Photosensitive resin composition, pattern formed therefrom and display device

Abstract

The present invention provides a photosensitive resin composition, a pattern formed therefrom, 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, a coating film having improved reliability due to a high refractive index, adhesion, and excellent heat and moisture resistance can be obtained by including at least one of chemical formulae 1 and 2, which is a novel high refractive monomer containing at least three substituents having an ethylenically unsaturated double bond, of the monomer (A). In the chemical formulas 1 and 2, R1 is hydrogen or methyl independently, R2 is-OH group or a substituent group containing more than one ethylene unsaturated double bond or carboxyl, R3 is-OH group or a substituent group containing more than one (methyl) acrylate group, more than one benzene ring or more than one carboxyl, R4 is a substituent group containing more than one (methyl) acrylate group, and n is an integer of 1 to 2. R5 is-O-or-S-, and n is an integer of 0 or 1. Chemical formula 1 and chemical formula 2

Description

TECHNICAL FIELD

[0001] The present application relates to a photosensitive resin composition exhibiting high refractive index and high reliability by containing a novel monomer, and a pattern and a display device formed therefrom. BACKGROUND

[0002] In recent years, with the development of the information society, the demand for display fields is also increasingly diversified. For example, liquid crystal display devices, plasma display panel devices, electro luminescent display devices, organic light-emitting diode display devices, etc. having thinness, lightness, low power consumption, etc. are being studied. Organic light-emitting diodes (hereinafter referred to as OLEDs) are expected to be the next generation display and lighting devices due to their fast response speed and wide viewing angle, low voltage driving, etc. Generally, in OLEDs, an organic layer composed of a light-emitting material or a charge transporting material, etc. is located between a top electrode and a bottom electrode. OLEDs have a structure in which layers of materials having different refractive indices are stacked, and reflection occurs at the interfaces of these materials, so the light extraction efficiency toward the outside is low. Specifically, the refractive index of the organic light-emitting layer constituting the OLED is about 1.7, the refractive index of ITO used as a transparent electrode is 2.0, and the refractive index of a glass substrate is 1.5. In this case, the ratio of guided waves trapped in the transparent electrode or the organic layer and unable to be extracted is about 45%, and the ratio of substrate guided waves trapped in the substrate and unable to be extracted is about 35%. Therefore, of the light emitted from the OLED, only about 20% of the light is extracted to the outside. Various studies have been conducted to solve this problem, and a representative one is to improve the light extraction efficiency by forming a low-refractive-index and high-refractive-index coating layer. In particular, in order to realize a high-refractive-index coating layer, it is well known that introducing a halogen atom (except fluorine) into the molecular structure is an effective method for increasing the refractive index of an organic compound as a monomer. For example, in Japanese Laid-Open Patent Publication No. 1993-170702, a high-refractive-index aggregate in which a halogen atom is introduced into a biphenyl ring is used in order to utilize the high intrinsic refractive index of the halogen atom. However, in the case of containing such a monomer, there is a problem that the heat resistance and light resistance are significantly deteriorated due to halogenation, and since a difunctional (methyl) aryl group is contained, there is a problem that it is difficult to ensure the heat and humidity resistance of the coating layer when applied to a high-refractive-index photosensitive resin composition. Therefore, in reality, there is a need to develop a photosensitive resin suitable for displays that exhibits a high refractive index and high reliability and has excellent adhesion to a substrate by containing a new type of monomer that can solve the above problems.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Patent Publication No. 1993-170702 Summary of the Invention

[0006] The problem to be solved

[0007] The present invention aims to solve the problems of the prior art, and its purpose is to provide a photosensitive resin composition with excellent refractive index, high adhesion and reliability, comprising a novel monomer represented by chemical formula 1 or 2 and containing 3 or more ethylene unsaturated double bonds, and patterns and display devices formed therefrom.

[0008] However, the problems to be solved by this application are not limited to those mentioned above, and those skilled in the art should be able to clearly understand other problems not mentioned based on the following description.

[0009] Methods for solving problems

[0010] A photosensitive resin composition, characterized in that it comprises (A) a monomer, (B) an alkali-soluble resin, (C) a photopolymerization initiator and (D) a solvent, wherein the monomer (A) comprises one or more of the following chemical formulas 1 and 2, and the following chemical formulas 1 and 2 comprise three or more substituents having vinyl unsaturated double bonds.

[0011] [Chemical Formula 1]

[0012]

[0013] [Chemical Formula 2]

[0014]

[0015] (in chemical formulas 1 and 2,

[0016] R1 can be either hydrogen or methyl.

[0017] R2 is a -OH group, a substituent containing one or more vinyl unsaturated double bonds or a carboxyl group.

[0018] R3 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.

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

[0020] R5 is either -O- or -S-.

[0021] (n is an integer that is either 0 or 1.)

[0022] In one example of the present invention, the substituent having an ethylene unsaturated double bond may be a substituent containing a (meth)acrylate group.

[0023] In one example of the present invention, the R2 mentioned above can be the following chemical formula 1-1.

[0024] [Chemical Formula 1-1]

[0025]

[0026] (in chemical formula 1-1,

[0027] R1 can be either hydrogen or methyl.

[0028] R5 is either -O- or -S-.

[0029] n is an integer that is either 0 or 1.

[0030] The asterisk (*) indicates a bond.

[0031] In one example of the present invention, R3 may be selected from the group consisting of the following chemical formulas 1-2 to 1-14-1.

[0032]

[0033] [Chemical Formulas 1-9]

[0034]

[0035] [Chemical Formulas 1-10]

[0036]

[0037] [Chemical Formula 1-11]

[0038]

[0039] [Chemical Formula 1-12]

[0040]

[0041] [Chemical Formula 1-13]

[0042]

[0043] [Chemical Formula 1-14]

[0044]

[0045] [Chemical Formula 1-14-1]

[0046]

[0047] (In chemical formulas 1-2 to 1-14-1,

[0048] R1 can be either hydrogen or methyl.

[0049] R 1k (This is a -OH group or a substituent containing one or more benzene rings; * indicates a bond.)

[0050] In one example of the present invention, the R4 mentioned above may be selected from the group consisting of the following chemical formulas 1-15 to 1-21-1.

[0051] [Chemical Formula 1-15]

[0052]

[0053] [Chemical Formula 1-16]

[0054]

[0055] [Chemical Formula 1-17]

[0056]

[0057] [Chemical Formula 1-18]

[0058]

[0059] [Chemical Formula 1-19]

[0060]

[0061] [Chemical Formula 1-20]

[0062]

[0063] [Chemical Formula 1-21]

[0064]

[0065] [Chemical Formula 1-21-1]

[0066]

[0067] (In chemical formulas 1-15 to 1-21-1,

[0068] R1 can be either hydrogen or methyl.

[0069] R 1k It is a -OH group or a substituent containing one or more benzene rings.

[0070] The asterisk (*) indicates a bond.

[0071] In one example of the present invention, the monomer (A) may comprise chemical formula 1 and chemical formula 2.

[0072] In one embodiment of the present invention, an additive (E) is also included, wherein the additive (E) may be one or more selected from surfactants, adhesion promoters and thiol compounds.

[0073] In another example of the present invention, the above-mentioned thiol compounds, as sulfur-containing monomers, can be polyfunctional thiol compounds having 2 to 5 thiol groups (-SH) at the end.

[0074] In another example of the present invention, the above-mentioned polyfunctional thiol compound may contain one or more of the following chemical formulas 3-1 to 3-5.

[0075]

[0076] [Chemical Formula 3-5]

[0077]

[0078] In one example of the present invention, the acid value of the alkali-soluble resin (B) described above can be from 20 mg KOH / g to 200 mg KOH / g.

[0079] In one example of the present invention, the above-mentioned (B) alkali-soluble resin may include Cardo-based resin.

[0080] In another example of the present invention, the Cardo-based resin may contain at least one repeating unit of chemical formula 4 to 9.

[0081] [Chemical Formula 4]

[0082]

[0083] [Chemical Formula 5]

[0084]

[0085] [Chemical Formula 6]

[0086]

[0087] [Chemical Formula 7]

[0088]

[0089] [Chemical Formula 8]

[0090]

[0091] [Chemical Formula 9]

[0092]

[0093] (Among the above chemical formulas 4 to 9,

[0094] X and X' are each independently a single bond, -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-,

[0095] Y represents an acid anhydride residue.

[0096] Z represents an acid dianhydride residue.

[0097] R' can be a hydrogen atom, ethyl group, phenyl group, -C2H4Cl, -C2H4OH, or -CH2CH=CH2.

[0098] R1a, R1', R2a, R2', R3a, R3', R4a, R4', R5a, R5', R6a, and R6' are each independently a hydrogen atom or a methyl group.

[0099] R7a, R7', R8a, and R8' are each independently a C1-C6 alkylene group, wherein the alkylene group is inserted into at least one of an ester bond, a C6-C14 cycloalkylene group, and an aryl group, or is not inserted.

[0100] R9a, R9', R10a, R10', R11a, R11', R12a, and R12' are each independently a hydrogen atom, a halogen atom, or a C1-C6 alkyl group.

[0101] m and n1 are each independent integers from 1 to 30.

[0102] t and u are each an independent integer from 0 to 1.

[0103] P is independent of each

[0104] R13 and R14 are each independently a hydrogen atom, hydroxyl group, thiol group, amino group, nitro group, or halogen atom.

[0105] Ar1 is an aryl group, each of which is independent.

[0106] Y' represents an acid anhydride residue.

[0107] Z' is an acid dianhydride residue.

[0108] A can be -O-, -S-, -NR'-, -Si(R')2-, or -Se-.

[0109] a and b are each independent integers from 1 to 6.

[0110] p and q are each independent integers from 1 to 30.

[0111] The present invention provides a pattern of a cured product comprising a photosensitive resin composition of an example of the present invention described above.

[0112] In one example of the present invention, the refractive index of the above pattern can be 1.60 or higher.

[0113] In one example of the present invention, the above-mentioned pattern can be any one of the following selected from the group consisting of 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.

[0114] The present invention provides a display device incorporating a pattern from an example of the present invention described above.

[0115] Invention Effects

[0116] This invention manufactures a coating with a high refractive index by comprising the above-described photosensitive resin composition, thereby providing a pattern with excellent adhesion, heat resistance, moisture resistance, and high reliability. In particular, the pattern manufactured according to this invention has a refractive index of 1.60 or higher, achieving a very high refractive index, and therefore has advantages in terms of high brightness when applied to display devices. Attached Figure Description

[0117] Figure 1 This is a diagram illustrating the adhesion force evaluation criteria of the present invention. Detailed Implementation

[0118] This invention relates to photosensitive resin compositions, patterns formed therefrom, and display devices. The photosensitive resin compositions comprise (A) a monomer, (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) a solvent. The photosensitive resin compositions utilize a novel high-refractive-index monomer characterized by containing one or more of the following chemical formulas 1 and 2, each containing three or more substituents having vinyl unsaturated double bonds. Here, chemical formula 1 or 2 containing three or more substituents having vinyl unsaturated double bonds refers to the presence of three or more vinyl unsaturated double bonds due to the presence of substituents having vinyl unsaturated double bonds in chemical formula 1 or 2. The monomer (A) can exist as a mixture comprising chemical formulas 1 and / or 2.

[0119] According to the present invention, by manufacturing a coating comprising the above-described photosensitive resin composition, a coating with a high refractive index can be achieved, providing a pattern with excellent adhesion, excellent heat and moisture resistance, and high reliability. In particular, the above-described pattern is characterized by a refractive index of 1.60 or higher, thus enabling a display device with excellent brightness. In the present invention, the refractive index can be measured at a wavelength of 550 nm by optimizing the polarization ellipticity measured by ellipsometry using a Cauchy model to achieve an MSE of 3 or less.

[0120] [Chemical Formula 1]

[0121]

[0122] [Chemical Formula 2]

[0123]

[0124] (in chemical formulas 1 and 2,

[0125] R1 can be either hydrogen or methyl.

[0126] R2 is a -OH group, a substituent containing one or more vinyl unsaturated double bonds or a carboxyl group.

[0127] R3 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.

[0128] R4 is a substituent containing one or more (meth)acrylate groups.

[0129] R5 is either -O- or -S-.

[0130] (n is an integer that is either 0 or 1.)

[0131] 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, the change in film thickness or appearance is minimized, while the heat resistance and moisture resistance are excellent.

[0132] 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.

[0133] Hereinafter, embodiments of the present invention will be described in more detail. However, the terminology used in this specification is intended to describe the embodiments and is not intended to limit the invention. In this specification, unless specifically stated in the context, the singular form also includes the plural form.

[0134] 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.

[0135] <Photosensitive Resin Composition>

[0136] The photosensitive resin composition of the present invention is characterized in that (A) the monomer contains one or more of chemical formulas 1 and 2, which include three or more substituents having vinyl unsaturated double bonds. More specifically, the photosensitive resin composition of the present invention may contain the above-mentioned (A) monomer, (B) alkali-soluble resin, (C) photopolymerization initiator, and (D) solvent. That is, the above-mentioned (A) monomer contains monomers represented by the structures of chemical formulas 1 and / or 2, and in particular, the above-mentioned chemical formulas 1 and 2 are characterized by having three or more vinyl unsaturated double bonds within the molecule. By including monomers having the structure of chemical formula 1 or 2, the refractive index can be significantly increased, and since the above-mentioned chemical formulas 1 or 2 contain three or more vinyl unsaturated double bonds as functional groups, it is beneficial to improve reliability and adhesion.

[0137] Additionally, it may contain a polyfunctional thiol compound with 2 to 5 thiol groups (-SH) at the end as an (E) additive, and may also contain other additives.

[0138] (A) monomer

[0139] The monomer (A) described above is a substance that polymerizes and cures upon exposure to light such as ultraviolet light, which can increase the crosslinking density in the manufacturing process and enhance the optical properties of the photocured pattern. The monomer (A) described above is a compound that can be polymerized by the photopolymerization initiator (C) described below, which can impart high refractive index and adhesion to the cured film of the photosensitive resin composition of the present invention. Due to improved heat and moisture resistance, the reliability of displays containing the cured film is also excellent. The monomer (A) described above is characterized in that it may contain one or more of the following chemical formulas 1 and 2, wherein chemical formulas 1 and 2 contain three or more substituents having vinyl unsaturated double bonds; more preferably, chemical formulas 1 and 2 may be trifunctional or tetrafunctional compounds.

[0140] [Chemical Formula 1]

[0141]

[0142] [Chemical Formula 2]

[0143]

[0144] (in chemical formulas 1 and 2,

[0145] R1 can be either hydrogen or methyl.

[0146] R2 is a -OH group, a substituent containing one or more vinyl unsaturated double bonds or a carboxyl group.

[0147] R3 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.

[0148] R4 is a substituent containing one or more (meth)acrylate groups.

[0149] R5 is either -O- or -S-.

[0150] (n is an integer that is either 0 or 1.)

[0151] The substituents having vinyl unsaturated double bonds described above may include one or more substituents selected from the group consisting of substituents derived from acrylic acid or methacrylic acid and substituents derived therefrom. More preferably, in this invention, the substituents having vinyl unsaturated double bonds described above preferably include (meth)acrylate groups.

[0152] In this invention, if monomer (A) contains the aforementioned substituents having vinyl unsaturated double bonds, the adhesion to the substrate during the developing process is improved, preventing pattern peeling, and the straightness of the formed pattern is enhanced, resulting in a stable pattern. Furthermore, due to improved moisture and heat resistance, it is suitable for display devices incorporating the aforementioned patterns.

[0153] The monomer (A) above preferably contains a monomer with three or more substituents having ethylene-like unsaturated double bonds (a multifunctional monomer) to improve adhesion and moisture and heat resistance. However, generally, if the number of functional groups increases, the refractive index tends to decrease, but the monomer of this application contains a structure of chemical formula 1 or 2 containing a fluorene ring, thereby achieving a high refractive index.

[0154] However, since it is also known that the refractive index generally increases with the increase of the amount of aromatic ring per unit volume, it is more preferable to have a structure containing chemical formula 1 or 2, as in the monomer of this application, but containing 3 to 4 substituents having ethylene unsaturated double bonds. In this case, the refractive index, adhesion, and moisture and heat resistance can all be well balanced and exhibit excellent performance. Therefore, in the monomer (A) of this application, as a novel structure synthesized to improve adhesion, moisture and heat resistance, and refractive index, it can contain one or more of chemical formulas 1 and 2 containing 3 or more substituents having ethylene unsaturated double bonds.

[0155] In the above chemical formulas 1 and 2, R5 is -O- or -S-. When R5 is O, it is excellent in terms of stability and lightfastness. When R5 is S, it can increase the dielectric constant of the monomer, and therefore is excellent in terms of high refractive index.

[0156] R2 in the above chemical formula 1 contains a -OH group or a substituent containing one or more ethylene unsaturated double bonds. Specifically, R2 can be the following chemical formula 1-1.

[0157] (In the formula, "*" represents a bonding bond, R1 and R5 are defined as described above, and n is an integer of 0 or 1.)

[0158] [Chemical Formula 1-1]

[0159]

[0160] R3 in the above chemical formula 2 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 1-2 to 1-14-1.

[0161] As an example, the substituents containing benzene rings mentioned above may include aromatic ring compounds such as naphthyl, or may include benzene rings adjacent to heteroatoms such as thiophene.

[0162] (In the formula, "*" represents a bonding bond, R1 and R...) 1k The definition is as described above.

[0163]

[0164]

[0165] [Chemical Formulas 1-9]

[0166]

[0167] [Chemical Formulas 1-10]

[0168]

[0169] [Chemical Formula 1-11]

[0170]

[0171] [Chemical Formula 1-12]

[0172]

[0173] [Chemical Formula 1-13]

[0174]

[0175] [Chemical Formula 1-14]

[0176]

[0177] [Chemical Formula 1-14-1]

[0178]

[0179] R4 in the above chemical formula 2 is a substituent containing one or more (meth)acrylate groups. Specifically, the substituent containing (meth)acrylate groups can be selected from the group consisting of chemical formulas 1-15 to 1-21-1.

[0180] (In the formula, "*" represents a bonding bond, R1 and R...) 1k The definition is as described above.

[0181] [Chemical Formula 1-15]

[0182]

[0183] [Chemical Formula 1-16]

[0184]

[0185] [Chemical Formula 1-17]

[0186]

[0187] [Chemical Formula 1-18]

[0188]

[0189] [Chemical Formula 1-19]

[0190]

[0191] [Chemical Formula 1-20]

[0192]

[0193] [Chemical Formula 1-21]

[0194]

[0195] [Chemical Formula 1-21-1]

[0196]

[0197] More specifically, the chemical formula 1 of the present invention can be chemical formula 1a and / or chemical formula 1b.

[0198] [Chemical Formula 1a]

[0199]

[0200] [Chemical Formula 1b]

[0201]

[0202] More specifically, the chemical formula 2 of the present invention can be one or more of chemical formulas 2a to 2o.

[0203] [Chemical Formula 2a]

[0204]

[0205] [Chemical Formula 2b]

[0206]

[0207] [Chemical formula 2c]

[0208]

[0209] [Chemical formula 2d]

[0210]

[0211] [Chemical formula 2e]

[0212]

[0213] [Chemical formula 2f]

[0214]

[0215] [Chemical formula 2g]

[0216]

[0217] [Chemical formula 2h]

[0218]

[0219] [Chemical Formula 2i]

[0220]

[0221] [Chemical Formula 2j]

[0222]

[0223] [Chemical formula 2k]

[0224]

[0225] [Chemical formula 2l]

[0226]

[0227] [Chemical formula 2m]

[0228]

[0229] [Chemical formula 2n]

[0230]

[0231] [Chemical formula 2o]

[0232]

[0233] The photosensitive resin composition of the present invention may contain two or more (A) monomers. For example, it may contain both the monomer represented by chemical formula 1 and the monomer represented by chemical formula 2.

[0234] The content of monomer (A) is preferably 20 to 80% by weight, more preferably 40 to 60% by weight, relative to 100 parts by weight of the total solid components in the photosensitive resin composition. When monomers having three or more vinyl unsaturated double bonds are included within the above range, the adhesion is improved.

[0235] (B) alkali-soluble resin

[0236] The alkali-soluble resin (B) included in the photosensitive resin composition of the present invention may include a thermosetting resin or an alkali-soluble resin. Specifically, examples include carboxyl-containing monomers and copolymers with other monomers that can be copolymerized with the aforementioned carboxyl-containing monomers.

[0237] More preferably, the alkali-soluble resin (B) included in the photosensitive resin composition of the present invention can be a Cardo-based adhesive resin. When used with a Cardo-based adhesive resin in conjunction with the monomers of the present invention, it has the advantage of ensuring development properties, which is beneficial for pattern formation, and achieving a refractive index of 1.6 or higher. Specifically, the Cardo-based adhesive resin may contain at least one repeating unit from the following chemical formulas 4 to 9.

[0238] [Chemical Formula 4]

[0239]

[0240] [Chemical Formula 5]

[0241]

[0242] [Chemical Formula 6]

[0243]

[0244] [Chemical Formula 7]

[0245]

[0246] [Chemical Formula 8]

[0247]

[0248] [Chemical Formula 9]

[0249]

[0250] Among the above chemical formulas 4 to 9,

[0251] X and X' are each independently a single bond, -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-,

[0252] Y represents an acid anhydride residue.

[0253] Z represents an acid dianhydride residue.

[0254] R' can be a hydrogen atom, ethyl group, phenyl group, -C2H4Cl, -C2H4OH, or -CH2CH=CH2.

[0255] R1a, R1', R2a, R2', R3a, R3', R4a, R4', R5a, R5', R6a, and R6' are each independently a hydrogen atom or a methyl group.

[0256] R7a, R7', R8a, and R8' are each independently a C1-C6 alkylene group, wherein the alkylene group is inserted into at least one of an ester bond, a C6-C14 cycloalkylene group, and an aryl group, or is not inserted.

[0257] R9a, R9', R10a, R10', R11a, R11', R12a, and R12' are each independently a hydrogen atom, a halogen atom, or a C1-C6 alkyl group.

[0258] m and n1 are each independent integers from 1 to 30.

[0259] t and u are each an independent integer from 0 to 1.

[0260] P is independent of each

[0261] R13 and R14 are each independently a hydrogen atom, hydroxyl group, thiol group, amino group, nitro group, or halogen atom.

[0262] Ar1 is an aryl group, each of which is independent.

[0263] Y' represents an acid anhydride residue.

[0264] Z' is an acid dianhydride residue.

[0265] A can be -O-, -S-, -NR'-, -Si(R')2-, or -Se-.

[0266] a and b are each independent integers from 1 to 6.

[0267] p and q are each independent integers from 1 to 30.

[0268] 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.

[0269] In one embodiment of the present invention, the aforementioned acid dianhydride may be selected from the group consisting of pyromellitic dianhydride, benzophenone dianhydride, biphenyl dianhydride, and diphenyl ether dianhydride.

[0270] The alkali-soluble resin of the present invention can influence the patterning process of the photosensitive resin composition according to the acid value and molecular weight.

[0271] The weight-average molecular weight (Mw) of the aforementioned alkali-soluble resin (e.g., measured by gel permeation chromatography using polystyrene as a standard) can be between 2000 and 20000, preferably between 2000 and 10000, considering the improvement of the reactivity of the photosensitive resin composition under low-temperature conditions and the improvement of chemical resistance. When the aforementioned weight-average molecular weight (Mw) is satisfied, a CD bias (CD-Bias) of the pattern can be achieved within an appropriate range to form a pattern with excellent resolution, and the chemical resistance of the pattern can also be improved. On the other hand, when the weight-average molecular weight of the binder resin is greater than 20000, the molecular weight becomes too large, leading to reduced compatibility with other components of the photosensitive resin composition. This may result in whitening of the coating during the development step, an increase in the linewidth of the pattern, a possible decrease in CD bias characteristics, and a decrease in the alkali solubility of the unexposed areas, potentially causing residue buildup on the underlying substrate. Furthermore, when the weight-average molecular weight of the aforementioned binder resin is less than 2000, reliability issues may arise.

[0272] The acid value is a value determined by the amount of potassium hydroxide (mg) required to neutralize 1g of acrylic polymer. It is usually obtained by titration using an aqueous potassium hydroxide solution and can affect pattern formation during the process. The acid value of the aforementioned adhesive resin is preferably between 20 and 200 mg KOH / g. If the acid value is within this range, the solubility in the developer is improved, non-exposed areas dissolve easily, sensitivity is increased, and as a result, the pattern on exposed areas is retained during development, thus improving the film retention ratio, which is therefore preferred.

[0273] Furthermore, the alkali-soluble resin contained in the photosensitive resin composition of the present invention is also a soluble component in the alkaline developing solution used in the developing process, and can be used without limitation as long as it can be dissolved in the alkaline developing solution.

[0274] 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 content of the adhesive resin is within the above range, it is preferred from the perspective of confirming 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 above the above range, the resolution may be reduced.

[0275] (C) photopolymerization initiator

[0276] The initiator described above (C) functions to initiate a free radical reaction in the photosensitive resin composition, thereby causing curing and increasing sensitivity. There are no particular limitations in this invention; any compound that generates free radicals capable of polymerizing 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 the polymerizable functional groups of the monomers having vinyl unsaturated double bonds of this invention.

[0277] Representative examples of the aforementioned 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.

[0278] Examples of the aforementioned acetophenone compounds include, for example, 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.

[0279] Examples of the aforementioned benzophenone compounds include benzophenone, 2,2'-hydroxy-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.

[0280] Examples of the aforementioned biimidazole compounds include, for instance, 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.

[0281] Examples of the aforementioned triazine compounds include, for instance, 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.

[0282] Examples of the aforementioned oxime ester compounds include, for example, o-ethoxycarbonyl-α-oximino-1-phenylpropane-1-one, 1-(4-phenylthio)phenyl-1,2-octanedione-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetophenone-1-(O-acetyl oxime), and commercially available products include CGI-124 (Ciba Gelatin), CGI-224 (Ciba Gelatin), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (ADEKA), and NCI-831 (ADEKA).

[0283] Examples of the aforementioned thioxanthone compounds include, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0284] The aforementioned initiators can be used in conjunction with photopolymerization initiation aids. These photopolymerization initiation aids can be used to promote the polymerization of photocurable compounds initiated by the initiator.

[0285] Examples of photopolymerization initiators include amine compounds and alkoxyanthracene compounds. Specific examples of the aforementioned 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.

[0286] 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 individually or in combination of two or more. Furthermore, commercially available products such as EAB-F (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used as photopolymerization initiators.

[0287] Specific examples of preferred combinations of the above-mentioned initiators and photopolymerization initiation aids include: a combination of diethoxyacetophenone and 4,4'-bis(diethylamino)benzophenone; a combination of 2-methyl-2-morpholino-1-(4-methylphenylthio)propane-1-one and 4,4'-bis(diethylamino)benzophenone; a combination of 2-hydroxy-2-methyl-1-phenylpropane-1-one and 4,4'-bis(diethylamino)benzophenone; a combination of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one and 4,4'-bis(diethylamino)benzophenone; and a combination of 1-hydroxycyclohexylphenyl one and 4,4'-bis(diethylamino)benzophenone. Combinations of ketones; combinations of oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one with 4,4'-bis(diethylamino)benzophenone; combinations of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one with 4,4'-bis(diethylamino)benzophenone, etc., preferably combinations of 2-methyl-2-morpholino-1-(4-methylphenylthio)propane-1-one with 4,4'-bis(diethylamino)benzophenone, combinations of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one with 4,4'-bis(N,N'-dimethylamino)benzophenone, etc.

[0288] When using both the initiator and the photopolymerization initiation aid described above, the content of the photopolymerization initiation aid is preferably 0.01 to 5 mol relative to 1 mol of the initiator. If the content of the photopolymerization initiation aid is within the above range, the sensitivity of the photosensitive resin composition is further improved, and the productivity of the cured film formed using the composition is also improved, which is therefore preferred.

[0289] 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. If the content is within this range, the photosensitive resin composition will be highly sensitive, resulting in shorter exposure time, easier pattern formation adjustment, and is preferred from the perspective of improving cure rate and straightness. If the content is higher than 10 parts by weight, the linewidth will be excessively broadened, making it impossible to maintain high resolution.

[0290] (D) solvent

[0291] In this invention, (D) solvent can be any solvent commonly used in photosensitive resin compositions, as long as it is effective in dissolving the other components contained in the photosensitive resin composition of this invention. Ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are particularly preferred.

[0292] 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. Alkylene glycol alkyl ether acetates, propylene glycol monopropyl ether acetates, methoxybutyl acetates, methoxypentyl acetates, and other alkylene glycol alkyl ether acetates; 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.

[0293] 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.

[0294] The solvents mentioned above can be used individually or in combination.

[0295] The solvent content can be such 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 and other additional components is 100% by weight, and the meaning of "balance" does not limit the composition of this invention to not containing additional components. For example, relative to the total weight of the photosensitive resin composition of this invention, it can be 10 to 90% by weight, preferably 50 to 80% by weight. If the solvent content is within the above range, improved coatability will be provided when coating with coating equipment such as roller coaters, spin coaters, slot coaters, slot coating machines (sometimes also called die coaters), inkjet printers, etc.

[0296] (E) additive

[0297] The additive (E) of this invention may further include surfactants for improving coating flatness, adhesion promoters for improving coating adhesion, and thiol compounds for improving the refractive index and reliability of the coating. In addition, it may further include additives commonly used in the art to which this invention pertains. These additives may be used alone or in any combination and ratio of two or more.

[0298] Specifically, the aforementioned thiols, as sulfur-containing monomers, can be polyfunctional thiols with 2 to 5 thiol groups (-SH) at the end.

[0299] More specifically, the aforementioned polyfunctional thiol compounds may consist of a mixture of one or more of the following chemical formulas 3-1 to 3-5.

[0300]

[0301] [Chemical Formula 3-5]

[0302]

[0303] The photosensitive resin composition of this application containing the above-mentioned thiol compounds has excellent properties of water resistance, heat resistance, alkali resistance and chemical resistance due to its resistance to solvent decomposition.

[0304] The content of the thiol compound can be 0.1 to 10 parts by weight, preferably 1 to 8 parts by weight, and more preferably 3 to 6 parts by weight, relative to 100 parts by weight of the total solid components in the photosensitive resin composition. If the content is below the above range, an increase in refractive index may not be observed; if the content is above the above range, the unexposed portion may not dissolve in the developer, potentially resulting in residue and reduced resolution.

[0305] Specifically, the surfactants mentioned above may include, for example, silicone-based, fluorinated, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. They may be used individually or in combination of two or more. Silicone-based and / or fluorinated surfactants are preferred, but not limited thereto.

[0306] The aforementioned silicone-based surfactants include, for example, commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicones Co., Ltd., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 from GE Toshiba Silicones Co., Ltd. The aforementioned fluorinated surfactants include, for example, commercially available products such as MEGAFAC F-470, F-471, F-475, F-482, F-489, and F-554 from Dai Nippon Ink Chemical Co., Ltd. Each of the surfactants listed above can be used alone or in combination of two or more.

[0307] 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. Each of the aforementioned adhesion promoters can be used alone or in combination of two or more.

[0308] Regarding the above-mentioned additives, those skilled in the art may make appropriate additional use without impairing the effects of the present invention. For example, the above-mentioned additives may be used at 0.01 to 10% by weight, preferably 0.1 to 9% by weight, and 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 are not limited thereto.

[0309] <Pattern>

[0310] The present invention includes photocurable patterns formed on a substrate using a photosensitive resin composition.

[0311] The patterns of the present invention can be manufactured by methods known in the art, in addition to being formed from the aforementioned photosensitive resin composition. When forming a photocurable pattern, the aforementioned photosensitive resin composition can be coated onto a substrate and then exposed and developed to form the pattern. Pre-baking or post-baking processes can be performed between these steps. The heating temperature and time of the pre-baking are selected according to the solvent used; for example, it can be performed at a temperature of 80°C to 100°C for 1 to 3 minutes. The exposure is performed using an exposure machine and through a photomask, thereby exposing only the portion corresponding to the pattern to light. The irradiated light can be, for example, visible light, ultraviolet light, X-rays, and 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. However, the preferred exposure time can be varied within the range of 5 to 250 seconds.

[0312] Then, 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 heating plate, etc., and is not limited thereto.

[0313] At this point, the thickness of the cured pattern is 2 to 15 μm, more specifically, 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 patternability; if it is greater than the above range, problems may occur in terms of reduced transmittance or affected optical properties.

[0314] Patterns manufactured from the photosensitive resin composition of the present invention exhibit particularly excellent refractive index, and their physical properties such as adhesion, moisture resistance, and heat resistance are improved, resulting in excellent reliability. Specifically, the refractive index of the aforementioned pattern can be 1.60 or higher. This refractive index can be achieved by optimizing the polarization ellipticity measured by ellipsometry using the Cauchy model of Equation 1 below, so that the MSE is 3 or lower, resulting in a refractive index of 1.60 or higher measured at a wavelength of 550 nm. Therefore, when the pattern of the present invention is used in the interlayer material of a display, it has the advantage of achieving high brightness.

[0315] 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.

[0316] <Display Device>

[0317] The present invention provides a display device comprising a pattern made from the above-described photosensitive resin composition.

[0318] The aforementioned display devices may include, but are not limited to, liquid crystal displays (LCDs), organic EL displays (OLEDs and QLEDs), flexible displays, liquid crystal projectors, display devices for game consoles, display devices for portable terminals such as mobile phones, display devices for digital cameras, and display devices for navigators.

[0319] In addition to the aforementioned pattern, the display device may also include configurations commonly used in the art.

[0320] The following experimental examples, including specific embodiments and comparative examples, are provided to aid in understanding the present invention. However, it will be apparent to those skilled in the art that these are merely illustrative of the invention and do not limit the scope of the appended claims. Various changes and modifications can be made to the embodiments within the scope and technical concept of the present invention, and such changes and modifications also fall within the scope of the appended claims. Unless otherwise stated, "%" and "parts" in the examples refer to "mass %" and "parts by mass," respectively.

[0321] Furthermore, the synthetic examples are merely one example of compound manufacturing, 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.

[0322] Synthesis Example 1-1: Production of monomer A1

[0323] A thermometer and dropping funnel were set up on a 100 mL three-necked flask. 30 mmol (11.95 g) of 1,1,2,2-tetra(p-hydroxyphenyl)ethane, 121 mmol (12.24 g) of triethylamine, and 50 mL of THF were added to the flask and stirred until dissolved. Under ice bath conditions, a solution of 121 mmol (10.95 g) of acryloyl chloride dissolved in 50 mL of THF was added dropwise over 30 minutes using a dropping funnel. After the addition was complete, the reaction temperature was raised to 50 °C and stirred for 3 hours, then the temperature was lowered to stop the reaction. The reaction solution was allowed to cool to room temperature, and unreacted acryloyl chloride was quenched using ice water. Then, the reaction mixture was separated using a saturated sodium bicarbonate aqueous solution to remove the decomposition product of acryloyl chloride, acrylic acid. Finally, THF was removed using an evaporator to obtain the final product with the following structure.

[0324] [Chemical Formula 1a]

[0325]

[0326] Synthesis Example 1-2: Production of monomer A2

[0327] A thermometer and dropping funnel were set up on a three-necked flask. 30 mmol (18.20 g) of (((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl)diacrylate, 61 mmol (6.17 g) of triethylamine, and 50 ml of THF were added to the flask and stirred until dissolved. 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 using a dropping funnel. After the addition was complete, the reaction temperature was raised to 50°C and stirred for 3 hours, then the temperature was lowered to stop the reaction. The reaction solution was allowed to cool to room temperature, and unreacted acryloyl chloride was quenched using ice water. Then, the reaction mixture was separated using a saturated sodium bicarbonate aqueous solution to remove the decomposition product of acryloyl chloride, acrylic acid. Finally, THF was removed using an evaporator to obtain the final product with the following structure.

[0328] [Chemical Formula 2a]

[0329]

[0330] Synthesis Example 1-3: Production of monomer A3

[0331] A thermometer and a dropping funnel were set up on a three-necked flask. 30 mmol (18.20 g) of (((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl)diacrylate, 61 mmol (9.04 g) of phthalic anhydride, and 100 ml of 1,4-dioxane were added to the flask. The reaction was carried out at 65 °C for 6 hours. 20 mmol (18.06 g) of the resulting product was then taken and 41 mmol (5.25 g) of glycidyl acrylate, 1 g of triethylamine, and 100 ml of 1,4-dioxane were added. The reaction was carried out at 78 °C for 8 hours. The product was then purified, filtered, and dried to obtain the final product with the following structure.

[0332] [Chemical Formula 2b]

[0333]

[0334] Synthesis Example 1-4: Production of monomer A4

[0335] In the manufacturing methods of Synthetic Examples 1-3, phenyl maleic anhydride was used instead of phthalate, and otherwise the final product with the following structure was obtained by the same method.

[0336] [Chemical formula 2c]

[0337]

[0338] Synthesis Example 1-5: Production of monomer A5

[0339] In the manufacturing methods of Synthetic Examples 1-3, 2,3-diphenylsuccinic anhydride was used instead of phthalic anhydride, and otherwise the final product with the following structure was obtained by the same method.

[0340] [Chemical formula 2d]

[0341]

[0342] Synthesis Example 1-6: Production of monomer A6

[0343] In the manufacturing methods of Synthetic Examples 1-3, 1-phenyl-2,3-naphthalenedicarboxylic anhydride was used instead of phthalic anhydride, and otherwise the final products with the following structures were obtained by the same method.

[0344] [Chemical formula 2e]

[0345]

[0346] Synthesis Example 1-7: Production of monomer A7

[0347] In the manufacturing methods of Synthetic Examples 1-3, tetraphenylphthalic anhydride was used instead of phthalic anhydride, and otherwise, the final product with the following structure was obtained by the same method.

[0348] [Chemical formula 2f]

[0349]

[0350] Synthesis Example 1-8: Production of monomer A8

[0351] In the manufacturing methods of Synthetic Examples 1-3, 4-phenylthio-1,8-naphthalenedicarboxylic anhydride was used instead of phthalic anhydride, and otherwise the final product with the following structure was obtained by the same method.

[0352] [Chemical formula 2g]

[0353]

[0354] Synthesis Example 1-9: Production of monomer A9

[0355] In the manufacturing method of Synthetic Example 1-1, 91 mmol (8.24 g) of acryloyl chloride was used instead of 121 mmol (10.95 g) of acryloyl chloride, and the final product with the following structure was obtained by the same method.

[0356] [Chemical Formula 1b]

[0357]

[0358] Synthesis Example 1-10: Production of monomer A10

[0359] In the manufacturing methods of Synthetic Examples 1-2, 31 mmol (2.81 g) of acryloyl chloride was used instead of 61 mmol (5.52 g) of acryloyl chloride, and otherwise the final product with the following structure was obtained by the same method.

[0360] [Chemical formula 2h]

[0361]

[0362] Synthesis Example 1-11: Production of monomer A11

[0363] A thermometer and dropping funnel were set up on a three-necked flask. 60 mmol (22.95 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 were added to the flask. The reaction was carried out at 80°C. After the reaction was completed, unreacted material was removed using a rotary evaporator. A 10 wt% potassium hydroxide aqueous solution was slowly added dropwise to carry out a terminal epoxidation reaction. 60 mmol (29.68 g) of the product obtained was taken and 121 mmol (8.72 g) of acrylic acid and 1.55 mmol (0.16 g) of triethylamine were added. The reaction was carried out at 90°C. 30 mmol (19.16 g) of the product obtained was taken and 61 mmol (6.17 g) of triethylamine and 50 ml of THF were added. The mixture was stirred and dissolved. 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 using a dropping funnel. After the addition was complete, the reaction temperature was raised to 50°C and stirred for 3 hours, then the temperature was lowered to stop the reaction. The reaction solution was allowed to cool to room temperature, and unreacted acryloyl chloride was quenched using ice water. Then, the reaction mixture was separated using a saturated sodium bicarbonate aqueous solution to remove the decomposition product of acryloyl chloride, acrylic acid. Finally, THF was removed using an evaporator to obtain the final product with the following structure.

[0364] [Chemical Formula 2i]

[0365]

[0366] Synthesis Example 1-12: Production of monomer A12

[0367] A thermometer and dropping funnel were set up on a three-necked flask. 60 mmol (36.4 g) of (((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl)diacrylate, 61 mmol (6.17 g) of triethylamine, and 100 ml of THF were added to the flask and stirred until dissolved. 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 using a dropping funnel. After the addition was complete, the reaction temperature was raised to 50°C and stirred for 3 hours, then the temperature was lowered to stop the reaction. The reaction solution was allowed to cool to room temperature, and unreacted acryloyl chloride was quenched using ice water. Then, the reaction mixture was separated using a saturated sodium bicarbonate aqueous solution to remove the decomposition product of acryloyl chloride, acrylic acid. Next, THF was removed using an evaporator, and 30 mmol (19.82 g) of the obtained product was added to a three-necked flask. Then, 31 mmol (4.59 g) of phthalic anhydride and 100 ml of 1,4-dioxane were added. The reaction was carried out at 65 °C for 6 hours. After purification, filtration and drying, the final product with the following structure was obtained.

[0368] [Chemical Formula 2j]

[0369]

[0370] Synthesis Example 1-13: Production of monomer A13

[0371] In the manufacturing methods of Synthetic Examples 1-12, 1-phenyl-2,3-naphthalenedicarboxylic anhydride was used instead of phthalic anhydride, and otherwise the final product with the following structure was obtained by the same method.

[0372] [Chemical formula 2k]

[0373]

[0374] Synthesis Example 1-14: Production of monomer A14

[0375] In the manufacturing methods of Synthetic Examples 1-3, 21 mmol (2.69 g) of glycidyl acrylate and 0.5 g of triethylamine were used instead of 41 mmol (5.25 g) of glycidyl acrylate and 1 g of triethylamine. Otherwise, the final product with the following structure was obtained by the same method.

[0376] [Chemical formula 2l]

[0377]

[0378] Synthesis Example 1-15: Production of monomer A15

[0379] A thermometer and dropping funnel were set up on a three-necked flask. 60 mmol (22.95 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 were added to the flask. The reaction was carried out at 80°C. After the reaction was complete, unreacted materials were removed using a rotary evaporator. A 10 wt% potassium hydroxide aqueous solution was slowly added dropwise to carry out a terminal epoxidation reaction. 60 mmol (29.68 g) of the product obtained was taken, and 121 mmol (8.72 g) of acrylic acid and triethylamine were added. 1.55 mmol (0.16 g) of amine was reacted at 90 °C. 30 mmol (19.16 g) of the resulting product was taken and 61 mmol (9.04 g) of phthalic anhydride and 100 ml of 1,4-dioxane were added. The reaction was carried out at 65 °C for 6 hours. 20 mmol (18.06 g) of the resulting product was taken and 41 mmol (5.25 g) of glycidyl acrylate, 1 g of triethylamine and 100 ml of 1,4-dioxane were added. The reaction was carried out at 78 °C for 8 hours. The product was then purified, filtered and dried to obtain the final product with the following structure.

[0380] [Chemical formula 2m]

[0381]

[0382] Examples and Comparative Examples: Production of photosensitive resin composition

[0383] 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%)

[0384] [Table 1]

[0385]

[0386] [Table 2]

[0387]

[0388] -Monomers A1 to A15: Monomers prepared according to Synthesis Examples 1-1 to 1-15;

[0389] -Monomer A16: 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (TR-FR-302, TRONLY);

[0390] - Monomer A17: o-phenylphenoxyethyl acrylate (A001, Green Chemicals);

[0391] - Monomer A18: A blend of pentaerythritol triacrylate and pentaerythritol tetraacrylate (molar ratio, 0.6:0.4) (A-TMM-3LM-N, Shin-Nakamura Chemical Co., Ltd.);

[0392] -Alkali-soluble resin B1: Cardo adhesive resin, molecular weight 5400;

[0393]

[0394] - Photopolymerization initiator: C1 (Irgaqure-907, manufactured by BASF);

[0395] - Solvent: D1 (propylene glycol monomethyl ether acetate, PGMEA);

[0396] - Thiol compound T1: Polythiol compound represented by chemical formula 3-1.

[0397] [Chemical Formula 3-1]

[0398]

[0399] Experimental Example

[0400] (1) Refractive index measurement

[0401] The compositions of Examples 1 to 17 and Comparative Examples 1 to 4 were applied to a 4-inch silicon wafer. For the resulting coating, linear polarization in the wavelength range of 380 nm to 1000 nm was measured using a JAWoollam Co.M-2000 device at 25°C and 50% RH with an incident angle of 70°.

[0402] For the coating of the above optical laminate, the measured ellipsometry data (Ψ,Δ) was optimized using the Cauchy model of Equation 1 to make the MSE less than 3, and the refractive index at 550 nm wavelength was calculated.

[0403] <Formula 1>

[0404]

[0405] 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.

[0406] (2) Assessment of Adhesion (Cross Cut)

[0407] The evaluation criteria were determined by performing a cross-cut test on the coatings formed using Examples 1 to 17 and Comparative Examples 1 to 4 of Experimental Example 1 described above. The evaluation criteria are shown in... Figure 1 In the middle. For example Figure 1 As shown, for patterned substrates, lines are scribed on the coating using a cutter to form a 10x10 grid. Then, tape is applied to the coating and instantly peeled off. The number of remaining grids and the level of coating peeling are then assessed. The evaluation is based on ASTM D3359 and is shown in Table 3 below.

[0408] (3) Evaluation of heat and moisture resistance

[0409] For the films formed using Examples 1 to 17 and Comparative Examples 1 to 4 of Experimental Example 1 above, they were placed under high temperature (85°C) and high humidity (85% RH), and the observed changes in the appearance of the patterns were recorded.

[0410] <Evaluation Criteria>

[0411] ◎: No change in appearance;

[0412] ○: Excellent appearance condition;

[0413] △: Wrinkles appear on the surface;

[0414] X: Peeling and / or solvent discoloration.

[0415] [Table 3]

[0416]

[0417] Based on the experimental data in Table 3 above, in Examples 1 to 17 where patterns were formed using the photosensitive resin composition of the present invention, excellent results were observed in adhesion (cross-cut) and heat and moisture resistance evaluations. The refractive index, measured by ellipsometry, was 1.62 or higher, which is exceptionally good. In particular, Example 17, which contains both monomer A1 of Formula 1 and monomer A2 of Formula 2, exhibited the best results in terms of refractive index.

[0418] On the other hand, in Comparative Example 1, which contained a difunctional monomer that did not satisfy Chemical Formula 1 or 2 of this application, and in Comparative Example 2, which contained a monofunctional monomer that did not satisfy Chemical Formula 1 or 2 of this application, very poor heat and moisture resistance was observed, resulting in insufficient reliability and reduced adhesion. Furthermore, in Comparative Example 3, which contained a polyfunctional monomer that did not satisfy Chemical Formula 1 or 2 of this application, it was confirmed that although excellent adhesion and reliability were achieved using a conventional tetrafunctional monomer, the refractive index was 1.51, significantly lower than that of the examples. In Comparative Example 4, monomers A16 and A18 were mixed to improve refractive index, adhesion, and reliability simultaneously; however, since it did not contain a monomer that satisfied Chemical Formula 1 or 2 of this application, the adhesion and reliability were at an unusable level, and the refractive index was below 1.6.

[0419] Based on the above results, it can be confirmed that the photosensitive resin composition of this application can obtain a coating with excellent refractive index, adhesion, heat and moisture resistance. The above 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, characterized in that, It contains (A) monomers, (B) alkali-soluble resins, (C) photopolymerization initiators, and (D) solvents. The monomer (A) comprises one or more of the following chemical formulas 1 and 2, wherein chemical formulas 1 and 2 contain three or more substituents having ethylene-like unsaturated double bonds. Chemical Formula 1 Chemical formula 2 In chemical formulas 1 and 2, R1 can be either hydrogen or methyl. R2 is an -OH group, or a substituent containing one or more vinyl unsaturated double bonds or carboxyl groups. R3 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. R4 is a substituent containing one or more (meth)acrylate groups. R5 is either -O- or -S-. n is an integer that is either 0 or 1.

2. The photosensitive resin composition according to claim 1, wherein the substituent having an ethylene unsaturated double bond comprises a (meth)acrylate group.

3. The photosensitive resin composition according to claim 1 or 2, wherein R2 has the following chemical formula 1-1. Chemical Formula 1-1 In chemical formula 1-1, R1 can be either hydrogen or methyl. R5 is either -O- or -S-. n is an integer that is either 0 or 1. "*" represents a binding bond.

4. The photosensitive resin composition according to claim 1 or 2, wherein R3 is selected from the group consisting of chemical formulas 1-2 to 1-14-1. In chemical formulas 1-2 to 1-14-1, R1 can be either hydrogen or methyl. R 1k It is a -OH group or a substituent containing one or more benzene rings. "*" represents a binding bond.

5. The photosensitive resin composition according to claim 1 or 2, wherein R4 is selected from the group consisting of chemical formulas 1-15 to 1-21-1. Chemical formula 1-15 Chemical formula 1-16 Chemical formula 1-17 Chemical formula 1-18 Chemical formula 1-19 Chemical formula 1-20 Chemical formula 1-21 Chemical formula 1-21-1 In chemical formulas 1-15 to 1-21-1, R1 can be either hydrogen or methyl. R 1k It is a -OH group or a substituent containing one or more benzene rings. "*" represents a binding bond.

6. The photosensitive resin composition according to claim 1 or 2, wherein the monomer (A) comprises chemical formula 1 and chemical formula 2.

7. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition further comprises (E) an additive. The additive (E) is selected from one or more of surfactants, adhesion promoters and thiol compounds.

8. The photosensitive resin composition according to claim 7, wherein the thiol compound, as a sulfur-containing monomer, is a polyfunctional thiol compound having 2 to 5 thiol groups -SH at the end.

9. The photosensitive resin composition according to claim 8, wherein the polyfunctional thiol compound comprises one or more of the following chemical formulas 3-1 to 3-5.

10. The photosensitive resin composition according to claim 1 or 2, characterized in that, The acid value of the alkali-soluble resin (B) is from 20 mg KOH / g to 200 mg KOH / g.

11. The photosensitive resin composition according to claim 1 or 2, wherein the (B) alkali-soluble resin comprises a Cardo resin.

12. The photosensitive resin composition according to claim 11, wherein the Cardo-based resin comprises at least one repeating unit of chemical formulas 4 to 9. Chemical Formula 4 Chemical formula 5 Chemical Formula 6 Chemical Formula 7 Chemical Formula 8 Chemical formula 9 Among the chemical formulas 4 to 9, X and X' are each independently a single bond, -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, 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 or not inserted by 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 independent integers from 1 to 30. t and u are each an independent integer from 0 to 1. P is independent of each R13 and R14 are each independently a hydrogen atom, hydroxyl group, thiol 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.

13. A pattern comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 12.

14. The pattern according to claim 13, characterized in that, The refractive index of the pattern is greater than 1.

60.

15. The pattern according to claim 13 or 14, wherein the pattern is selected from any one of the following groups: array planarization film pattern, protective film pattern, microlens pattern, insulating film pattern, photoresist pattern, black matrix pattern, columnar spacer pattern, black columnar spacer, colored resist pattern, pattern containing scatterers, and pattern containing quantum dots.

16. A display device comprising the pattern of any one of claims 13 to 15.

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