] The present invention aims to provide a polymerizable composition having excellent high refractive index, light efficiency, and lens pattern characteristics, in which sulfur is absent or present in a minimal amount within the structure to suppress yellowing, a cured film thereof, and an optical member and a display device including the same.

[0008] The above tasks and additional tasks are described in detail below.

[0009] In order to solve the aforementioned problem,

[0010] In one embodiment, the present invention provides a high-refractive index polymerizable composition comprising a first monomer having at least one functional group and a binder comprising a repeating unit of the following chemical formula 1.

[0011] <Chemical Formula 1>

[0012]

[0013] In the above chemical formula 1,

[0014] Ar1 is selected from the following chemical formulas 1-1 to 1-6, and

[0015] R1 and R2 are each independently a substituted or unsubstituted C1-C50 alkylene group, a substituted or unsubstituted C1-C50 alkoxylene group, a substituted or unsubstituted C2-C50 alkenylene group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkylene group, a substituted or unsubstituted C1-C50 heterocycloalkylene group, a substituted or unsubstituted C3-C50 cycloalkenylene group, a substituted or unsubstituted C2-C50 heterocycloalkenylene group, a substituted or unsubstituted C3-C50 arylene group, or a substituted or unsubstituted C2-C50 heteroarylene group, or a combination thereof, and the -CH2- present in L1 and L2 is -O-, -S-, -CO-, -C(OR4)R3-, -NR3-, It can be replaced with -C(=NR3)-, -Si(R3)2- or -P(R3)2-, and -CH3 can be replaced with -OH,

[0016] R3 is each independently hydrogen, deuterium, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C2-C50 alkenyl group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkyl group, a substituted or unsubstituted C1-C50 heterocycloalkyl group, a substituted or unsubstituted C3-C50 cycloalkenyl group, a substituted or unsubstituted C2-C50 heterocycloalkenyl group, a substituted or unsubstituted C3-C50 aryl group, or a substituted or unsubstituted C2-C50 heteroaryl group, or a combination thereof.

[0017] One or more of the above R1s include a polymerizable functional group, and

[0018] <Chemical Formula 1-1>

[0019]

[0020] <Chemical Formula 1-2>

[0021]

[0022] <Chemical Formula 1-3>

[0023]

[0024] <Chemical Formula 1-4>

[0025]

[0026] <Chemical Formula 1-5>

[0027]

[0028] <Chemical Formula 1-6>

[0029]

[0030] In the above chemical formulas 1-1 to 1-6,

[0031] R4 and R5 are each independently identical to the definition of R3 above, and

[0032] X are each independently O, S, Se, NR6, and SiR6R7, and R6 and R7 are each independently identical to the definition of R3 above, and

[0033] a is independently an integer from 0 to 4, and b is independently an integer from 0 to 3, and

[0034] "*" indicates the connection position.

[0035] In addition, the present invention provides, in one embodiment, a cured film comprising a cured product of the polymerizable composition.

[0036] In addition, the present invention provides an optical member comprising the hardened film in one embodiment.

[0037] In addition, the present invention provides a display device comprising the cured film as an optical film in one embodiment.

[0038] The polymerizable composition, cured film, optical member, and display device according to one embodiment of the present invention suppress yellowing phenomena by having no sulfur or a minimal amount of sulfur present in the structure, and have excellent high refractive index, light efficiency, and lens pattern characteristics.

[0039] The above effects and additional effects are described in detail below.

[0040] Before describing the present invention in detail below, it should be understood that the terms used in this specification are intended only to describe specific embodiments and are not intended to limit the scope of the invention, which is defined solely by the appended claims. Unless otherwise stated, all technical and scientific terms used in this specification have the same meaning as generally understood by those skilled in the art.

[0041] Throughout this specification and claims, unless otherwise noted, the terms "comprise," "comprising," and "comprising" mean including the mentioned article, step, or group of articles and steps, and are not used to mean excluding any other article, step, or group of articles or groups of steps.

[0042] Throughout this specification and claims, the term "aryl" means comprising an aromatic hydrocarbon ring group of C5-50 condensation or non-condensation, e.g., phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perylenyl, crisenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzocrisenyl, anthracenyl, stilbenyl, pyrenyl, etc., and "heteroaryl" means an aromatic ring of C2-50 condensation or non-condensation comprising at least one heteroatom, e.g., pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, quinolyl, isoquinolyl, It may mean that it includes heterocyclic rings formed from quinoxalinil, carbazolyl, phenantridinyl, acridinyl, phenanthrolinyl, thienyl, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadiazole ring, benzofuran ring, thiazole ring, thiadiazole ring, benzothiophen ring, triazole ring, imidazole ring, benzimidazole ring, pyran ring, dibenzofuran ring, etc. Additionally, the term "arylene" means that a hydrogen in the aryl group is replaced by a direct bond to become a divalent substituent, and specific examples are not limited to cases where the aryl structure described above becomes a divalent substituent. Likewise, the term "heteroarylene" means that a hydrogen in the heteroaryl group is replaced by a direct bond to become a divalent substituent, and specific examples are not limited to cases where the heteroaryl structure described above becomes a divalent substituent.

[0043] Also, in the chemical formula, Ar x(where x is an integer) means, unless specifically defined, a substituted or unsubstituted C6–C50 aryl group, or a substituted or unsubstituted C2–C50 heteroaryl group, and L x (where x is an integer) means a directly bonded, substituted, or unsubstituted C6–C50 arylene group, or a substituted or unsubstituted C2–C50 heteroarylene group, unless specifically defined, and R x (where x is an integer) means, unless specifically defined, hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 sulfide group, substituted or unsubstituted C6-C50 aryl group, or substituted or unsubstituted C2-C50 heteroaryl group.

[0044] Throughout this specification and claims, the term “substituted or unsubstituted” refers to a halogen such as deuterium, fluorine, or chlorine, an amino group, a cyano group, a nitrile group, a nitro group, a nitroso group, a sulfamoyl group, an isothiocyanate group, a thiocyanate group, a carboxyl group, a carbonyl group, or a C1-C30 alkyl group, a C1-C30 alkylsulfinyl group, a C1-C30 alkylsulfonyl group, a C1-C30 alkylsulfanyl group, a C1-C12 fluoroalkyl group, a C2-C30 alkenyl group, a C1-C30 alkoxy group, a C1-C12 N-alkylamino group, a C2-C20 N,N-dialkylamino group, a substituted or unsubstituted C1-C30 sulfide group, a C1-C6 N-alkylsulfamoyl group, or a C2-C12 It may mean that it is substituted or not substituted with one or more groups selected from the group consisting of N,N-dialkylsulfamoyl groups, C0-C30 silyl groups, C3-C20 cycloalkyl groups, C3-C20 heterocycloalkyl groups, C6-C50 aryl groups, and C3-C50 heteroaryl groups. Additionally, throughout this specification, the same symbols may have the same meaning unless specifically stated otherwise.

[0045] Meanwhile, matters described in the specification using the above-defined terms such as "aryl," "heteroaryl," "arylene," "heteroarylene," and "substitution" are deemed to include the examples listed above and their combinations; accordingly, the above-mentioned terms may be replaced by the examples listed above or subsequently modified.

[0046] In addition, when ranges such as "C2 to C50" or "0 to 7" are described in this specification, they may be reduced to various ranges within the described ranges even without special description, and are deemed to be described in this specification. For example, C2 to C50 is deemed to describe various reduced ranges such as C5 to C50, C6 to C30, C6 to C20, C6 to C15, C6 to C10, and C12 to C30, in addition to C2 to C50. Accordingly, the description of numerical ranges in this specification may be reduced and corrected later.

[0047] In addition, in this specification, high refractive index means a refractive index of 1.60 or higher at a wavelength of 565 nm, and specifically, may mean 1.62 or higher, 1.65 or higher, 1.70 or higher, 1.75 or higher, or 1.80 or higher.

[0048] Meanwhile, various embodiments of the present invention may be combined with any other embodiments unless explicitly stated otherwise. Hereinafter, embodiments of the present invention and the effects thereof will be described.

[0049] A polymerizable composition according to one embodiment of the present invention comprises a binder comprising a first monomer having at least one functional group and a repeating unit of the following chemical formula 1.

[0050] Binder

[0051] A polymerizable composition according to one embodiment of the present invention comprises a binder having a repeating unit of the following chemical formula 1. The weight-average molecular weight of the binder is not limited and may be within the range of 1,000 to 20,000. Specifically, it may be within the range of 1,000 to 15,000, within the range of 1,000 to 10,000, within the range of 1,000 to 8,000, within the range of 2,000 to 20,000, within the range of 2,000 to 15,000, within the range of 2,000 to 10,000, within the range of 3,000 to 20,000, within the range of 3,000 to 15,000, within the range of 3,000 to 10,000, within the range of 3,000 to 8,000, within the range of 4,000 to 20,000, within the range of 4,000 to 15,000, within the range of 4,000 to 10,000, or within the range of 4,000 to 8,000. More specifically, it may be within the range of 2,000 to 8,000. Within the above range, thermal reflow characteristics are excellent, and the degree of curing can be excellent.

[0052] <Chemical Formula 1>

[0053]

[0054] In the above chemical formula 1,

[0055] Ar1 is selected from the following chemical formulas 1-1 to 1-6, and

[0056] Q are each independently O, S, or NR', specifically O or NR', and,

[0057] R1 and R2 are each independently a substituted or unsubstituted C1-C50 alkylene group, a substituted or unsubstituted C1-C50 alkoxylene group, a substituted or unsubstituted C2-C50 alkenylene group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkylene group, a substituted or unsubstituted C1-C50 heterocycloalkylene group, a substituted or unsubstituted C3-C50 cycloalkenylene group, a substituted or unsubstituted C2-C50 heterocycloalkenylene group, a substituted or unsubstituted C3-C50 arylene group, or a substituted or unsubstituted C2-C50 heteroarylene group, or a combination thereof, and the -CH2- present in R1 and R2 is -O-, -S-, -SO2-, -CO-, -C(OR4)R3-, -NR3-, It can be replaced with -C(=NR3)-, -Si(R3)2- or -P(R3)2-, and -CH3 can be replaced with -OH,

[0058] R' and R3 are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C2-C50 alkenyl group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkyl group, a substituted or unsubstituted C1-C50 heterocycloalkyl group, a substituted or unsubstituted C3-C50 cycloalkenyl group, a substituted or unsubstituted C2-C50 heterocycloalkenyl group, a substituted or unsubstituted C3-C50 aryl group, or a substituted or unsubstituted C2-C50 heteroaryl group, or a combination thereof.

[0059] One or more of the above R1s include a polymerizable functional group, and

[0060] <Chemical Formula 1-1>

[0061]

[0062] <Chemical Formula 1-2>

[0063]

[0064] <Chemical Formula 1-3>

[0065]

[0066] <Chemical Formula 1-4>

[0067]

[0068] <Chemical Formula 1-5>

[0069]

[0070] <Chemical Formula 1-6>

[0071]

[0072] In the above chemical formulas 1-1 to 1-6,

[0073] R4 and R5 are each independently identical to the definition of R3 above, and

[0074] X are each independently O, S, Se, NR6, and SiR6R7, and R6 and R7 are each independently identical to the definition of R3 above, and

[0075] a is independently an integer from 0 to 4, and b is independently an integer from 0 to 3, and

[0076] "*" indicates the connection position.

[0077] The above repeating units may exist within a range of 1 to 20, and specifically, may be 1 to 10, 1 to 5, 1 to 3, 2 to 20, 2 to 10, 2 to 5, or 2 to 3.

[0078] Specifically, the above chemical formula 1 can be represented by the following chemical formula 2.

[0079] <Chemical Formula 2>

[0080]

[0081] In the above chemical formula 2,

[0082] The symbols identical to Chemical Formula 1 above have the same definition, and

[0083] L1 is each independently a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 alkoxylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C0-C30 silyl group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C1-C30 heterocycloalkylene group, a substituted or unsubstituted C3-C30 cycloalkenylene group, a substituted or unsubstituted C2-C30 heterocycloalkenylene group, a substituted or unsubstituted C3-C30 arylene group, or a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof, and the -CH2- present in L1 is -O-, -S-, -SO2-, -CO-, -C(OR4)R3-, -NR3-, It can be replaced with -C(=NR3)-, -Si(R3)2- or -P(R3)2-, and -CH3 can be replaced with -OH,

[0084] Each of the above R3s is independently identical in definition to R3 of Chemical Formula 1, and

[0085] Ra is each independently hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C0-C30 silyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 heterocycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C2-C30 heterocycloalkenyl group, a substituted or unsubstituted C3-C30 aryl group, or a substituted or unsubstituted C2-C30 heteroaryl group, a polymerizable functional group, or a combination thereof, wherein some or all of these include a polymerizable functional group, and the type of the polymerizable functional group is not limited, and specifically may be an acryloyloxy group, a methacryloyloxy group, or a vinyl group.

[0086] “*” indicates the connection position.

[0087] The above repeating units may exist within a range of 1 to 20, and specifically, may be 1 to 10, 1 to 5, 1 to 3, 2 to 20, 2 to 10, 2 to 5, or 2 to 3.

[0088]

[0089] According to one embodiment of the present invention, in Formula 1, R2 may be derived from the ring-opening reaction of a dianhydride compound.

[0090] According to one embodiment of the present invention, the dianhydride compound may be represented by any one of the following chemical formulas 3-1 to 3-3.

[0091] <Chemical Formula 3-1>

[0092]

[0093] <Chemical Formula 3-2>

[0094]

[0095] <Chemical Formula 3-3>

[0096]

[0097] In the above chemical formulas 3-1 to 3-3,

[0098] L1 to L3 are each independently a directly bonded, substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 alkoxylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C0-C30 silyl group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C1-C30 heterocycloalkylene group, a substituted or unsubstituted C3-C30 cycloalkenylene group, a substituted or unsubstituted C2-C30 heterocycloalkenylene group, a substituted or unsubstituted C3-C30 arylene group, or a substituted or unsubstituted C2-C30 heteroarylene group, -O-, -S-, -CO-, -C(OR4)R3- -NR3-, -C(=NR3)-, -Si(R3)2-, -P(R3)2- or a combination thereof, and -CH2- present in L1 to L3 can be replaced with -O-, -S-, -SO2-, -CO-, -C(OR4)R3-, -NR3-, -C(=NR3)-, -Si(R3)2- or -P(R3)2-, and

[0099] R3 is each independently hydrogen, deuterium, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C2-C50 alkenyl group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkyl group, a substituted or unsubstituted C1-C50 heterocycloalkyl group, a substituted or unsubstituted C3-C50 cycloalkenyl group, a substituted or unsubstituted C2-C50 heterocycloalkenyl group, a substituted or unsubstituted C3-C50 aryl group, or a substituted or unsubstituted C2-C50 heteroaryl group, or a combination thereof.

[0100] The G ring is a substituted or unsubstituted C4–C30 cycloalkyl group, or a substituted or unsubstituted C6–C50 aryl group.

[0101] In the above chemical formula 3-1, -L1-L2-L3- may be -SO2- or -S-. This allows for a further increase in the refractive index. Additionally, if -L1-L2-L3- is a direct bond, it is structurally stable and may exhibit excellent refractive index characteristics. Furthermore, if -COO- or -CO- structures are present in -L1-L2-L3-, molecular flexibility increases, resulting in good thermal reflow characteristics and being advantageous for fabricating spherical lens patterns; however, as the -L1-L2-L3- chain becomes longer, the electron density decreases, which may lead to a decrease in the refractive index. Moreover, if a phenylene structure is present in the -L1-L2-L3- structure, excessive flexibility can be compensated for compared to structures composed of simple alkylene, ether, or carbonyl groups, and the refractive index can be further improved.

[0102] In the case of the structure of Chemical Formula 3-3 above, it is structurally rigid and has a high electron density, so the refractive index may be high, but the thermal flow characteristics may be low.

[0103] Although not limited, dianhydride compounds may specifically be selected from the following chemical formulas.

[0104]

[0105]

[0106] In the above compounds, in the case of a compound in which -CF3 is not present, the performance may be superior, as shown in the examples described below.

[0107] <First Monomer>

[0108] The first monomer according to one embodiment of the present invention has a functional group. The functional group may include at least one polymerizable group, a hydroxyl group, or a phenolic group, although it is not limited to the above. The type of the polymerizable group is not limited and, specifically, may be an acryloyloxy group, a methacryloyloxy group, or a vinyl group. The hydroxyl group and the phenolic group may react with epoxy, etc., to participate in a polymerization reaction or react with an epoxy crosslinking agent to contribute to membrane formation.

[0109] In addition, according to one embodiment, the moles of the polymerizable groups relative to the total of 100 moles of the polymerizable groups and the hydroxyl or phenolic groups present in the molecule may be 0 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, and specifically 50 mol% or more. When the above ranges are satisfied, the light efficiency and refractive index may be excellent.

[0110] According to one embodiment of the present invention, the moles of the hydroxyl group relative to the total of 100 moles of the polymerizable group and the hydroxyl group or phenol group of the first monomer may be 0 mol% or more, 15 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, and specifically may be 30 mol% or more or 50 mol% or more. When the above range is satisfied, the refractive index may be excellent.

[0111] The first monomer may have one or two triazine groups within the molecule. The presence of triazine groups can result in excellent high refractive index properties.

[0112] According to one embodiment of the present invention, the first monomer may include one or more monomers represented by the following chemical formulas 4-1 to 4-3.

[0113] <Chemical Formula 4-1>

[0114]

[0115] <Chemical Formula 4-2>

[0116]

[0117] <Chemical Formula 4-3>

[0118]

[0119] In the above chemical formula 4-1,

[0120] The above Ra and Rd are each independently any one substituent selected from hydrogen, deuterium, substituted or unsubstituted C1-C6 alkyl groups, and

[0121] The above L1 is any one selected from a single bond, O, and -N(-R5)-, and

[0122] The above L2 is any one selected from single bond, O, and -N(-R6)-, and

[0123] The above X1 to X3 are each independently selected from a single bond, O, -N(-R7)-, and -O((CH2)mO)n-, wherein m and n are each the same or different and are integers independently selected from 1 to 4, and in the case where two or more of X1 to X3 each select -N(-R7)- or two or more of X1 to X3 each select -O((CH2)mO)n-, each -N(-R7)- and -O((CH2)mO)n- are each the same or different, and

[0124] The above R4 to R7 are each the same or different and are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, or a substituted or unsubstituted C7-C24 arylalkyl group.

[0125] The above W1 is any one selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C1-C12 alkylene group, and

[0126] The above W2 and W3 are each identical or different and are independently selected from single bonds, substituted or unsubstituted C1-C30 alkylene groups, substituted or unsubstituted C6-C30 arylene groups, substituted or unsubstituted C2-C30 alkenylene groups, substituted or unsubstituted C3-C30 cycloalkylene groups, substituted or unsubstituted C5-C30 cycloalkenylene groups, substituted or unsubstituted C2-C50 heteroarylene groups, and substituted or unsubstituted C2-C30 heterocycloalkylene groups.

[0127] The above Y1 and Y2 are each the same or different and are independently selected from a hydrogen, deuterium-substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C5-C30 cycloalkenyl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylsilyl group, and any one of the substituents represented by [Structural Formula 1] or [Structural Formula 2] below.

[0128] [Structural Formula 1]

[0129]

[0130] [Structural Formula 2]

[0131]

[0132] In the above [Structural Formula 1] and [Structural Formula 2],

[0133] The above Rb and Rc are each the same or different and are independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C6 alkyl groups, and

[0134] "-*" in the above structural formulas 1 and 2 each represent a binding site that is bonded to X2 or X3 in the above chemical formula A, and

[0135] In the above chemical formula 4-2,

[0136] The above Ar1 is any one selected from a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C3-C30 cycloalkylene group, and a substituted or unsubstituted C5-C30 cycloalkenylene group.

[0137] L6 is any one selected from single bond, O, and -N(-R11)-, and

[0138] L7 is any one selected from a single bond, O, and -N(-R12)-, and

[0139] In the above chemical formula 4-3,

[0140] The above Ar2 is any one selected from hydrogen, deuterium, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, and a substituted or unsubstituted C5-C30 cycloalkenyl group.

[0141] In the above chemical formulas 4-2 to 4-3,

[0142] The above Rd is any one substituent selected from hydrogen, deuterium, substituted or unsubstituted C1-C6 alkyl groups, and

[0143] The above L3 to L5 are each identical or different and are independently selected from single bond, O, and -N(-R9)-, and

[0144] In the case where two or more of the above L3 to L5 each select -N(-R9)-, each -N(-R9) is the same or different, and

[0145] The above X4 to X7 are each identical or different and are independently selected from a single bond, O, -N(-R10)-, and -O((CH2)mO)n-, wherein m and n are each identical or different and are independently selected from integers 1 to 4.

[0146] In the case where two or more of the above X4 to X7 each select -N(-R10)- or two or more of the above X4 to X7 each select -O((CH2)mO)n-, each -N(-R10)- and -O((CH2)mO)n- is the same or different, and

[0147] The above R8 to R12 are each the same or different and are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, or a substituted or unsubstituted C7-C24 arylalkyl group.

[0148] The above W4 is any one selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C1-C12 alkylene group, and

[0149] The above W5 to W7 are each identical or different and are independently selected from single bonds, substituted or unsubstituted C1-C30 alkylene groups, substituted or unsubstituted C6-C30 arylene groups, substituted or unsubstituted C2-C30 alkenylene groups, substituted or unsubstituted C3-C30 cycloalkylene groups, substituted or unsubstituted C5-C30 cycloalkenylene groups, substituted or unsubstituted C2-C50 heteroarylene groups, and substituted or unsubstituted C2-C30 heterocycloalkylene groups.

[0150] The above Y3 to Y5 are each identical or different and are independently selected from a hydrogen, deuterium-substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylsilyl group, and a substituent represented by [Structural Formula 1] or [Structural Formula 2].

[0151] The term "substituted" in "substituted or unsubstituted" in the above Chemical Formulas 4-1 to 4-3 refers to deuterium, cyano group, halogen group, hydroxyl group, nitro group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C2-C24 alkenyl group, C2-C24 alkynyl group, C1-24 heteroalkyl group, C6-C24 aryl group, C7-C24 arylalkyl group, C2-C24 heteroaryl group, C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylthionyl group, C1-C24 alkylamino group, C6-C24 arylamino group, C1-C24 heteroarylamino group, C1-C24 alkylsilyl group, It means being substituted with one or more substituents selected from the group consisting of C6-C24 arylsilyl groups, C6-C24 aryloxy groups, and C6-C24 arylthionyl groups.

[0152]

[0153] Specifically, the first monomer may be exemplified by the following compounds.

[0154]

[0155] [Compound 1][Compound 2]

[0156]

[0157] [Compound 3] [Compound 4]

[0158]

[0159] [Compound 5] [Compound 6]

[0160]

[0161] [Compound 7] [Compound 8]

[0162]

[0163] [Compound 9] [Compound 10]

[0164]

[0165] [Compound 11][Compound 12]

[0166]

[0167] [Compound 13] [Compound 14]

[0168]

[0169] [Compound 15] [Compound 16]

[0170]

[0171] [Compound 17][Compound 18]

[0172]

[0173] [Compound 19] [Compound 20]

[0174]

[0175] [Compound 21] [Compound 22]

[0176]

[0177] [Compound 23] [Compound 24]

[0178]

[0179] [Compound 25][Compound 26]

[0180]

[0181] [Compound 27] [Compound 28]

[0182]

[0183] [Compound 29] [Compound 30]

[0184]

[0185] [Compound 31] [Compound 32]

[0186]

[0187] [Compound 33] [Compound 34]

[0188] Monofunctional or difunctional secondary monomer

[0189] A monofunctional or difunctional second monomer according to one embodiment of the present invention may include one or more compounds represented by the following chemical formula 5.

[0190] <Chemical Formula 5>

[0191]

[0192] In the above chemical formula 5,

[0193] A1 is a polymerizable functional group, and

[0194] A2 is a hydrogen or polymerizable functional group, and

[0195] L1 and L2 are each independently a directly bonded, substituted, or unsubstituted C1-C50 alkylene group, a substituted or unsubstituted C1-C50 alkoxy group, a substituted or unsubstituted C2-C50 alkenylene group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkylene group, a substituted or unsubstituted C1-C50 heterocycloalkylene group, a substituted or unsubstituted C3-C50 cycloalkenylene group, a substituted or unsubstituted C2-C50 heterocycloalkenylene group, a substituted or unsubstituted C3-C50 arylene group, or a substituted or unsubstituted C2-C50 heteroarylene group, or a combination thereof, and the -CH2- present in L1 and L2 is -O-, -S-, SO2-, -CO-, -C(OR4)R4-, -NR4-, It can be replaced with -C(=NR4)-, -Si(R4)2- or -P(R4)2-, and

[0196] R4 is each independently hydrogen, deuterium, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C2-C50 alkenyl group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkyl group, a substituted or unsubstituted C1-C50 heterocycloalkyl group, a substituted or unsubstituted C3-C50 cycloalkenyl group, a substituted or unsubstituted C2-C50 heterocycloalkenyl group, a substituted or unsubstituted C3-C50 aryl group, or a substituted or unsubstituted C2-C50 heteroaryl group, or a combination thereof.

[0197] X1 is a directly bonded oxygen, sulfur, an ethyleneoxy group with 1 to 20 repeating structures, or a propyleneoxy group with 1 to 20 repeating structures, and

[0198] Ar is a substituted or unsubstituted C3–C50 aryl group, or a substituted or unsubstituted C2–C50 heteroaryl group, or a combination thereof, and

[0199] n is an integer from 1 to 3.

[0200] The types of the above polymerizable functional groups are not limited and, specifically, may be acryloyloxy groups, methacryloyloxy groups, or vinyl groups.

[0201] According to one embodiment of the present invention, the second monomer may include two or three non-condensing aryl ring structures or one aryl condensing ring. This allows the refractive index to be further improved.

[0202] According to one embodiment of the present invention, the second monomer may be a monofunctional monomer. This allows for further improvement of performance, such as light efficiency.

[0203] According to one embodiment of the present invention, when A2 in Chemical Formula 5 is a polymerizable functional group, it becomes a difunctional monomer, and in this case, X1 may be oxygen, sulfur, an ethyleneoxy group with 1 to 20 repeating structures, or a propyleneoxy group with 1 to 20 repeating structures.

[0204] According to one embodiment of the present invention, when A1 or A2 in the above chemical formula 5 is a polymerizable functional group, it may be selected from -OC(=O)CH=CH2, -CH=CH2, and -OC(=O)C(=CH2)CH3, and when it is -OC(=O)CH=CH2 or -OC(=O)C(=CH2)CH3, the length of the functional group is long, so the bonding strength with the benzene ring or styrene is excellent, and the light efficiency may be high.

[0205] According to one embodiment of the present invention, the monofunctional or difunctional second monomer may comprise a compound represented by any one of the following chemical structural formulas B.

[0206] Chemical Structure Formula B

[0207]

[0208]

[0209]

[0210] According to one embodiment of the present invention, the content of each component of the polymerizable composition may be as follows.

[0211] With respect to 100 parts by weight of the binder above, the first monomer may be included in the range of 10 to 60 parts by weight, and the second monomer may be included in the range of 5 to 20 parts by weight. Specifically, the first monomer may be included in an amount of 10 to 60 parts by weight, 10 to 50 parts by weight, 10 to 40 parts by weight, 10 to 30 parts by weight, 10 to 20 parts by weight, 15 to 60 parts by weight, 15 to 50 parts by weight, 15 to 40 parts by weight, 15 to 30 parts by weight, 15 to 20 parts by weight, 20 to 60 parts by weight, 20 to 50 parts by weight, 20 to 40 parts by weight, or 20 to 30 parts by weight, and the second monomer may be included in an amount of 5 to 15 parts by weight, 5 to 12 parts by weight, 8 to 20 parts by weight, 8 to 15 parts by weight, or 8 to 12 parts by weight. When the above ranges are satisfied, lens moldability can be maintained, so the light efficiency can be excellent.

[0212] In addition, the weight ratio of the first monomer and the second monomer may be within the range of 1:1 to 7:1. Specifically, it may be 2:1 to 7:1, 3:1 to 7:1, 4:1 to 7:1, 5:1 to 7:1, 1:1 to 6:1, 2:1 to 6:1, 3:1 to 6:1, 4:1 to 6:1, 5:1 to 6:1, 1:1 to 5:1, 2:1 to 5:1, 3:1 to 5:1, 4:1 to 5:1, 1:1 to 4:1, 2:1 to 4:1, or 3:1 to 4:1. Within the above range, the light efficiency may be excellent.

[0213] <Cross-linking agent>

[0214] According to one embodiment of the present invention, a crosslinking agent may be included.

[0215] As the above-mentioned crosslinking agent, a polyfunctional acrylate monomer or oligomer may be used and may have 2 to 20 functional groups. For example, aliphatic urethane acrylate oligomer, aromatic urethane acrylate oligomer, epoxy acrylate oligomer, epoxy methacrylate oligomer, polyester acrylate oligomer, silicone acrylate oligomer, melamine acrylate oligomer, and dendritic acrylate oligomer may be used, and these may be used alone or in a mixture of two or more types.

[0216] The content of the crosslinking agent may be included in an amount of 5 to 30 parts by weight relative to 100 parts by weight of the binder, specifically in an amount of 5 to 25 parts by weight, 10 to 30 parts by weight, 20 to 30 parts by weight, 10 to 25 parts by weight, 15 to 25 parts by weight, 20 to 25 parts by weight, 5 to 20 parts by weight, 10 to 20 parts by weight, or 15 to 20 parts by weight.

[0217] Photopolymerization Initiator

[0218] According to one embodiment of the present invention, a photopolymerization initiator may be included. The photopolymerization initiator may include at least one of a phosphine oxide-based compound, an acetophenone-based compound, an acylphosphine oxide-based compound, (E)-2-(acetoxyimino)-1-(9,9-diethyl-9H-fluorene-2-yl)butanone, [1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazoyl-3-yl]-1-(O-acetyloxime), an oxime-based compound, and an oxime ester-based compound. Specifically, the photopolymerization initiator may include at least a phosphine oxide-based compound. When using the aforementioned types of photopolymerization initiators, stable photocuring of the polymerizable composition can be induced, thereby improving the optical properties of the cured product of the polymerizable composition. As the above photopolymerization initiator, for example, phosphine oxide-based compound Irgacure 819, acetophenone-based compounds Irgacure 369 and Irgacure 907, oxime-based compound OXE-01, and oxime ester-based compound OXE-04 may be used.

[0219] According to one embodiment of the present invention, with respect to 100 parts by weight of the composition, the content of the photopolymerization initiator may be 1 part by weight or more and 20 parts by weight or less, 1 part by weight or more and 10 parts by weight or less, 5 parts by weight or more and 15 parts by weight or less, 5 parts by weight or more and 10 parts by weight or less, 10 parts by weight or more and 20 parts by weight or less, 10 parts by weight or more and 15 parts by weight or less, or 15 parts by weight or more and 20 parts by weight or less. By controlling the content of the photopolymerization initiator to the aforementioned range, the polymerization reaction of the monomer included in the polymerizable composition can be carried out effectively and stably.

[0220] Other ingredients

[0221] In addition to the components described above, the polymerizable composition according to one embodiment of the present invention may optionally include, but is not limited to, solvents, antioxidants, UV absorbers, thermal polymerization inhibitors, leveling agents, surfactants, lubricants, etc.

[0222] According to one embodiment of the present invention, the viscosity of the polymerizable composition may be 5 cP or more and 30 cP or less. The viscosity of the polymerizable composition may be measured at 25 ℃.

[0223] According to one embodiment of the present invention, sulfur atoms may be included in an amount of 2 parts by weight or less per 100 parts by weight of the total polymerizable composition. Specifically, sulfur atoms may be included in an amount of 1.5 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, or 0 parts by weight.

[0224] As another embodiment, the present invention provides a cured film comprising a cured product of the aforementioned polymerizable composition, wherein the refractive index of the cured film may be 1.60 or higher. Specifically, the cured film may have a refractive index of 1.60 or higher when measured at a wavelength of 565 nm. More specifically, the cured film may have a refractive index of 1.62 or higher when measured at a wavelength of 565 nm. The cured film exhibits high refractive index characteristics with a refractive index of 1.60 or higher, thereby enabling the realization of an optical member and a display device with excellent optical properties.

[0225] According to one embodiment of the present invention, sulfur atoms may be included in an amount of 2 parts by weight or less relative to a total of 100 parts by weight of the cured film. Specifically, sulfur atoms may be included in an amount of 1.5 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, or 0 parts by weight.

[0226] One embodiment of the present invention provides an optical member comprising the hardened film.

[0227] According to one embodiment of the present invention, the optical member includes the cured film, thereby enabling excellent optical properties such as increased light efficiency and high refractive index. In addition, the optical member may have excellent durability due to its excellent chemical resistance even under high temperature and high humidity conditions.

[0228] According to one embodiment of the present invention, the optical member may include a substrate; and the cured film provided on the substrate. Additionally, the cured film may be formed by photocuring after the polymerizable composition is applied onto the substrate by an inkjet process. In this case, a well-known substrate, such as bare glass, may be used as the substrate.

[0229] Additionally, the optical member may be manufactured by applying the polymerizable composition onto the substrate using a Mayer bar, a coating applicator, or inkjet equipment, and then performing photocuring by exposure using, for example, an LED lamp or a metal halide lamp in an air atmosphere. At this time, the polymerizable composition may be applied in a single film form and then photocured to form an optical member in the form of a general optical film, but if necessary, it may also be applied using the inkjet equipment to form a specific pattern and then photocured. In this case, the optical member may take the form of a pattern film in which a cured film patterned in the form of, for example, a prism structure or a lens structure is formed on the substrate.

[0230] Hereinafter, the present invention will be described in detail with reference to examples to specifically explain the invention. However, the embodiments according to the present invention may be modified in various different forms, and the scope of the present invention is not to be interpreted as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain the present invention to those with average knowledge in the art.

[0231] First monomer

[0232] As the first monomer, the first monomer of Table 1 below was prepared.

[0233] <Synthesization Example 1> Synthesis of First Monomer A1

[0234] 250 ml of THF was added to a 1 L reactor, and 15.0 g (81.3 mmol) of 2,4,6-trichloro-1,3,5-triazine was added under a nitrogen atmosphere. After cooling the reaction flask to 0°C, 26.6 g (244.0 mmol) of 4-aminophenol was slowly added over 30 minutes while stirring, followed by the addition of 20.0 g (244.0 mmol) of sodium acetate. The reaction vessel was heated to 80°C and stirred for 10 hours. After the reaction was complete, 250 ml of distilled water was added and stirred to prepare a white solid of 4,4',4''-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))triphenol.

[0235] 100 mL of THF, 30 mL of triethylamine, and 10.0 g (24.9 mmol) of 4,4',4''-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))triphenol were sequentially added to a 250 mL reactor, followed by cooling to 0 °C under nitrogen. 7.4 g (82.2 mmol) of acryloyl chloride was slowly added to the reaction vessel over 30 minutes, followed by stirring at room temperature for 5 hours. After the reaction was complete, the mixture was extracted with distilled water and ethyl acetate, and the organic layer was dried using MgSO4. Compound A1 was prepared by column purification with ethyl acetate : hexane = 1:3 after concentration under reduced pressure.

[0236] <Synthesized Examples 2 to 4>

[0237] Compounds A-1, A-2, A-3, and A-4 were prepared by varying the addition moles of 4-aminophenol and aniline instead of 4-aminophenol in Synthesis Example 1 above, and varying the addition moles of acryloyl chloride, thereby adjusting the ratio of terminal polymerization groups, hydroxyl groups, and phenol groups as shown in Table 1 below.

[0238] Synthetic Pre-monomer Symbol Terminal Photopolymerizer Ratio Photopolymerizer (mole) Hydroxyl group (mole) Phenol group (mole) Synthesis Example 1A-1100 3.00.00.0 Synthesis Example 2A-250 1.50.5 1.0 Synthesis Example 3A-350 1.5 1.00.5 Synthesis Example 4A-4000.03

[0239] Second monomer

[0240] BPMA was prepared as the second monomer.

[0241] (BPMA: 4-Biphenylylmethyl acrylate)

[0242] bookbinder

[0243] <Synthetic Example B>

[0244] 165 g of propylene glycol methyl ether acetate, 74.1 g (0.5 equivalents) of 3-acryloyloxypropoxy)phenylfluorene, and 35.9 g (0.5 equivalents) of 4,4'-Biphthalic Anhydride (BPDA) were added to a reactor and stirred at 25°C for 2 hours. The temperature was raised to 120–140°C to dissolve all the reactants, and after 12 hours of reaction, the reaction mixture was cooled to room temperature to obtain a binder having an acid value (converted to solid content) of 50 mgKOH / g and a weight-average molecular weight (Mw) of 2,000.

[0245] <Synthesized Examples 1 to 14>

[0246] Synthesis Example B above was carried out in the same manner except that the compound of Table 2 was used as the dianhydride, and the reaction time was varied from 12 hours to 24 hours to control the molecular weight, and a binder having a weight-average molecular weight (Mv) of 2000 to 15000 was obtained.

[0247]

[0248]

[0249] Photoinitiator

[0250] PHT-21 was used as a photoinitiator.

[0251] crosslinking agent

[0252] DPHA (Dipentaerythritol hexaacrylate) was prepared as a crosslinking agent.

[0253] surfactants

[0254] A nonionic surfactant was used as the surfactant.

[0255] Examples 1 to 71 and Comparative Examples 1 to 11

[0256] Preparation of polymerizable compositions

[0257] Compounds were prepared with the components and content of Table 3 below, and a monomer mixture was prepared. Subsequently, other components of Table 3 were added and mixed, and a polymerizable composition was prepared using 350 weight of PGMEA solvent based on 100 weight of solid content.

[0258] Preparation of hardened film

[0259] The compositions prepared in the above examples and comparative examples were applied to a SiNx substrate using a slit coater, respectively, and then pre-cured at 85°C for 240 seconds to form a film with a thickness of 11.0 μm. The resulting film was exposed using a mask designed to allow 100 to 30% exposure. The exposure was performed for a set period of time to achieve 240 mJ / cm² based on 365 nm. Subsequently, the film was developed at 23°C with an aqueous solution of TMAH diluted to 2.38 wt% until the unexposed areas were completely washed away. The formed pattern was post-cured in an 85°C oven for 40 minutes to obtain a lens pattern with a thickness of 10.0 μm (±0.1 μm).

[0260] Classification First Monomer Second Monomer Binder Photoinitiator Crosslinking Agent Surfactant Type Content Content Type Content Content Content Content Example 1A-11010C-11001.7212 Example 2A-12010C-11001.7212 Example 3A-12010C-01001.7212 Example 4A-13010C-11001.7212 Example 5A-15010C-11001.7212 Example 6A-1500C-11001.7212 Example 7A-21010C-11001.7212 Example 8A-22010C-11001.7212 Example 9A-23010C-11001.7212 Example 10A-25010C-11001.7212 Example 11A-31010C-11001.7212 Example 12A-32010C-11001.7212 Example 13A-33010C-11001.7212 Example 14A-35010C-11001.7212 Example 15A-41010C-11001.7212 Example 16A-42010C-11001.7212 Example 17A-43010C-11001.7212 Example 18A-45010C-11001.7212 Example 19A-11010C-21001.7212 Example 20A-12010C-21001.7212 Example 21A-13010C-21001.7212 Example 22A-15010C-21001.7212 Example 23A-11010C-31001.7212 Example 24A-12010C-31001.7212 Example 25A-13010C-31001.7212 Example 26A-15010C-31001.7212 Example 27A-11010C-41001.7212 Example 28A-12010C-41001.7212 Example 29A-13010C-41001.7212 Example 30A-15010C-41001.7212 Example 31A-11010C-51001.7212 Example 32A-12010C-51001.7212 Example 33A-13010C-51001.7212 Example 34A-15010C-51001.7212 Example 35A-11010C-61001.7212 Example 36A-12010C-61001.7212 Example 37A-13010C-61001.7212 Example 38A-15010C-61001.7212 Example 39A-11010C-71001.7212 Example 40A-12010C-71001.7212 Example 41A-13010C-71001.7212 Example 42A-15010C-71001.7212 Example 43A-11010C-81001.7212 Example 44A-12010C-81001.7212 Example 45A-13010C-81001.7212 Example 46A-15010C-81001.7212 Example 47A-11010C-91001.7212 Example 48A-12010C-91001.7212 Example 49A-13010C-91001.7212 Example 50A-15010C-91001.7212 Example 51A-11010C-101001.7212 Example 52A-12010C-101001.7212 Example 53A-13010C-101001.7212 Example 54A-15010C-101001.7212 Example 55A-12010C-111001.7212 Example 56A-12010C-121001.7212 Example 57A-16010C-11001.7212 Example 58A-26010C-11001.7212 Example 59A-36010C-11001.7212 Example 60A-46010C-11001.7212 Example 61A-16010C-21001.7212 Example 62A-16010C-31001.7212 Example 63A-16010C-41001.7212 Example 64A-16010C-51001.7212 Example 65A-16010C-61001.7212 Example 66A-16010C-71001.7212 Example 67A-16010C-81001.7212 Example 68A-16010C-91001.7212 Example 69A-16010C-101001.7212 Example 70A-1200C-131001.7212 Example 71A-1200C-141001.7212 Comparative Example 1-010C-11001.7212 Comparative Example 2-010C-21001.7212 Comparative Example 3-010C-31001.7212 Comparative Example 4-010C-41001.7212 Comparative Example 5-010C-51001.7212 Comparative Example 6-010C-61001.7212 Comparative Example 7-010C-71001.7212 Comparative Example 8-010C-81001.7212Comparative Example 9-010C-91001.7212Comparative Example 10-010C-101001.7212Comparative Example 11A-12010-01.7212.

[0261] Experimental Example

[0262] The following experiments were conducted on the polymerizable compositions and cured films prepared in the above examples and the polymerizable compositions and cured films prepared in the comparative examples, and the results are listed in Table 4 below.

[0263] 1) Luminous efficiency (%)

[0264] Measurements were taken using the OPI-305 instrument to compare the photometric characteristics in the frontal direction.

[0265] After supplying a constant current of 20mA to the LED element, photometric data was measured.

[0266]

[0267] 2) Refractive index

[0268] For the 2㎛ thick cured film formed on the glass substrate above, the refractive index (average of 555 to 575 nm) was measured using an ellipsometer.

[0269] 3) Lens pattern

[0270] The hemispherical lens was measured by analyzing the above-mentioned fabricated pattern with SEM.

[0271] Decision

[0272] O: Thickness / CD > 0.2

[0273] X: Thickness / CD ≤ 0.2

[0274] 4) Yellowing

[0275] Under the process conditions for producing the lens pattern, a single film was produced under the same conditions excluding mask application, and then a reliability evaluation device (QUV tester) was used to conduct the test for 120 hours by repeating the process at 60°C, 1J UVA lamp for 8 hours, and 85% humidity for 8 hours, after which the △YI value, which is the change from the initial Yellow Index value, was measured.

[0276] The yellowing test evaluated some of the examples and comparative examples.

[0277] Classification Luminous Efficiency (%) Refractive Index Lens Pattern Yellowing (ΔYI) Example 1941.61O Example 2951.63O 0.1 Example 3931.62O 0.3 Example 4961.65O Example 5971.67O Example 6961.65O Example 7921.61O Example 8931.63O Example 9941.65O Example 10951.67O Example 11931.61O Example 12931.62O Example 13941.64O Example 14941.66O Example 15901.61O Example 16911.62O Example 17921.64O Example 18931.65O Example 19921.61O Example 20931.63O 0.2 Example 21941.65O Example 22951.67O Example 23911.61O Example 24921.63O 0.1 Example 25931.65O Example 26941.67O Example 27911.61O Example 28921.63O 0.2 Example 29931.65O Example 30941.67O Example 31901.61O Example 32911.63O 0.1 Example 33921.65O Example 34931.67O Example 35901.61O Example 36911.63O 0.2 Example 37921.65O Example 38931.67O Example 39921.61O Example 40931.63O0.5 Example 41941.65O Example 42951.67O Example 43921.61O Example 44931.63O0.6 Example 45941.65O Example 46951.67O Example 47931.61O Example 48941.63O0.6 Example 49951.65O Example 50961.67O Example 51931.61O Example 52941.63O0.7 Example 53951.65O Example 54961.67O Example 55941.65O4.9 Example 56941.65O5 Example 57841.66O Example 58831.68O Example 59821.67O Example 60811.66O Example 61841.69O Example 62831.69O Example 63831.69O Example 64821.69O Example 65841.69O Example 66841.70O Example 67851.70O Example 68851.70O Example 69851.700 Example 70801.600.1 Example 71801.60 Comparative Example 1671.57X Comparative Example 2681.57X Comparative Example 3641.57X Comparative Example 4681.57X Comparative Example 5681.57X Comparative Example 6681.57X Comparative Example 7621.59X Comparative Example 8611.59X Comparative Example 9601.59X Comparative Example 10631.59X Comparative Example 11381.51X .

[0278] As can be seen from the results in Table 4 above,

[0279] It can be confirmed that the high-refractive index polymerizable composition according to one embodiment of the present invention exhibits superior light efficiency, refractive index, lens pattern, and yellowing reduction characteristics compared to the polymerizable composition of the comparative example.

[0280] In some examples, specifically Examples 55 and 56, the yellowing characteristics were slightly reduced as the sulfur content of the binder increased, and in Examples 57 to 71, it can be seen that the light efficiency was slightly reduced depending on the presence or content of each component.

[0281] When comparing the embodiments and comparative examples of the present invention,

[0282] In the case of Comparative Examples 1 to 10, it can be confirmed that the light efficiency, refractive index, and lens pattern characteristics are reduced because the first monomer is not contained, and

[0283] In the case of Comparative Example 11, it can be seen that the light efficiency, refractive index, and lens pattern characteristics are significantly reduced because it does not contain a binder.

[0284] Furthermore, a person skilled in the art will be able to fully understand the effects of the present invention from the experimental results of the above examples and comparative examples and Table 4.

Claims

A first monomer having at least one functional group; and A high-refractive index polymerizable composition comprising a binder containing a repeating unit of the following chemical formula 1. <Chemical Formula 1> In the above chemical formula 1, Ar1 is selected from the following chemical formulas 1-1 to 1-6, and Q is independently O, S, or NR', and R1 and R2 are each independently a substituted or unsubstituted C1-C50 alkylene group, a substituted or unsubstituted C1-C50 alkoxylene group, a substituted or unsubstituted C2-C50 alkenylene group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkylene group, a substituted or unsubstituted C1-C50 heterocycloalkylene group, a substituted or unsubstituted C3-C50 cycloalkenylene group, a substituted or unsubstituted C2-C50 heterocycloalkenylene group, a substituted or unsubstituted C3-C50 arylene group, or a substituted or unsubstituted C2-C50 heteroarylene group, or a combination thereof, and the -CH2- present in R1 and R2 is -O-, -S-, -SO2-, -CO-, -C(OR4)R3-, -NR3-, It can be replaced with -C(=NR3)-, -Si(R3)2- or -P(R3)2-, and -CH3 can be replaced with -OH, R' and R3 are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C2-C50 alkenyl group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkyl group, a substituted or unsubstituted C1-C50 heterocycloalkyl group, a substituted or unsubstituted C3-C50 cycloalkenyl group, a substituted or unsubstituted C2-C50 heterocycloalkenyl group, a substituted or unsubstituted C3-C50 aryl group, or a substituted or unsubstituted C2-C50 heteroaryl group, or a combination thereof. One or more of the above R1s include a polymerizable functional group, and <Chemical Formula 1-1> <Chemical Formula 1-2> <Chemical Formula 1-3> <Chemical Formula 1-4> <Chemical Formula 1-5> <Chemical Formula 1-6> In the above chemical formulas 1-1 to 1-6, R4 and R5 are each independently identical to the definition of R3 above, and X are each independently O, S, Se, NR6, and SiR6R7, and R6 and R7 are each independently identical to the definition of R3 above, and a is independently an integer from 0 to 4, and b is independently an integer from 0 to 3, and "*" indicates the connection position. In paragraph 1, The above chemical formula 1 is a high-refractive index polymerizable composition represented by the following chemical formula 2. <Chemical Formula 2> In the above chemical formula 2, The symbols identical to Chemical Formula 1 above have the same definition, and L1 is each independently a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C0-C30 silyl group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C1-C30 heterocycloalkylene group, a substituted or unsubstituted C3-C30 cycloalkenylene group, a substituted or unsubstituted C2-C30 heterocycloalkenylene group, a substituted or unsubstituted C3-C30 arylene group, or a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof, and the -CH2- present in L1 is -O-, -S-, -SO2-, -CO-, -C(OR4)R3-, -NR3-, It can be replaced with -C(=NR3)-, -Si(R3)2- or -P(R3)2-, and -CH3 can be replaced with -OH, Each of the above R3s is independently identical in definition to R3 of Chemical Formula 1, and Ra is each independently hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C0-C30 silyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 heterocycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C2-C30 heterocycloalkenyl group, a substituted or unsubstituted C3-C30 aryl group, or a substituted or unsubstituted C2-C30 heteroaryl group, a polymerizable functional group, or a combination thereof, wherein some or all of these include a polymerizable functional group. "*" indicates the connection position. In paragraph 1, R2 of the above chemical formula 1 is a high-refractive index polymerizable composition derived from the ring-opening reaction of a dianhydride compound. In paragraph 3, The above dianhydride compound is a high-refractive index polymerizable composition represented by any one of the following chemical formulas 3-1 to 3-3. <Chemical Formula 3-1> <Chemical Formula 3-2> <Chemical Formula 3-3> In the above chemical formulas 3-1 to 3-3, L1 to L3 are each independently a directly bonded, substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C0-C30 silyl group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C1-C30 heterocycloalkylene group, a substituted or unsubstituted C3-C30 cycloalkenylene group, a substituted or unsubstituted C2-C30 heterocycloalkenylene group, a substituted or unsubstituted C3-C30 arylene group, or a substituted or unsubstituted C2-C30 heteroarylene group, -O-, -S-, -CO-, -C(OR4)R3- -NR3-, -C(=NR3)-, -Si(R3)2-, -P(R3)2- or a combination thereof, and -CH2- present in L1 to L3 can be replaced with -O-, -S-, -SO2-, -CO-, -C(OR4)R3-, -NR3-, -C(=NR3)-, -Si(R3)2- or -P(R3)2-, and R3 is each independently hydrogen, deuterium, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C2-C50 alkenyl group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkyl group, a substituted or unsubstituted C1-C50 heterocycloalkyl group, a substituted or unsubstituted C3-C50 cycloalkenyl group, a substituted or unsubstituted C2-C50 heterocycloalkenyl group, a substituted or unsubstituted C3-C50 aryl group, or a substituted or unsubstituted C2-C50 heteroaryl group, or a combination thereof. The G ring is a substituted or unsubstituted C4–C30 cycloalkyl group, or a substituted or unsubstituted C6–C50 aryl group. In paragraph 3, The above dianhydride compound is a high-refractive index polymerizable composition selected from the following chemical formulas. In paragraph 1, A high-refractive index polymerizable composition further comprising a monofunctional or difunctional second monomer. In paragraph 1, A high-refractive index polymerizable composition having 2 parts by weight or less of sulfur atoms per 100 parts by weight of the total composition. In paragraph 1, A high-refractive index polymerizable composition comprising at least one polymerizable group, a hydroxyl group, or a phenolic group as the functional group of the first monomer. In paragraph 8, A high-refractive index polymerizable composition in which the moles of the polymerizable groups are 50 mol% or more relative to the total moles of the polymerizable groups, hydroxyl groups, or phenol groups of the first monomer above, and 100 mol. In paragraph 8, A high-refractive index polymerizable composition in which the moles of hydroxyl groups are 30 mol% or more relative to the total moles of polymerizable groups, hydroxyl groups, or phenolic groups of the first monomer. In paragraph 1, The above first monomer is a high-refractive index polymerizable composition having one or two triazine groups in the molecule. In paragraph 1, A high-refractive index polymerizable composition wherein the first monomer comprises one or more monomers represented by the following chemical formulas 4-1 to 4-3; <Chemical Formula 4-1> <Chemical Formula 4-2> <Chemical Formula 4-3> In the above chemical formula 4-1, The above Ra and Rd are each independently any one substituent selected from hydrogen, deuterium, substituted or unsubstituted C1-C6 alkyl groups, and The above L1 is any one selected from a single bond, O, and -N(-R5)-, and The above L2 is any one selected from single bond, O, and -N(-R6)-, and The above X1 to X3 are each independently selected from a single bond, O, -N(-R7)-, and -O((CH2)mO)n-, wherein m and n are each the same or different and are integers independently selected from 1 to 4, and in the case where two or more of X1 to X3 each select -N(-R7)- or two or more of X1 to X3 each select -O((CH2)mO)n-, each -N(-R7)- and -O((CH2)mO)n- are each the same or different, and The above R4 to R7 are each the same or different and are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, or a substituted or unsubstituted C7-C24 arylalkyl group. The above W1 is any one selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C1-C12 alkylene group, and The above W2 and W3 are each identical or different and are independently selected from single bonds, substituted or unsubstituted C1-C30 alkylene groups, substituted or unsubstituted C6-C30 arylene groups, substituted or unsubstituted C2-C30 alkenylene groups, substituted or unsubstituted C3-C30 cycloalkylene groups, substituted or unsubstituted C5-C30 cycloalkenylene groups, substituted or unsubstituted C2-C50 heteroarylene groups, and substituted or unsubstituted C2-C30 heterocycloalkylene groups. The above Y1 and Y2 are each the same or different and are independently selected from a hydrogen, deuterium-substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C5-C30 cycloalkenyl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylsilyl group, and any one of the substituents represented by [Structural Formula 1] or [Structural Formula 2] below. [Structural Formula 1] [Structural Formula 2] In the above [Structural Formula 1] and [Structural Formula 2], The above Rb and Rc are each the same or different and are independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C6 alkyl groups, and "-*" in the above structural formulas 1 and 2 each represent a binding site that is bonded to X2 or X3 in the above chemical formula A, and In the above chemical formula 4-2, The above Ar1 is any one selected from a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C3-C30 cycloalkylene group, and a substituted or unsubstituted C5-C30 cycloalkenylene group. L6 is any one selected from single bond, O, and -N(-R11)-, and L7 is any one selected from a single bond, O, and -N(-R12)-, and In the above chemical formula 4-3, The above Ar2 is any one selected from hydrogen, deuterium, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, and a substituted or unsubstituted C5-C30 cycloalkenyl group. In the above chemical formulas 4-2 to 4-3, The above Rd is any one substituent selected from hydrogen, deuterium, substituted or unsubstituted C1-C6 alkyl groups, and The above L3 to L5 are each identical or different and are independently selected from single bond, O, and -N(-R9)-, and In the case where two or more of the above L3 to L5 each select -N(-R9)-, each -N(-R9) is the same or different, and The above X4 to X7 are each identical or different and are independently selected from a single bond, O, -N(-R10)-, and -O((CH2)mO)n-, wherein m and n are each identical or different and are independently selected from integers 1 to 4. In the case where two or more of the above X4 to X7 each select -N(-R10)- or two or more of the above X4 to X7 each select -O((CH2)mO)n-, each -N(-R10)- and -O((CH2)mO)n- is the same or different, and The above R8 to R12 are each the same or different and are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, or a substituted or unsubstituted C7-C24 arylalkyl group. The above W4 is any one selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C1-C12 alkylene group, and The above W5 to W7 are each identical or different and are independently selected from single bonds, substituted or unsubstituted C1-C30 alkylene groups, substituted or unsubstituted C6-C30 arylene groups, substituted or unsubstituted C2-C30 alkenylene groups, substituted or unsubstituted C3-C30 cycloalkylene groups, substituted or unsubstituted C5-C30 cycloalkenylene groups, substituted or unsubstituted C2-C50 heteroarylene groups, and substituted or unsubstituted C2-C30 heterocycloalkylene groups. The above Y3 to Y5 are each identical or different and are independently selected from a hydrogen, deuterium-substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylsilyl group, and a substituent represented by [Structural Formula 1] or [Structural Formula 2]. The term "substituted" in "substituted or unsubstituted" in the above Chemical Formulas 4-1 to 4-3 refers to deuterium, cyano group, halogen group, hydroxyl group, nitro group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C2-C24 alkenyl group, C2-C24 alkynyl group, C1-24 heteroalkyl group, C6-C24 aryl group, C7-C24 arylalkyl group, C2-C24 heteroaryl group, C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylthionyl group, C1-C24 alkylamino group, C6-C24 arylamino group, C1-C24 heteroarylamino group, C1-C24 alkylsilyl group, It means being substituted with one or more substituents selected from the group consisting of C6-C24 arylsilyl groups, C6-C24 aryloxy groups, and C6-C24 arylthionyl groups. In paragraph 6, The above second monomer is a high-refractive index polymerizable composition represented by the following chemical formula 5. <Chemical Formula 5> In the above chemical formula 5, A1 is a polymerizable functional group, and A2 is a hydrogen or polymerizable functional group, and L1 and L2 are each independently a directly bonded, substituted, or unsubstituted C1-C50 alkylene group, a substituted or unsubstituted C1-C50 alkoxy group, a substituted or unsubstituted C2-C50 alkenylene group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkylene group, a substituted or unsubstituted C1-C50 heterocycloalkylene group, a substituted or unsubstituted C3-C50 cycloalkenylene group, a substituted or unsubstituted C2-C50 heterocycloalkenylene group, a substituted or unsubstituted C3-C50 arylene group, or a substituted or unsubstituted C2-C50 heteroarylene group, or a combination thereof, and the -CH2- present in L1 and L2 is -O-, -S-, -SO2-, -CO-, -C(OR4)R4- It can be replaced with -NR4-, -C(=NR4)-, -Si(R4)2- or -P(R4)2-, and R4 is each independently hydrogen, deuterium, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C2-C50 alkenyl group, a substituted or unsubstituted C0-C50 silyl group, a substituted or unsubstituted C3-C50 cycloalkyl group, a substituted or unsubstituted C1-C50 heterocycloalkyl group, a substituted or unsubstituted C3-C50 cycloalkenyl group, a substituted or unsubstituted C2-C50 heterocycloalkenyl group, a substituted or unsubstituted C3-C50 aryl group, or a substituted or unsubstituted C2-C50 heteroaryl group, or a combination thereof. X1 is a directly bonded oxygen, sulfur, an ethyleneoxy group with 1 to 20 repeating structures, or a propyleneoxy group with 1 to 20 repeating structures, and Ar is a substituted or unsubstituted C3–C50 aryl group, or a substituted or unsubstituted C2–C50 heteroaryl group, or a combination thereof, and n is an integer from 1 to 3. In paragraph 6, The above second monomer is a high-refractive index polymerizable composition represented by any one of the following chemical structural formulas B. Chemical Structure Formula B In paragraph 1, A high-refractive index polymerizable composition in which the weight-average molecular weight of the binder is within the range of 2,000 to 15,000. In paragraph 1, A high-refractive index polymerizable composition in which the first monomer is included in an amount of 10 to 60 parts by weight per 100 parts by weight of the binder. In paragraph 6, A high-refractive index polymerizable composition in which the weight ratio of the first monomer to the second monomer is 1:1 to 7:

1. A display device comprising a cured film of the high-refractive index polymerizable composition of claim 1. In Paragraph 18, The above-mentioned hardened film is a display device containing 2 parts by weight or less of sulfur atoms. In Paragraph 18, The above-mentioned hardened film has a refractive index of 1.60 or higher at a wavelength of 565 nm, and A display device having a light efficiency of 80% or more of the above-mentioned cured film.

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