Photosensitive resin composition, pattern formed from the same, and display device

Abstract

The present application provides a photosensitive resin composition, a pattern formed from the composition, and a display device, the photosensitive resin composition comprising (A) a monomer, (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) a solvent, wherein the (A) monomer comprises a novel high-refractive monomer chemical formula 1 comprising three or more ethylenically unsaturated double bonds and a polycyclic aromatic structure having a heteroatom, thereby enabling a coating film with a high refractive index, a high cone angle, and excellent heat and moisture resistance to be obtained, and the reliability of the coating film to be improved.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a pattern formed from the composition, and a display device, the composition comprising novel monomers and exhibiting high refractive index, high reliability, and high cone angle during pattern formation. Background Technology

[0002] With the development of the information society, people are making various demands on the display field. For example, research is being conducted on liquid crystal display devices (LCDs), plasma display panels (PLPs), electroluminescent display devices (EMDs), and organic light-emitting diode (OLED) display devices, which feature thinness, lightweight design, and low power consumption. Organic light-emitting diodes (OLEDs) have recently gained significant attention as next-generation display and lighting devices due to their advantages such as fast response speed, wide viewing angle, and low-voltage driving. Typically, in an OLED, an organic layer composed of luminescent or charge-moving materials is located between the upper and lower electrodes. OLEDs are structures composed of layers of materials with different refractive indices. Therefore, reflections occur at the interfaces of these materials, resulting in low efficiency in extracting light to the outside. Specifically, the refractive index of the organic luminescent layer constituting an OLED is approximately 1.7, the refractive index of ITO used as the transparent electrode is 2.0, and the refractive index of the glass substrate is 1.5. In this scenario, approximately 45% of the waveguide light is trapped within the transparent electrode or organic layer and cannot be extracted, while approximately 35% of the substrate waveguide light is trapped within the substrate and cannot be extracted. Therefore, only about 20% of the light emitted from the OLED is extracted to the outside. To address this issue, various studies are underway, with a notable approach being to improve light extraction efficiency by achieving low-refractive-index and high-refractive-index coatings.

[0003] In particular, as a method to increase the refractive index of organic compounds as monomers to achieve high refractive index coatings, it is well known that introducing halogen atoms (except fluorine) into the molecular structure is a useful approach. For example, in Japanese Patent Publication No. 1993-170702, a high refractive index aggregate with halogen atoms introduced into the biphenyl ring was used to utilize the high inherent refractive index of halogen atoms. However, when such monomers are included, environmental problems arise due to the introduction of halogens, and there is a problem of significant deterioration in heat resistance and lightfastness due to halogenation. Furthermore, since difunctional (methyl)aryl groups are included, it is difficult to ensure a high taper angle during patterning when applied to high refractive index photosensitive resin compositions. Therefore, there is a current need to develop a photosensitive resin suitable for displays by including novel monomers that can solve the above problems, thereby exhibiting high refractive index and excellent reliability, and exhibiting a high taper angle during patterning.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Publication No. 1993-170702 Summary of the Invention

[0007] The technical problem to be solved

[0008] The present invention aims to solve the problems of the prior art and its purpose is to provide a photosensitive resin composition, a pattern formed from the composition and a display device, wherein the composition contains a novel monomer represented by chemical formula 1 and having three or more ethylene unsaturated double bonds and a polycyclic aromatic structure having heteroatoms, thereby having excellent refractive index and high cone angle and high reliability during pattern formation.

[0009] However, the problems to be solved by this application are not limited to those mentioned above, and those skilled in the art will be able to clearly understand other problems not mentioned from the following description.

[0010] Technical solution

[0011] A photosensitive resin composition comprising (A) a monomer, (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) a solvent, characterized in that the monomer (A) comprises a compound represented by the following chemical formula 1.

[0012] [Chemical Formula 1]

[0013]

[0014] (in chemical formula 1,

[0015] X is any one of the following chemical formulas 2-1 to 2-16.

[0016] R1 can be either hydrogen or methyl.

[0017] R2 can be -O- or -S- independently.

[0018] R3 is an -OH group, or a substituent containing one or more (meth)acrylate groups, one or more benzene rings, or one or more carboxyl groups.

[0019] R4 is a substituent containing one or more (meth)acrylates.

[0020] [Chemical Formula 2-1]

[0021]

[0022] [Chemical Formula 2-2]

[0023]

[0024] [Chemical Formula 2-3]

[0025]

[0026] [Chemical Formula 2-4]

[0027]

[0028] [Chemical Formula 2-5]

[0029]

[0030] [Chemical Formula 2-6]

[0031]

[0032] [Chemical Formula 2-7]

[0033]

[0034] [Chemical Formula 2-8]

[0035]

[0036] [Chemical Formula 2-9]

[0037]

[0038] [Chemical Formula 2-10]

[0039]

[0040] [Chemical Formula 2-11]

[0041]

[0042] [Chemical Formula 2-12]

[0043]

[0044] [Chemical Formula 2-13]

[0045]

[0046] [Chemical Formula 2-14]

[0047]

[0048] [Chemical Formula 2-15]

[0049]

[0050] [Chemical Formula 2-16]

[0051]

[0052] (in chemical formulas 2-13 to 16,

[0053] R5 is -H, -CH3, -CH2CH3, -CH2CH2CH3, , , , , , , or ,

[0054] In chemical formulas 2-1 to 2-16, "*" indicates a bonding bond.

[0055] In one example of the present invention, R3 can be one selected from the group consisting of chemical formulas 3-1 to 3-16:

[0056] [Chemical Formula 3-1]

[0057]

[0058] [Chemical Formula 3-2]

[0059]

[0060] [Chemical Formula 3-3]

[0061]

[0062] [Chemical Formula 3-4]

[0063]

[0064] [Chemical Formula 3-5]

[0065]

[0066] [Chemical Formula 3-6]

[0067]

[0068] [Chemical Formula 3-7]

[0069]

[0070] [Chemical Formula 3-8]

[0071]

[0072] [Chemical Formula 3-9]

[0073]

[0074] [Chemical Formula 3-10]

[0075]

[0076] [Chemical Formula 3-11]

[0077]

[0078] [Chemical Formula 3-12]

[0079]

[0080] [Chemical Formula 3-13]

[0081]

[0082] [Chemical Formula 3-14]

[0083]

[0084] [Chemical Formula 3-15]

[0085]

[0086] [Chemical Formula 3-16]

[0087]

[0088] (In chemical formulas 3-1 to 3-16,

[0089] R1 can be either hydrogen or methyl.

[0090] R6 is an -OH group, or a substituent containing one or more benzene rings or sulfur atoms.

[0091] R7 is -H, -CH3, or ,

[0092] n is an integer from 0 to 3.

[0093] The asterisk (*) indicates a bond.

[0094] In one example of the invention, R4 can be one selected from the group consisting of chemical formulas 4-1 to 4-11:

[0095] [Chemical Formula 4-1]

[0096]

[0097] [Chemical Formula 4-2]

[0098]

[0099] [Chemical Formula 4-3]

[0100]

[0101] [Chemical Formula 4-4]

[0102]

[0103] [Chemical Formula 4-5]

[0104]

[0105] [Chemical Formula 4-6]

[0106]

[0107] [Chemical Formula 4-7]

[0108]

[0109] [Chemical Formula 4-8]

[0110]

[0111] [Chemical Formula 4-9]

[0112]

[0113] [Chemical Formula 4-10]

[0114]

[0115] [Chemical Formula 4-11]

[0116]

[0117] (In chemical formulas 4-1 to 4-11,

[0118] R1 can be either hydrogen or methyl.

[0119] R6 is an -OH group, or a substituent containing one or more benzene rings or sulfur atoms.

[0120] R7 is -H, -CH3, or ,

[0121] n is an integer from 0 to 3.

[0122] The asterisk (*) indicates a bond.

[0123] In one embodiment of the invention, an additive (E) is also included, which may be one or more selected from surfactants, adhesion promoters and thiols.

[0124] In another example of the invention, the thiol compound may be a sulfur-containing monomer, which is a polyfunctional thiol compound having 2 to 5 thiol groups (-SH) at the end.

[0125] In another embodiment of the invention, the polyfunctional thiol compound may comprise one or more of the following chemical formulas 5-1 to 5-5:

[0126] [Chemical Formula 5-1]

[0127]

[0128] [Chemical Formula 5-2]

[0129]

[0130] [Chemical Formula 5-3]

[0131]

[0132] [Chemical Formula 5-4]

[0133] [Chemical Formula 5-5]

[0134]

[0135] In one embodiment of the present invention, the acid value of the (B) alkali-soluble resin is from 20 mgKOH / g to 200 mgKOH / g.

[0136] In one example of the invention, the (B) alkali-soluble resin may comprise a Cardo resin.

[0137] In another example of the invention, the calo-based resin comprises at least one repeating unit of chemical formula 6-1 to 6-6.

[0138] [Chemical Formula 6-1]

[0139]

[0140] [Chemical Formula 6-2]

[0141]

[0142] [Chemical Formula 6-3]

[0143]

[0144] [Chemical Formula 6-4]

[0145]

[0146] [Chemical Formula 6-5]

[0147]

[0148] [Chemical Formula 6-6]

[0149]

[0150] The present invention provides a pattern comprising a cured product of a photosensitive resin composition according to an example of the present invention.

[0151] In one embodiment of the present invention, the refractive index of the pattern may be 1.62 or higher.

[0152] In one embodiment of the present invention, the pattern may be any one of the following: an array planarization film pattern, a protective film pattern, a microlens pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a columnar spacer pattern, a black columnar spacer, a colored photoresist pattern, a pattern containing a scatterer, and a pattern containing quantum dots.

[0153] The present invention provides a display device that includes a pattern according to an example of the present invention.

[0154] The effects of the invention

[0155] This invention, manufactured from a photosensitive resin composition comprising the monomer (A) represented by Chemical Formula 1 described above, enables the production of coatings with high refractive indices, the formation of patterns with high cone angles, and the provision of highly reliable patterns exhibiting excellent heat and moisture resistance. In particular, the patterns manufactured according to this invention have a refractive index of 1.62 or higher, achieving a very high refractive index, thus offering advantages in terms of high brightness when applied to display devices. Attached Figure Description

[0156] Figure 1 This is a diagram illustrating the method for evaluating the cone angle of the pattern according to the present invention. Detailed Implementation

[0157] This invention relates to a photosensitive resin composition, a pattern formed from the photosensitive resin composition, and a display device, the photosensitive resin composition comprising (A) a monomer, (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) a solvent; as the monomer, the photosensitive resin composition utilizes a novel high-refractive-index monomer characterized by comprising a compound represented by chemical formula 1. The monomer (A) may exist in the form of a mixture comprising a plurality of compounds represented by chemical formula 1.

[0158] According to the present invention, by manufacturing a coating comprising the aforementioned photosensitive resin composition, it is possible to achieve a coating with a high refractive index, resulting in a pattern with excellent cone angles, and a pattern exhibiting excellent heat resistance, moisture resistance, and high reliability. In particular, the pattern is characterized by a refractive index of 1.62 or higher, thereby enabling a display device with excellent brightness.

[0159] In this invention, the refractive index can be measured at a wavelength of 550 nm by optimizing and fitting the ellipticity of polarization measured by the ellipsometry method using the Cauchy model until the MSE is below 3.

[0160] [Chemical Formula 1]

[0161]

[0162] (in chemical formula 1,

[0163] X is any one of the following chemical formulas 2-1 to 2-16.

[0164] R1 can be either hydrogen or methyl.

[0165] R2 can be -O- or -S- independently.

[0166] R3 is an -OH group, or a substituent containing one or more (meth)acrylate groups, one or more benzene rings, or one or more carboxyl groups.

[0167] R4 is a substituent containing one or more (meth)acrylates.

[0168] [Chemical Formula 2-1]

[0169]

[0170] [Chemical Formula 2-2]

[0171]

[0172] [Chemical Formula 2-3]

[0173]

[0174] [Chemical Formula 2-4]

[0175]

[0176] [Chemical Formula 2-5]

[0177]

[0178] [Chemical Formula 2-6]

[0179]

[0180] [Chemical Formula 2-7]

[0181]

[0182] [Chemical Formula 2-8]

[0183]

[0184] [Chemical Formula 2-9]

[0185]

[0186] [Chemical Formula 2-10]

[0187]

[0188] [Chemical Formula 2-11]

[0189]

[0190] [Chemical Formula 2-12]

[0191]

[0192] [Chemical Formula 2-13]

[0193]

[0194] [Chemical Formula 2-14]

[0195]

[0196] [Chemical Formula 2-15]

[0197]

[0198] [Chemical Formula 2-16]

[0199]

[0200] (in chemical formulas 2-13 to 2-16,

[0201] R5 is -H, -CH3, -CH2CH3, -CH2CH2CH3, , , , , , , or ,

[0202] In chemical formulas 2-1 to 2-16, "*" indicates a bonding bond.

[0203] Patterns made from the photosensitive resin composition of the present invention can achieve high refractive index, and even under high temperature and / or high humidity conditions, changes in film thickness or appearance are minimized, resulting in excellent heat resistance and moisture resistance.

[0204] Furthermore, patterns made from the photosensitive resin composition of the present invention exhibit excellent cone angles.

[0205] The "high temperature" of this invention can be a temperature of 50°C or higher, preferably a temperature of 70°C or higher, and more preferably a temperature of 80°C to 90°C. The "high humidity" of this invention can be a condition of 70%RH or higher, preferably a condition of 85%RH.

[0206] The embodiments of the present invention will now be described in more detail. However, the terminology used in this specification is for describing the embodiments and not for limiting the invention. In this specification, the singular form also includes the plural form unless the context specifically indicates otherwise.

[0207] The terms “comprises” and / or “comprising” as used in this specification are used to mean, without excluding, one or more other constituent elements, steps and / or ingredients besides those mentioned.

[0208] <Photosensitive Resin Composition>

[0209] The photosensitive resin composition of the present invention is characterized in that (A) the monomer comprises a compound of formula 1. More specifically, the photosensitive resin composition of the present invention may comprise said (A) monomer, (B) alkali-soluble resin, (C) photopolymerization initiator, and (D) solvent. In particular, the photosensitive resin composition of the present invention is characterized in that the above-mentioned formula 1 comprises a polycyclic aromatic structure having heteroatoms within the molecule and having three or more vinyl unsaturated double bonds.

[0210] In addition, as an (E) additive, it may contain a polyfunctional thiol compound having 2 to 5 thiol groups (-SH) at the end, and may also contain other additives.

[0211] (A) Monomer

[0212] The monomer (A) described above is a substance that polymerizes and cures upon exposure to light such as ultraviolet light. It can increase the crosslinking density during the manufacturing process and enhance the optical properties of the photocured pattern. The monomer (A) described above is a compound that can polymerize under the action of the photopolymerization initiator (C) described below. It can impart a high refractive index to the cured film of the photosensitive resin composition of the present invention, increase the cone angle of the pattern within an appropriate range, and improve heat and moisture resistance, thereby resulting in excellent reliability of the display containing the cured film. The monomer (A) described above comprises a compound represented by the following chemical formula 1, which may contain three or more vinyl unsaturated double bonds, more preferably four or more vinyl unsaturated double bonds.

[0213] Furthermore, X in the above chemical formula 1 can possess a polycyclic aromatic structure with heteroatoms, preferably represented by chemical formulas 2-1 to 2-16:

[0214] [Chemical Formula 1]

[0215]

[0216] In chemical formula 1,

[0217] X is any one of the following chemical formulas 2-1 to 2-16.

[0218] R1 can be either hydrogen or methyl.

[0219] R2 can be -O- or -S- independently.

[0220] R3 is an -OH group, or a substituent containing one or more (meth)acrylate groups, one or more benzene rings, or one or more carboxyl groups.

[0221] R4 is a substituent containing one or more (meth)acrylates.

[0222] [Chemical Formula 2-1]

[0223]

[0224] [Chemical Formula 2-2]

[0225]

[0226] [Chemical Formula 2-3]

[0227]

[0228] [Chemical Formula 2-4]

[0229]

[0230] [Chemical Formula 2-5]

[0231]

[0232] [Chemical Formula 2-6]

[0233]

[0234] [Chemical Formula 2-7]

[0235]

[0236] [Chemical Formula 2-8]

[0237]

[0238] [Chemical Formula 2-9]

[0239]

[0240] [Chemical Formula 2-10]

[0241]

[0242] [Chemical Formula 2-11]

[0243]

[0244] [Chemical Formula 2-12]

[0245]

[0246] [Chemical Formula 2-13]

[0247]

[0248] [Chemical Formula 2-14]

[0249]

[0250] [Chemical Formula 2-15]

[0251]

[0252] [Chemical Formula 2-16]

[0253]

[0254] In chemical formulas 2-13 to 2-16,

[0255] R5 is -H, -CH3, -CH2CH3, -CH2CH2CH3, , , , , , , or ,

[0256] In chemical formulas 2-1 to 2-16, "*" represents a bonding bond. In this invention, the position of the bonding bond "*" within the structure is exemplary. Structures formed by bonding bonds at positions other than those shown are obviously also within the scope of this invention without prejudice to its purpose.

[0257] In this invention, (A) monomer contains the polycyclic aromatic structure and sulfur or nitrogen as heteroatoms, thereby significantly increasing the refractive index, and during pattern formation, the polycyclic aromatic structure affects the dissolution rate during development, so that an appropriate cone angle can be formed within a range that does not result in an inverted cone.

[0258] Furthermore, since the monomer (A) contains the vinyl unsaturated double bond, its adhesion to the substrate is improved during the development process, thereby preventing the pattern from peeling and deteriorating even under high temperature and / or high humidity conditions, which helps to form a pattern with excellent cone angle.

[0259] Generally, if the number of functional groups such as ethylene unsaturated double bonds increases, the refractive index tends to decrease. However, the monomer of this application can achieve a high refractive index by having a structure of chemical formula 1 containing a polycyclic aromatic structure with sulfur or nitrogen as heteroatoms.

[0260] That is, the refractive index is significantly improved by a polycyclic aromatic structure containing heteroatoms, and when the chemical formula contains three or more substituents having vinyl unsaturated double bonds, it can simultaneously exhibit excellent refractive index, cone angle, and moisture and heat resistance. Therefore, the monomer (A) of this application is a novel structure synthesized to simultaneously and excellently improve cone angle, moisture and heat resistance, and refractive index, and may contain at least one selected from the group represented by chemical formula 1 containing substituents having three or more vinyl unsaturated double bonds.

[0261] In the above chemical formula 1, R2 is independently either -O- or -S-. When R2 is -O-, it exhibits excellent stability and lightfastness; when R2 is -S-, it can improve the dielectric constant of the monomer, thus exhibiting excellent high refractive index.

[0262] R3 in the above chemical formula 1 is a -OH group, or a substituent containing one or more (meth)acrylate groups, one or more benzene rings or one or more carboxyl groups. Specifically, the substituent containing one or more (meth)acrylate groups, one or more benzene rings or one or more carboxyl groups can be selected from the group consisting of the following chemical formulas 3-1 to 3-16.

[0263] In the formula, "*" represents a bonding bond, n is an integer from 0 to 3, and R1, R6 and R7 are defined as described above.

[0264] In the formula, n=0 indicates direct binding.

[0265] [Chemical Formula 3-1]

[0266]

[0267] [Chemical Formula 3-2]

[0268]

[0269] [Chemical Formula 3-3]

[0270]

[0271] [Chemical Formula 3-4]

[0272]

[0273] [Chemical Formula 3-5]

[0274]

[0275] [Chemical Formula 3-6]

[0276]

[0277] [Chemical Formula 3-7]

[0278]

[0279] [Chemical Formula 3-8]

[0280]

[0281] [Chemical Formula 3-9]

[0282]

[0283] [Chemical Formula 3-10]

[0284]

[0285] [Chemical Formula 3-11]

[0286]

[0287] [Chemical Formula 3-12]

[0288]

[0289] [Chemical Formula 3-13]

[0290]

[0291] [Chemical Formula 3-14]

[0292]

[0293] [Chemical Formula 3-15]

[0294]

[0295] [Chemical Formula 3-16]

[0296]

[0297] R4 in the above chemical formula 1 is a substituent containing one or more (meth)acrylate groups. Specifically, the substituent containing (meth)acrylate groups can be one selected from the group consisting of chemical formulas 4-1 to 4-11.

[0298] In the formula, "*" represents a bonding bond, n is an integer from 0 to 3, and R1, R6 and R7 are defined as described above.

[0299] [Chemical Formula 4-1]

[0300]

[0301] [Chemical Formula 4-2]

[0302]

[0303] [Chemical Formula 4-3]

[0304]

[0305] [Chemical Formula 4-4]

[0306]

[0307] [Chemical Formula 4-5]

[0308]

[0309] [Chemical Formula 4-6]

[0310]

[0311] [Chemical Formula 4-7]

[0312]

[0313] [Chemical Formula 4-8]

[0314]

[0315] [Chemical Formula 4-9]

[0316]

[0317] [Chemical Formula 4-10]

[0318]

[0319] [Chemical Formula 4-11]

[0320]

[0321] In one embodiment, the monomer of the present invention may be one or more of chemical formulas 1a to 1j.

[0322] [Chemical Formula 1a]

[0323]

[0324] [Chemical Formula 1b]

[0325]

[0326] [Chemical Formula 1c]

[0327]

[0328] [Chemical formula 1d]

[0329]

[0330] [Chemical formula 1e]

[0331]

[0332] [Chemical Formula 1f]

[0333]

[0334] [Chemical formula 1g]

[0335]

[0336] [Chemical formula 1h]

[0337]

[0338] [Chemical Formula 1i]

[0339]

[0340] [Chemical Formula 1j]

[0341]

[0342] The photosensitive resin composition of the present invention may contain two or more (A) monomers, for example, it may simultaneously contain a monomer represented by chemical formula 1a and a monomer represented by chemical formula 1j.

[0343] The content of monomer (A) is preferably 20 to 80 parts by weight, more preferably 40 to 60 parts by weight, relative to 100 parts by weight of the total solid components in the photosensitive resin composition. When monomers having a polycyclic aromatic structure and three or more vinyl unsaturated double bonds are included within the above range, the refractive index, cone angle, and moisture and heat resistance all become excellent.

[0344] (B) Alkali-soluble resin

[0345] The alkali-soluble resin (B) included in the photosensitive resin composition of the present invention can be used without particular limitation on its type, as long as it is a resin that can be dissolved in an alkaline developing solution. Furthermore, resins with further reactive properties can also be used. Specifically, examples include carboxyl-containing monomers and copolymers with other monomers capable of copolymerizing with the aforementioned carboxyl-containing monomers.

[0346] Preferably, the alkali-soluble resin (B) included in the photosensitive resin composition of the present invention can be a calomel resin. When used with the monomer of the present invention, the calomel resin has the advantage of ensuring development properties and facilitating pattern formation while achieving a high refractive index. Specifically, the calomel resin may contain at least one repeating unit of the following chemical formulas 6-1 to 6-6.

[0347] [Chemical Formula 6-1]

[0348]

[0349] [Chemical Formula 6-2]

[0350]

[0351] [Chemical Formula 6-3]

[0352]

[0353] [Chemical Formula 6-4]

[0354]

[0355] [Chemical Formula 6-5]

[0356]

[0357] [Chemical Formula 6-6]

[0358]

[0359] Among the above chemical formulas 6-1 to 6-6,

[0360] X' and X'' are each independently a single bond, -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, , , , , , , , , , , , or ,

[0361] Y represents an acid anhydride residue.

[0362] Z represents an acid dianhydride residue.

[0363] R' can be a hydrogen atom, ethyl group, phenyl group, -C2H4Cl, -C2H4OH, or -CH2CH=CH2.

[0364] R1a, R1', R2a, R2', R3a, R3', R4a, R4', R5a, R5', R6a, and R6' are each independently a hydrogen atom or a methyl group.

[0365] R7a, R7', R8a, and R8' are each independently a C1-C6 alkylene group, wherein the alkylene group is inserted into or not inserted into at least one of an ester bond, a C6-C14 cycloalkylene group, and an aryl group.

[0366] R9a, R9', R10a, R10', R11a, R11', R12a, and R12' are each independently a hydrogen atom, a halogen atom, or a C1-C6 alkyl group.

[0367] m and n1 are each an independent integer from 1 to 30.

[0368] t and u are each an independent integer from 0 to 1.

[0369] P is independent of each , , , or ,

[0370] R13 and R14 are each independently a hydrogen atom, hydroxyl group, mercapto group, amino group, nitro group, or halogen atom.

[0371] Ar1 is an aryl group, each of which is independent.

[0372] Y' represents an acid anhydride residue.

[0373] Z' is an acid dianhydride residue.

[0374] A can be -O-, -S-, -NR'-, -Si(R')2-, or -Se-.

[0375] a and b are each independent integers from 1 to 6.

[0376] p and q are each independent integers from 1 to 30.

[0377] In one embodiment of the present invention, the aforementioned acid anhydride may be selected from the group consisting of maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylmethylenetetrahydrophthalic anhydride, chloramphenic anhydride, and methyltetrahydrophthalic anhydride.

[0378] In one embodiment of the present invention, the acid dianhydride may be selected from the group consisting of pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and diphenyl ether tetracarboxylic dianhydride.

[0379] The alkali-soluble resin of the present invention can influence the patterning process of the photosensitive resin composition according to its acid value and molecular weight.

[0380] From the perspective of improving the reactivity and chemical resistance of the photosensitive resin composition under low-temperature conditions, the weight-average molecular weight (e.g., determined by gel permeation chromatography (GPC) using polystyrene as a standard) of the aforementioned alkali-soluble resin can be between 2,000 and 20,000, preferably between 2,000 and 10,000. When the above-mentioned weight-average molecular weight (Mw) range is met, the CD-Bias (critical size deviation) of the pattern is within an appropriate range, thereby enabling the formation of patterns with excellent resolution and improving the chemical resistance of the pattern. On the other hand, when the weight-average molecular weight of the adhesive resin exceeds 20,000, the molecular weight becomes too large, which may lead to a decrease in compatibility with other components of the photosensitive resin composition, resulting in whitening of the coating during the development stage. Furthermore, the linewidth of the pattern may increase, leading to a decrease in CD-bias characteristics, and the alkali solubility of the unexposed areas may decrease, resulting in residue on the underlying substrate. In addition, when the weight-average molecular weight of the aforementioned adhesive resin is less than 2,000, it may cause problems with reliability.

[0381] Acid value refers to the amount (mg) of potassium hydroxide required to neutralize 1g of polymer, and is usually determined by titration with an aqueous solution of potassium hydroxide. It can affect pattern formation during the process. The acid value of the adhesive resin is preferably 20 to 200 mgKOH / g. If the acid value is within this range, the solubility in the developer is increased, making it easier to dissolve the non-exposed areas and increasing the sensitivity. As a result, the pattern on the exposed areas remains during development, thus improving the film retention ratio, which is therefore preferred.

[0382] In addition, the alkali-soluble resin contained in the photosensitive resin composition of the present invention can be used without limitation as long as it is soluble in the alkaline developing solution used in the developing process, serving as a component that imparts solubility to the alkaline developing solution.

[0383] Relative to 100 parts by weight of the total solid components in the photosensitive resin composition, the content of the alkali-soluble resin of the present invention can be 20 to 80 parts by weight, preferably 40 to 60 parts by weight. When the alkali-soluble resin is included within the above range, it is preferable in terms of ensuring high resolution and reliability. If the content is too low and below the above range, the degree of curing may be affected; if the content is greater than the above range, it may lead to a decrease in resolution.

[0384] (C) Photopolymerization initiator

[0385] The photopolymerization initiator described above (C) serves to induce a free radical reaction in the photosensitive resin composition, thereby causing curing and increasing sensitivity. This invention does not impose any particular limitation on it; any compound capable of generating free radicals that can initiate the polymerization of the aforementioned photocurable compound upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, or X-rays can be used without restriction. In particular, the photopolymerization initiator is a compound used to initiate or promote the reaction of polymerizable functional groups of monomers having the vinyl unsaturated double bonds of this invention.

[0386] Representative initiators include acetophenone compounds, benzophenone compounds, biimidazole compounds, triazine compounds, oxime ester compounds, and thioxanone compounds. In this invention, the initiator can be used alone or in combination of two or more, preferably one or more oxime ester compounds.

[0387] Examples of the aforementioned acetophenone compounds include, for instance, α-aminoacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzoyladium dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylphenylthio)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one, and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butane-1-one. Commercially available products include Irgacure-907 (BASF).

[0388] Examples of the aforementioned benzophenone compounds include: benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

[0389] Examples of the aforementioned biimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'- Tetraphenyl-1,2'-Biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc.

[0390] Examples of the aforementioned triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- [2-(2-(furan-2-yl)ethylene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethylene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethylene]-1,3,5-triazine, etc.

[0391] Examples of the aforementioned oxime ester compounds include: o-ethoxycarbonyl-α-oximino-1-phenylprop-1-one, 1,2-octanedione-1-(4-phenylthio)phenyl-2-(o-benzoyl oxime), acetone-1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-1-(o-acetyl oxime), etc. Commercially available products include CGI-124 (Ciba-Geigy), CGI-224 (Ciba-Geigy), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adico), NCI-831 (Adico), etc.

[0392] Examples of the above-mentioned thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0393] The aforementioned initiator can be used in conjunction with a photopolymerization initiation aid. The aforementioned photopolymerization initiation aid can be used to promote the polymerization of photocurable compounds initiated by the initiator.

[0394] Examples of photopolymerization initiators include amine compounds and alkoxyanthracene compounds. Specific examples of the amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as michalcone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, and 4,4'-bis(N,N'-dimethylamino)-benzophenone, with 4,4'-bis(N,N'-dimethylamino)-benzophenone being preferred.

[0395] Specific examples of the aforementioned alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photopolymerization initiators can be used alone or in combination of two or more. Furthermore, commercially available products such as EAB-F (trade name, manufactured by Hodogaya Chemical Co., Ltd.) can also be used as photopolymerization initiators.

[0396] Specific examples of preferred combinations of the above-mentioned initiators and photopolymerization initiation aids include: diethoxyacetophenone and 4,4'-bis(diethylamino)benzophenone; 2-methyl-2-morpholino-1-(4-methylthiophenyl)prop-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-phenylprop-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]prop-1-one and 4,4'-bis(diethylamino)benzophenone; 1-hydroxycyclohexylphenyl ketone and 4,4'-bis(diethylamino)benzophenone; 2 Oligomers of hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]prop-1-one and 4,4'-bis(diethylamino)benzophenone; combinations of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)but-1-one and 4,4'-bis(diethylamino)benzophenone, etc., preferably, combinations of 2-methyl-2-morpholino-1-(4-methylthiophenyl)prop-1-one and 4,4'-bis(diethylamino)benzophenone, combinations of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)but-1-one and 4,4'-bis(N,N'-dimethylamino)-benzophenone, etc.

[0397] When the above-mentioned initiator and photopolymerization initiation aid are used simultaneously, the content of the photopolymerization initiation aid is preferably 0.01 to 5 mol relative to 1 mol of the initiator. When the content of the photopolymerization initiation aid is within the above-mentioned range, the sensitivity of the photosensitive resin composition is higher, and the productivity of the cured film formed using the composition is improved, therefore it is preferred.

[0398] The initiator content can be from 0.01 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, relative to 100 parts by weight of the total solid components in the photosensitive resin composition. When the content is within the above range, the photosensitive resin composition has high sensitivity, shortens the exposure time, and is easy to adjust for pattern formation, and is preferred in terms of improving curing degree and straightness. When the content is greater than 10 parts by weight, the linewidth will be excessively broadened, making it impossible to maintain high resolution.

[0399] (D) Solvent

[0400] In this invention, (D) solvent can be any solvent commonly used in photosensitive resin compositions, provided that it is effective in dissolving other components contained in the photosensitive resin composition of this invention. Ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are particularly preferred.

[0401] Specific examples of the solvents mentioned above include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and other ethylene glycol monoalkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and other diethylene glycol dialkyl ethers; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; and propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Alkyl esters, such as propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl pentyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

[0402] From the perspective of coatability and drying properties, the solvents mentioned above are preferably organic solvents with a boiling point of 100°C to 200°C, and more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc.

[0403] The solvents mentioned above can be used individually or in combination.

[0404] The solvent described above can be included in such a quantity that the total weight of the photosensitive resin composition is 100% by weight. Specifically, in this invention, "balance" means that the total weight of the composition containing the essential components of this invention as well as other additional components is 100% by weight, and is not limited to the absence of additional components in the composition of this invention due to the meaning of "balance". For example, the content relative to the total weight of the photosensitive resin composition of this invention can be 10 to 90% by weight, preferably 50 to 80% by weight. When the solvent is included in the above range, it provides improved coatability when coated using coating apparatus such as roller coaters, spin coaters, slot coaters, slot die coaters (sometimes also called die coaters), inkjet printers, etc.

[0405] (E) Additives

[0406] The additive (E) of this invention may further include surfactants to improve film flatness; may further include adhesion promoters to improve film adhesion; and may further include additives such as thiol compounds to improve the refractive index and reliability of the film. In addition, it may further include additives commonly used in the art to which this invention pertains. These may be used alone or in combination or proportion of two or more in any combination.

[0407] Specifically, the thiol compound can be a sulfur-containing monomer, and is a polyfunctional thiol compound with 2 to 5 thiol groups (-SH) at the end.

[0408] More specifically, the polyfunctional thiol compound may consist of a mixture of one or more of the following chemical formulas 5-1 to 5-5.

[0409] [Chemical Formula 5-1]

[0410]

[0411] [Chemical Formula 5-2]

[0412]

[0413] [Chemical Formula 5-3]

[0414]

[0415] [Chemical Formula 5-4]

[0416]

[0417] [Chemical Formula 5-5]

[0418]

[0419] The photosensitive resin composition of this application containing the above-mentioned thiol compounds can have excellent properties such as high solvent resistance, water resistance, heat resistance, alkali resistance, and chemical resistance.

[0420] The content of the thiol compound can be 0.1 to 10 parts by weight relative to 100 parts by weight of the total solid components in the photosensitive resin composition, preferably 1 to 8 parts by weight, and more preferably 3 to 6 parts by weight. When the content is below the above range, the effect of increasing the refractive index may not be observed; while when the content is above the above range, the unexposed area may not be able to dissolve in the developer, resulting in residue, and a decrease in resolution may occur.

[0421] Specifically, examples of surfactants mentioned above include silicone-based, fluorinated, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. These surfactants can be used individually or in combination of two or more, with silicone-based and / or fluorinated surfactants being more preferred, but not limited thereto.

[0422] For the aforementioned silicone-based surfactants, commercially available examples include DC3PA, DC7PA, SH11PA, SH21PA, and SH-8400 from Dow Corning Toray Silicones, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 from GE Toshiba Silicones. For the aforementioned fluorinated surfactants, commercially available examples include MEGAFACE F-470, F-471, F-475, F-482, F-489, and F-554 from Dai Nippon Ink Chemical Co., Ltd. The surfactants described above can be used individually or in combination of two or more.

[0423] Specifically, examples of the aforementioned adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate-propyltrimethoxysilane, and 3-isocyanate-propyltriethoxysilane. The adhesion promoters exemplified above can be used individually or in combination of two or more.

[0424] The above-mentioned additives may be appropriately added and used by those skilled in the art without impairing the effects of the present invention. For example, the amount of the above-mentioned additives used may be 0.01 to 10% by weight, preferably 0.1 to 9% by weight, more preferably 0.1 to 8% by weight, relative to 100 parts by weight of the total solid components in the photosensitive resin composition, but is not limited thereto.

[0425] <Pattern>

[0426] The present invention includes photocurable patterns formed on a substrate using a photosensitive resin composition.

[0427] The patterns of the present invention, except that they are formed from the aforementioned photosensitive resin composition, can be manufactured using methods known in the art. When forming a photocurable pattern, the pattern can be formed by applying the aforementioned photosensitive resin composition onto a substrate followed by exposure and development, with pre-baking or post-baking processes performed between each step. The heating temperature and time for pre-baking are selected depending on the solvent used, for example, at a temperature of 80°C to 100°C for 1 to 3 minutes. The exposure is performed using an exposure machine, through a photomask, exposing only the portion corresponding to the pattern to light. The irradiated light can be, for example, visible light, ultraviolet light, X-rays, or electron beams. The exposure time is not particularly limited and can be appropriately varied depending on the exposure apparatus, the wavelength of the irradiated light, or the exposure intensity, but a preferred exposure time can vary within the range of 5 to 250 seconds.

[0428] Subsequently, as a step to increase hardness by improving the adhesion between the patterned film and the substrate, a heat treatment can be performed for 10 to 120 minutes at a curing temperature used to complete curing, preferably at a temperature of 80 to 230°C. The heat treatment can be performed using an oven or a hot plate, but is not limited thereto.

[0429] At this point, the thickness of the cured pattern is 2 to 15 μm, more preferably 5 to 10 μm. If the thickness of the pattern is less than the above range, problems may occur in terms of resolution and pattern formation; if it is greater than the above range, problems may occur in terms of decreased transmittance or affected optical properties.

[0430] Patterns manufactured from the photosensitive resin composition of the present invention exhibit particularly excellent refractive index and cone angle, and their physical properties, such as moisture and heat resistance, are improved, thereby achieving excellent reliability. Specifically, the refractive index of the aforementioned pattern can be 1.62 or higher. Regarding this refractive index, when the ellipticity of the polarization measured by ellipsometry is fitted to the Cauchy model according to Formula 1 below to achieve an MSE of 3 or lower, the refractive index measured at a wavelength of 550 nm can be 1.62 or higher. Therefore, when the pattern of the present invention is used in the interlayer material of a display, it has advantages in achieving high brightness.

[0431] The aforementioned pattern can be a photocurable pattern selected from the group consisting of array planarization film pattern, protective film pattern, microlens pattern, insulating film pattern, photoresist pattern, black matrix pattern, columnar spacer pattern, black columnar spacer, colored photoresist pattern, pattern containing scatterers, and pattern containing quantum dots.

[0432] <Display Device>

[0433] The present invention provides a display device comprising a pattern made of the above-described photosensitive resin composition.

[0434] Specifically, the display device may be a liquid crystal display (LCD), an organic EL display (including organic EL display devices, OLED and QLED), a flexible display, a liquid crystal projector, a display device for game consoles, a display device for mobile terminals such as mobile phones, a display device for digital cameras, a navigation display device, etc., but is not limited to these.

[0435] In addition to the above-described pattern, the display device may further include components commonly used in the art.

[0436] The following experimental examples, including specific embodiments and comparative examples, are provided to aid in understanding the present invention. However, these are merely illustrative and not intended to limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications can be made to the embodiments within the scope and technical concept of the present invention, and such variations and modifications obviously also fall within the scope of the appended claims. Unless otherwise specified, "%" and "parts" in the examples refer to "% by weight" and "parts by weight," respectively.

[0437] Furthermore, the synthetic examples are merely one example of the manufacture of the relevant compounds, and the following synthetic examples are only preferred synthetic examples of the present invention. The present invention is not limited to the following synthetic examples.

[0438] Synthesis Example 1-1: Production of Monomer A1

[0439] A three-necked flask equipped with a thermometer and a dropping funnel was used to add 50 mmol (15.82 g) of 3,11-dihydroxydinaphthalo[2,1-b:1',2'-d]thiophene, 101 mmol (12.94 g) of glycidyl acrylate, 1 g of triethylamine, and 100 ml of 1,4-dioxane. The reaction was carried out at 78°C for 8 hours. After purification, filtration, and drying, the reaction product was obtained. Then, 30 mmol (17.18 g) of the reaction product, 61 mmol (6.17 g) of triethylamine, and 50 ml of THF were added and stirred to dissolve. Under ice bath conditions, a solution of 61 mmol (5.52 g) of acryloyl chloride dissolved in 50 ml of THF was added dropwise over 30 minutes. After the addition was complete, the reaction temperature was raised to 50°C and stirred for 3 hours, then cooled to stop the reaction. After cooling the reaction solution to room temperature, unreacted acryloyl chloride was quenched with ice water. Then, the mixture was separated with a saturated sodium bicarbonate solution to remove acrylic acid, a decomposition product of acryloyl chloride. Next, THF was removed using an evaporator, thereby obtaining the final product with the structure shown in Formula 1a below.

[0440] [Chemical Formula 1a]

[0441]

[0442] Synthesis Example 1-2: Production of Monomer A2

[0443] The final product shown in Chemical Formula 1b was obtained by replacing 3,11-dihydroxydinaphtho[2,1-b:1',2'-d]thiophene-2,9-diol in the manufacturing method of Synthetic Example 1-1 with benzo[b]naphthalene[1,2-d]thiophene[2,1-b:1',2'-d]thiophene, except that the same method was used as in Synthetic Example 1-1.

[0444] [Chemical Formula 1b]

[0445]

[0446] Synthesis Examples 1-3: Production of Monomer A3

[0447] The final product with the structure shown in Chemical Formula 1c was obtained by replacing 3,11-dihydroxydinaphthalo[2,1-b:1',2'-d]thiophene in the manufacturing method of Synthetic Example 1-1 with benzo[b]naphthalene[2,3-d]thiophene-3,10-diol. Otherwise, the final product was obtained by the same method as in Synthetic Example 1-1.

[0448] [Chemical Formula 1c]

[0449]

[0450] Synthesis Examples 1-4: Production of Monomer A4

[0451] The final product shown in chemical formula 1d below was obtained by using 3,9-dihydroxy-11-phenylbenzo[a]carbazole instead of 3,11-dihydroxydinaphthalo[2,1-b:1',2'-d]thiophene in the manufacturing method of Synthetic Example 1-1, except that the final product was obtained by the same method as in Synthetic Example 1-1.

[0452] [Chemical formula 1d]

[0453]

[0454] Synthesis Examples 1-5: Production of Monomer A5

[0455] The final product shown in Chemical Formula 1e was obtained by using 3,6-bis(4-hydroxyphenyl)-N-phenylcarbazole instead of 3,11-dihydroxydinaphthalo[2,1-b:1',2'-d]thiophene in the manufacturing method of Synthetic Example 1-1, except that the final product was obtained by the same method as in Synthetic Example 1-1.

[0456] [Chemical formula 1e]

[0457]

[0458] Synthesis Examples 1-6: Production of Monomer A6

[0459] Acryloyl chloride 31 mmol (2.81 g) was used instead of 61 mmol (5.52 g) in the manufacturing method of Synthetic Examples 1-2. Otherwise, the final product shown in Chemical Formula 1f was obtained by the same method as in Synthetic Examples 1-2.

[0460] [Chemical Formula 1f]

[0461]

[0462] Synthesis Examples 1-7: Manufacturing of Monomer A7

[0463] A three-necked flask was equipped with a thermometer and a dropping funnel. 50 mmol (15.82 g) of 3,11-dihydroxydinaphthalo[2,1-b:1',2'-d]thiophene, 101 mmol (12.94 g) of glycidyl acrylate, 1 g of triethylamine, and 100 ml of 1,4-dioxane were added to the flask. The reaction was carried out at 78°C for 8 hours. After purification, filtration, and drying, the reaction product was obtained. Subsequently, 61 mmol (16.73 g) of 1-phenyl-2,3-naphthalenedicarboxylic anhydride and 100 ml of 1,4-dioxane were added to 30 mmol (17.18 g) of the reaction product, and the reaction was carried out at 65 °C for 6 hours. Then, 41 mmol (5.25 g) of glycidyl acrylate, 1 g of triethylamine, and 100 ml of 1,4-dioxane were added to 20 mmol (22.42 g) of the resulting reaction product, and the reaction was carried out at 78 °C for 8 hours. After purification, filtration, and drying, the final product with the structure shown in the following chemical formula (1 g) was obtained.

[0464] [Chemical formula 1g]

[0465]

[0466] Synthesis Examples 1-8: Manufacturing of Monomer A8

[0467] The final product with the structure shown in the chemical formula 1h was obtained by using 21 mmol (2.69 g) of glycidyl acrylate instead of 41 mmol (5.25 g) of glycidyl acrylate in the manufacturing method of Synthetic Examples 1-7, except that the same method was used as in Synthetic Examples 1-7.

[0468] [Chemical formula 1h]

[0469]

[0470] Synthesis Examples 1-9: Manufacturing of Monomer A9

[0471] A three-necked flask equipped with a thermometer and a dropping funnel was used to add 60 mmol (21.45 g) of 4,4'-(9H-fluorene-9,9-diyl)diphenylthiol, 240 mmol (22.20 g) of epichlorohydrin, 0.3 g of potassium hydroxide, and 100 g of methyl ethyl ketone. The reaction was carried out at 80 °C. After the reaction was completed, unreacted materials were removed using a rotary evaporator, and a 10 wt% potassium hydroxide aqueous solution was slowly added dropwise to carry out the terminal epoxylation reaction. Then, 121 mmol (8.72 g) of acrylic acid and 1.55 mmol (0.16 g) of triethylamine were added to 60 mmol (28.18 g) of the product obtained through the epoxylation reaction, and the reaction was carried out at 90 °C. Finally, 30 mmol (18.41 g) of the resulting product, 61 mmol (6.17 g) of triethylamine, and 50 ml of THF were added and stirred to dissolve. A solution containing 61 mmol (5.52 g) of acryloyl chloride dissolved in 50 ml of THF was added dropwise over 30 minutes using a dropping funnel under ice bath conditions. After the addition was complete, the reaction temperature was raised to 50°C, stirred for 3 hours, and then cooled to stop the reaction. The reaction solution was cooled to room temperature, and unreacted acryloyl chloride was quenched with ice water. Then, the solution was separated with a saturated sodium bicarbonate aqueous solution to remove acrylic acid, a decomposition product of acryloyl chloride. Finally, THF was removed using an evaporator, thereby obtaining the final product shown in the structure of formula 1i below.

[0472] [Chemical Formula 1i]

[0473]

[0474] Synthesis Examples 1-10: Manufacturing of Monomer A10

[0475] 61 mmol (6.17 g) of triethylamine and 50 ml of THF were added to 30 mmol (41.32 g) of the final product obtained by the method of Synthesis Examples 1-7, and the mixture was stirred to dissolve. A solution of 61 mmol (8.57 g) of benzoyl chloride dissolved in 50 ml of THF was added dropwise to this solution over 30 minutes using a dropping funnel under ice bath conditions. After the addition was complete, the reaction temperature was raised to 50°C, stirred for 3 hours, and then cooled to stop the reaction. The reaction solution was cooled to room temperature, and unreacted benzoyl chloride was quenched with ice water. Then, the mixture was separated using a saturated sodium bicarbonate aqueous solution to remove benzoic acid, which is a decomposition product of benzoyl chloride. Next, THF was removed using an evaporator, thereby obtaining the final product represented by the following chemical formula 1j.

[0476] [Chemical Formula 1j]

[0477]

[0478] Examples and Comparative Examples: Preparation of Photosensitive Resin Compositions

[0479] The photosensitive resin compositions of the examples and comparative examples were manufactured according to the compositions and weights described in Tables 1 and 2 below. (wt%)

[0480] [Table 1]

[0481]

[0482] [Table 2]

[0483]

[0484] - Monomers A1 ~ A10: Monomers prepared according to Synthesis Examples 1 to 10

[0485] - Monomer A11: 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (TR-FR-302, TRONLY)

[0486] - Monomer A12: o-Phenylenoxyethyl acrylate (A001, Green Chemical Company)

[0487] - Monomer A13: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (molar ratio, 0.6:0.4) (A-TMM-3LM-N, Shin-Nakamura Chemical Co., Ltd.)

[0488] - Alkali-soluble resin B1: A caloric adhesive resin represented by chemical formula 4a, with a molecular weight of 5400.

[0489] [Chemical Formula 4a]

[0490]

[0491] - Photopolymerization initiator: C1 (Irgacure-907, manufactured by BASF)

[0492] - Solvent: D1 (Propylene glycol monomethyl ether acetate, PGMEA)

[0493] - Thiol compounds: T1 (polythiol compounds represented by chemical formula 5-1)

[0494] [Chemical Formula 5-1]

[0495]

[0496] Experimental Example

[0497] (1) Refractive index measurement

[0498] For coatings formed on 4-inch silicon wafers using the compositions of Examples 1 to 12 and Comparative Examples 1 to 4, linear polarization was measured in the wavelength range of 380 nm to 1000 nm using an M-2000 device from JA Woollam at 25°C and 50%RH with an incident angle of 70°.

[0499] Based on the ellipsometry data (Ψ,Δ) obtained above, the coating of the optical laminate was optimized and fitted using the Cauchy model of Equation 1 below with the CompleteEASE software until the MSE was below 3. The refractive index at a wavelength of 550 nm was calculated and recorded in Table 3 below.

[0500] <Formula 1>

[0501]

[0502] In Equation 1 above, n(λ) is the refractive index at wavelength λ, λ is in the range of 300 nm to 1800 nm, and A, B and C are Cauchy parameters.

[0503] (2) Evaluation of heat and moisture resistance (grading)

[0504] The films formed using Examples 1 to 12 and Comparative Examples 1 to 4 were placed in a high temperature (85°C) and high humidity (85%RH) environment to observe the changes in the appearance of the patterns, and the results were recorded in Table 3 according to the following evaluation criteria.

[0505] <Evaluation Criteria>

[0506] ◎: No change in appearance

[0507] ○: Excellent appearance condition

[0508] △: Wrinkles appear on the surface.

[0509] X: Peeling and / or solvent color deterioration

[0510] (3) Cone angle evaluation

[0511] Regarding the films formed using Examples 1 to 12 and Comparative Examples 1 to 4 described above, such as Figure 1 The cone angle of the pattern was measured using a scanning electron microscope (SEM), and the results were recorded in Table 3 according to the evaluation criteria below.

[0512] <Evaluation Criteria>

[0513] ○: Cone angle of 40 degrees or more

[0514] X: Cone angle less than 40 degrees

[0515] [Table 3]

[0516]

[0517] Based on the experimental data in Table 3 above, Examples 1 to 12, which used the photosensitive resin composition of the present invention to form patterns, showed excellent results in terms of cone angle, heat and moisture resistance evaluation, and the refractive index, measured by ellipsometry, was 1.65 or higher, which was very excellent. In particular, Example 9 showed the best results in terms of refractive index because the photosensitive resin composition simultaneously contained a monomer with a structure containing carbazole and two sulfur atoms (S).

[0518] In contrast, Comparative Example 1, which contains a difunctional monomer that does not satisfy Formula 1 of this application, and Comparative Example 2, which contains a monofunctional monomer that does not satisfy Formula 1 of this application, showed very poor heat and moisture resistance, resulting in insufficient reliability and a poor cone angle. Furthermore, Comparative Example 3, which contains a polyfunctional monomer that does not satisfy Formula 1 of this application, demonstrated excellent reliability due to the use of a conventional tetrafunctional monomer, but its refractive index of 1.51 was significantly lower than that of the examples. Comparative Example 4 was manufactured by mixing monomers A11 and A13 to simultaneously improve refractive index, adhesion, and reliability; however, since it did not contain a monomer that satisfies Formula 1 of this application, its reliability and cone angle were poor, and its refractive index was below 1.6.

[0519] The above results confirm that the photosensitive resin composition of this application can obtain a coating with excellent refractive index, adhesion, heat and moisture resistance, and the coating is a high-quality, high-refractive-index cured film suitable for OLED interlayer materials used in display panels.

Claims

1. A photosensitive resin composition comprising (A) a monomer, (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) a solvent, wherein, The monomer (A) comprises chemical formula 1, Chemical Formula 1 In chemical formula 1, X is any one of the following chemical formulas 2-1 to 2-16. R1 can be either hydrogen or methyl. R2 can be -O- or -S- independently. R3 is an -OH group, or a substituent containing one or more (meth)acrylate groups, one or more benzene rings, or one or more carboxyl groups. R4 is a substituent containing one or more (meth)acrylates; Chemical formula 2-1 Chemical formula 2-2 Chemical formula 2-3 Chemical formula 2-4 Chemical formula 2-5 Chemical formula 2-6 Chemical formula 2-7 Chemical formula 2-8 Chemical formula 2-9 Chemical formula 2-10 Chemical formula 2-11 Chemical formula 2-12 Chemical formula 2-13 Chemical formula 2-14 Chemical formula 2-15 Chemical formula 2-16 In chemical formulas 2-13 to 2-16, R5 is -H, -CH3, -CH2CH3, -CH2CH2CH3, , , , , , , or , In chemical formulas 2-1 to 2-16, "*" represents a bonding bond.

2. The photosensitive resin composition according to claim 1, wherein, R3 is selected from the group consisting of chemical formulas 3-1 to 3-16: Chemical formula 3-1 Chemical formula 3-2 Chemical formula 3-3 Chemical formula 3-4 Chemical formula 3-5 Chemical formula 3-6 Chemical formula 3-7 Chemical formula 3-8 Chemical formula 3-9 Chemical formula 3-10 Chemical formula 3-11 Chemical formula 3-12 Chemical formula 3-13 Chemical formula 3-14 Chemical formula 3-15 Chemical formula 3-16 In chemical formulas 3-1 to 3-16, R1 can be either hydrogen or methyl. R6 is an -OH group, or a substituent containing one or more benzene rings or sulfur atoms. R7 is -H, -CH3, or , n is an integer from 0 to 3. "*" represents a binding bond.

3. The photosensitive resin composition according to claim 1, wherein, R4 is selected from the group consisting of chemical formulas 4-1 to 4-11: Chemical formula 4-1 Chemical formula 4-2 Chemical formula 4-3 Chemical formula 4-4 Chemical formula 4-5 Chemical formula 4-6 Chemical formula 4-7 Chemical formula 4-8 Chemical formula 4-9 Chemical formula 4-10 Chemical formula 4-11 In chemical formulas 4-1 to 4-11, R1 can be either hydrogen or methyl. R6 is an -OH group, or a substituent containing one or more benzene rings or sulfur atoms. R7 is -H, -CH3, or , n is an integer from 0 to 3. "*" represents a binding bond.

4. The photosensitive resin composition according to claim 1, wherein, The photosensitive resin composition also includes (E) additives. The additive (E) is selected from one or more surfactants, adhesion promoters and thiols.

5. The photosensitive resin composition according to claim 4, wherein, The thiol compound is a sulfur-containing monomer and is a polyfunctional thiol compound with 2 to 5 thiol groups (-SH) at the end.

6. The photosensitive resin composition according to claim 5, wherein, The polyfunctional thiol compound comprises one or more of the following chemical formulas 5-1 to 5-5. Chemical formula 5-1 Chemical formula 5-2 Chemical formula 5-3 Chemical formula 5-4 Chemical formula 5-5 。 7. The photosensitive resin composition according to claim 1, wherein, The acid value of the alkali-soluble resin (B) is from 20 mg KOH / g to 200 mg KOH / g.

8. The photosensitive resin composition according to claim 1, wherein, The alkali-soluble resin (B) comprises a calorie resin.

9. The photosensitive resin composition according to claim 8, wherein, The calool resin comprises at least one repeating unit of chemical formulas 6-1 to 6-6: Chemical formula 6-1 Chemical formula 6-2 Chemical formula 6-3 Chemical formula 6-4 Chemical formula 6-5 Chemical formula 6-6 Among the above chemical formulas 6-1 to 6-6, X' and X'' are each independently a single bond, -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, , , , , , , , , , , , or , Y represents an acid anhydride residue. Z represents an acid dianhydride residue. R' can be a hydrogen atom, ethyl group, phenyl group, -C2H4Cl, -C2H4OH, or -CH2CH=CH2. R1a, R1', R2a, R2', R3a, R3', R4a, R4', R5a, R5', R6a, and R6' are each independently a hydrogen atom or a methyl group. R7a, R7', R8a, and R8' are each independently a C1-C6 alkylene group, wherein the alkylene group is inserted into or not inserted into at least one of an ester bond, a C6-C14 cycloalkylene group, and an aryl group. R9a, R9', R10a, R10', R11a, R11', R12a, and R12' are each independently a hydrogen atom, a halogen atom, or a C1-C6 alkyl group. m and n1 are each an independent integer from 1 to 30. t and u are each an independent integer from 0 to 1. P is independent of each , , , or , R13 and R14 are each independently a hydrogen atom, hydroxyl group, mercapto group, amino group, nitro group, or halogen atom. Ar1 is an aryl group, each of which is independent. Y' represents an acid anhydride residue. Z' is an acid dianhydride residue. A can be -O-, -S-, -NR'-, -Si(R')2-, or -Se-. a and b are each independent integers from 1 to 6. p and q are each independent integers from 1 to 30.

10. A pattern comprising a cured product of the photosensitive resin composition of claim 1.

11. The pattern according to claim 10, wherein, The refractive index of the pattern is greater than 1.

62.

12. The pattern according to claim 10, wherein, The pattern is selected from any one of the following groups: free array planarization film pattern, protective film pattern, microlens pattern, insulating film pattern, photoresist pattern, black matrix pattern, columnar spacer pattern, black columnar spacer, colored photoresist pattern, pattern containing scatterers, and pattern containing quantum dots.

13. A display device comprising the pattern of any one of claims 10 to 12.

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