TW202309137A - Photosensitive resin composition, protrusion pattern and display device using the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, and a protrusion pattern and a display device using the same. The photosensitive resin composition according to the present invention can form a pattern exhibiting high refractive index without using inorganic particles and has excellent pattern characteristics and chemical resistance even at a low temperature curing.

Description

Photosensitive resin composition, projecting pattern using same, and display device using same

The present invention relates to a photosensitive resin composition, a protruding pattern using it and a display device using it. In particular, the present invention relates to a photosensitive resin composition capable of forming a pattern exhibiting a high refractive index without using inorganic particles and having excellent pattern characteristics and chemical resistance even at low temperature curing, and A protruding pattern and a display device using the composition.

Organic light emitting diodes (organic light emitting diodes, OLEDs) are expected to become the next generation of display devices and lighting devices due to their fast response rate, wide viewing angle, and low-voltage operation.

In general, an organic material layer made of light emitting material or charge transfer material is located between the upper and lower electrodes of the OLED. Since the OLED has a stacked structure of materials with different refractive indices, the reflection occurs at the interface of these materials, so the external light extraction efficiency is low.

In particular, the refractive index of the organic light emitting layer of the OLED is about 1.7, the refractive index of indium tin oxide (ITO) used as a transparent electrode is 2.0, and the refractive index of the glass substrate is 1.5. In this case, the proportion of non-extractable waveguided light trapped in the transparent electrode or organic material layer is about 45%, and the proportion of unextractable substrate waveguided light trapped in the substrate is about 35%. Therefore, only about 20% of the light emitted from the OLED is extracted to the outside.

Various studies have been conducted to solve this problem, and a representative example is a microlens array. The microlens array increases the light extraction effect by changing the incident angle at the interface between the glass substrate and the air surface in the OLED device.

The microlens array should exhibit a high refractive index greater than or equal to that of the glass substrate. Typically, inorganic particles have a higher refractive index than organic materials. However, when a pattern is formed using a photosensitive resin composition containing inorganic particles, the surface roughness of the pattern increases, cracks occur, and bending resistance is low. Therefore, it is not suitable for use in flexible display devices.

Therefore, there is a need to develop a photosensitive resin composition capable of forming a pattern exhibiting a high refractive index greater than or equal to that of a glass substrate without using inorganic particles.

Further, there is a need to develop a photosensitive resin for flexible display devices that exhibits excellent pattern characteristics even at low temperature curing and has excellent chemical resistance without changing the film thickness during post-processing combination.

An object of the present invention is to provide a photosensitive resin composition which can be formed without using inorganic particles, exhibits a high refractive index, and has excellent pattern characteristics and chemical resistance even at low temperature curing. sexual pattern.

Another object of the present invention is to provide a protruding pattern formed by using the photosensitive resin composition.

Yet another object of the present invention is to provide a display device comprising the protruding pattern.

（I） 其中， R係包含硫原子的k價的脂族烴基，或是包含硫原子的k價的脂環烴基；以及 k係2至6的整數。 According to one aspect of the present invention, there is provided a photosensitive resin composition comprising a polythiol compound represented by the following formula (I), an alkali-soluble resin, a polyfunctional acrylate photopolymerizable compound, a photopolymerization initiator, and Solvent:

(I) wherein, R is a k-valent aliphatic hydrocarbon group containing a sulfur atom, or a k-valent alicyclic hydrocarbon group containing a sulfur atom; and k is an integer of 2 to 6.

（II）

（III） 其中， R ^a、R ^b、R ^c及R ^d各自獨立為氫原子或-CH ₂-SH； R ^e、R ^f、R ^g及R ^h各自獨立為氫原子或-CH ₂-SH，並且R ^e、R ^f、R ^g及R ^h中的至少二者為-CH ₂-SH； d係1至2的整數；以及 e係0至2的整數。 In one embodiment of the present invention, the polythiol compound represented by formula (I) may include a polythiol compound represented by the following formula (II) or formula (III):

(II)

(III) Among them, R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom or -CH ₂ -SH; ^Re , R ^f , R ^g and ^Rh are each independently a hydrogen atom or -CH ₂ -SH , and at least two of R ^e , R ^f , R ^g and ^Rh are —CH ₂ —SH; d is an integer of 1 to 2; and e is an integer of 0 to 2.

（IV）

（V）

（VI）

（VII）

（VIII） In one embodiment of the present invention, the polythiol compound represented by formula (I) may comprise a polythiol compound represented by any one of the following formulas (IV) to (VIII):

(IV)

(V)

(VI)

(VII)

(VIII)

In one embodiment of the present invention, based on 100% by weight of the total solid content of the photosensitive resin composition, the content of the polythiol compound represented by formula (I) may be 0.1 to 10% by weight .

（IX）

（X）

（XI）

（XII）

（XIII）

（XIV） 其中， X及X'各自獨立為單鍵、-CO-、-SO ₂-、-C(CF ₃) ₂-、-Si(CH ₃) ₂-、-CH ₂-、-C(CH ₃) ₂-、-O-、

、

、

、

、

、

、

、

、

、

、

、

或

； Y係酸酐的殘基； Z係酸二酐的殘基； R'係氫原子、乙基、苯基、-C ₂H ₄Cl、-C ₂H ₄OH或-CH ₂CH=CH ₂， R1、R1'、R2、R2'、R3、R3'、R4、R4'、R5、R5'、R6及R6'各自獨立為氫原子或甲基； R7、R7'、R8及R8'各自獨立為C ₁至C ₆的伸烷基，其中該伸烷基係插入有酯鍵、C ₆至C ₁₄的伸環烷基、伸芳基之至少一者或沒有插入； R9、R9'、R10、R10'、R11、R11'、R12及R12'各自獨立為氫原子、鹵素原子或C ₁至C ₆的烷基； m及n各自獨立為1至30的整數； t及u各自獨立為0至1的整數； P各自獨立為

、

、

、

或

； R13及R14各自獨立為氫原子、羥基、硫醇基、胺基、硝基或鹵素原子； Ar1各自獨立為芳基； Y'係酸酐的殘基； Z'係酸二酐的殘基； A係O、S、NR'、Si(R') ₂或Se； a及b各自獨立為1至6的整數；以及 p及q各自獨立為1至30的整數。 In one embodiment of the present invention, the alkali-soluble resin may comprise at least one of the repeating units represented by the following formulas (IX) to (XIV):

(IX)

(X)

(XI)

(XII)

(XIII)

(XIV) Wherein, X and X' are each independently a single bond, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C( CH ₃ ) ₂ -, -O-,

,

,

,

,

,

,

,

,

,

,

,

or

; Y is the residue of an acid anhydride; Z is the residue of an acid dianhydride; R' is a hydrogen atom, ethyl, phenyl, -C ₂ H ₄ Cl, -C ₂ H ₄ OH or -CH ₂ CH=CH ₂ , R1, R1', R2, R2', R3, R3', R4, R4', R5, R5', R6 and R6' are each independently a hydrogen atom or a methyl group; R7, R7', R8 and R8' are independently C ₁ to C ₆ alkylene group, wherein the alkylene group is inserted with an ester bond, C ₆ to C ₁₄ cycloalkylene group, at least one of aryl group or no insertion; R9, R9', R10 , R10', R11, R11', R12 and R12' are each independently a hydrogen atom, a halogen atom or a C ₁ to C ₆ alkyl group; m and n are each independently an integer from 1 to 30; t and u are each independently 0 Integers from to 1; P are each independently

,

,

,

or

; R13 and R14 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogen atom; Ar1 is each independently an aryl group; Y' is an acid anhydride residue; Z' is an acid dianhydride residue; A is O, S, NR', Si(R') ₂ or Se; a and b are each independently an integer of 1 to 6; and p and q are each independently an integer of 1 to 30.

In one embodiment of the present invention, the acid anhydride may be selected from the following groups: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, formic Inner methylene tetrahydrophthalic anhydride (methylendomethylenetetrahydrophthalic anhydride), chlorine bridge anhydride and methyl tetrahydrophthalic anhydride.

In one embodiment of the present invention, the acid dianhydride may be selected from the following groups: pyromelteric dianhydride, benzophenonetetracarboxylic dianhydride (benzophenonetetracarboxylic dianhydride), biphenyltetracarboxylic dianhydride and biphenylethertetracarboxylic dianhydride.

（XV）

（XVI）

（XVII） 其中，R15及R16各自獨立為氫原子、羥基、硫醇基、胺基、硝基、鹵素原子或具有不飽和雙鍵的2至20個碳的聚合性官能基，並且R15及R16之至少一者係具有不飽和雙鍵的2至20個碳的聚合性官能基。 The photosensitive resin composition according to one embodiment of the present invention may further include a cardo-based photopolymerizable compound represented by any one of the following formula (XV) to formula (XVII):

(XV)

(XVI)

(XVII) wherein, R15 and R16 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a nitro group, a halogen atom, or a polymerizable functional group of 2 to 20 carbons having an unsaturated double bond, and R15 and R16 At least one of them is a polymerizable functional group of 2 to 20 carbons having an unsaturated double bond.

，並且R15及R16之至少一者係

， R17係C ₁至C ₆的伸烷基，並且該伸烷基係插入有酯鍵、C ₆至C ₁₄的伸環烷基、伸芳基之至少一者或沒有插入；以及 R18可為氫原子或甲基。 In one embodiment of the present invention, R15 and R16 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a nitro group, a halogen atom or

, and at least one of R15 and R16 is

, R17 is C ₁ to C ₆ alkylene group, and the alkylene system is inserted with an ester bond, C ₆ to C ₁₄ cycloalkylene group, at least one of arylene group or no insertion; and R18 can be hydrogen atom or methyl group.

The photosensitive resin composition according to one embodiment of the present invention may not contain inorganic particles.

According to another aspect of the present invention, a protrusion pattern formed by using the photosensitive resin composition is provided.

According to another aspect of the present invention, a display device including the protruding pattern is provided.

By including a polythiol compound having a specific structure, the photosensitive resin composition according to the present invention can be formed to exhibit a high refractive index of 1.60 or more than 1.60 at a wavelength of 550 nm without using inorganic particles, even if It also has excellent pattern properties such as developing speed, residue, adhesive properties, and surface hardness properties under low-temperature curing, and has excellent chemical resistance to developers and monomers.

The present invention is described in more detail below.

One embodiment of the present invention relates to a photosensitive resin composition comprising a polythiol compound (A), an alkali-soluble resin (B), a polyfunctional acrylate photopolymerizable compound (C), and a photopolymerization initiator (D) and solvent (E).

The photosensitive resin composition according to one embodiment of the present invention can form a photosensitive resin composition exhibiting 1.60 or more than 1.60 at a wavelength of 550 nm without using inorganic particles by using a polythiol compound having a specific structure. High refractive index, such as a refractive index of 1.60 to 1.7. Therefore, the insulating film patterned by the lithography process using the photosensitive resin composition according to an embodiment of the present invention can be used as a light extraction material of the self-luminous device, and thus the light emitted from the self-luminous device The light extraction effect and brightness of light can be greatly improved.

In addition, the photosensitive resin composition according to an embodiment of the present invention exhibits a ratio of developing speed so that the exposed portion and the non-exposed portion are clear even under low-temperature curing, and has, for example, residue, adhesive properties, and surface Excellent pattern properties of hardness properties, and excellent chemical resistance to developers and/or monomers used in post-processing due to excellent degree of curing.

polythiol compounds ( A )

In one embodiment of the present invention, the polythiol compound (A) is a component for increasing the refractive index and improving the curing degree, and is a compound having two or more thiol groups in the molecule.

（I） 其中， R係包含硫原子的k價的脂族烴基，或是包含硫原子的k價的脂環烴基；以及 k係2至6的整數。 The polythiol compound (A) is represented by the following formula (I):

(I) wherein, R is a k-valent aliphatic hydrocarbon group containing a sulfur atom, or a k-valent alicyclic hydrocarbon group containing a sulfur atom; and k is an integer of 2 to 6.

（II）

（III） 其中， R ^a、R ^b、R ^c及R ^d各自獨立為氫原子或-CH ₂-SH； R ^e、R ^f、R ^g及R ^h各自獨立為氫原子或-CH ₂-SH，並且R ^e、R ^f、R ^g及R ^h中的至少二者為-CH ₂-SH； d係1至2的整數；以及 e係0至2的整數。 The polythiol compound represented by formula (I) may include a polythiol compound represented by the following formula (II) or formula (III):

(II)

(III) Among them, R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom or -CH ₂ -SH; ^Re , R ^f , R ^g and ^Rh are each independently a hydrogen atom or -CH ₂ -SH , and at least two of R ^e , R ^f , R ^g and ^Rh are —CH ₂ —SH; d is an integer of 1 to 2; and e is an integer of 0 to 2.

（IV）

（V）

（VI）

（VII）

（VIII） The polythiol compound represented by formula (I) may comprise a polythiol compound represented by any one of the following formulas (IV) to (VIII):

(IV)

(V)

(VI)

(VII)

(VIII)

The polythiol compound may contain the exemplified polythiol compounds alone or in combination of two or more exemplified polythiol compounds.

By including the polythiol compound represented by formula (I), the photosensitive resin composition according to the present invention can be formed to exhibit a high refractive index of 1.60 or more than 1.60 at a wavelength of 550 nm, even under low temperature curing. A pattern with excellent pattern properties and excellent chemical resistance to developers and/or monomers used in post-processing.

In one embodiment of the present invention, based on 100% by weight of the total solid content in the photosensitive resin composition, the content of the polythiol compound represented by formula (I) may be 0.1 to 10% by weight, Preferably it is 1 to 10% by weight. When the content of the polythiol compound represented by the formula (I) is less than 0.1% by weight, the refractive index and/or the degree of curing may decrease, and when the polythiol compound represented by the formula (I) When the content is more than 10% by weight, the non-exposed portion may not be developed in a developer, for example, in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH).

In the present invention, the solid content in the photosensitive resin composition means the sum of components other than the solution.

Alkali-soluble resin ( B )

In one embodiment of the present invention, the alkali-soluble resin (B) is a reactive component by the action of light or heat, and when forming a pattern, it imparts Solubility.

（IX）

（X）

（XI）

（XII）

（XIII）

（XIV） 其中， X及X'各自獨立為單鍵、-CO-、-SO ₂-、-C(CF ₃) ₂-、-Si(CH ₃) ₂-、-CH ₂-、-C(CH ₃) ₂-、-O-、

、

、

、

、

、

、

、

、

、

、

、

或

； Y係酸酐的殘基； Z係酸二酐的殘基； R'係氫原子、乙基、苯基、-C ₂H ₄Cl、-C ₂H ₄OH或-CH ₂CH=CH ₂， R1、R1'、R2、R2'、R3、R3'、R4、R4'、R5、R5'、R6及R6'各自獨立為氫原子或甲基； R7、R7'、R8及R8'各自獨立為C ₁至C ₆的伸烷基，其中該伸烷基係插入有酯鍵、C ₆至C ₁₄的伸環烷基、伸芳基之至少一者或沒有插入； R9、R9'、R10、R10'、R11、R11'、R12及R12'各自獨立為氫原子、鹵素原子或C ₁至C ₆的烷基； m及n各自獨立為1至30的整數； t及u各自獨立為0至1的整數； P各自獨立為

、

、

、

或

； R13及R14各自獨立為氫原子、羥基、硫醇基、胺基、硝基或鹵素原子； Ar1各自獨立為芳基； Y'係酸酐的殘基； Z'係酸二酐的殘基； A係O、S、NR'、Si(R') ₂或Se； a及b各自獨立為1至6的整數；以及 p及q各自獨立為1至30的整數。 The alkali-soluble resin (B) may preferably include a cardole-based alkali-soluble resin. The cardole-based alkali-soluble resin may comprise at least one of the repeating units represented by the following formulas (IX) to (XIV):

(IX)

(X)

(XI)

(XII)

(XIII)

(XIV) Wherein, X and X' are each independently a single bond, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C( CH ₃ ) ₂ -, -O-,

,

,

,

,

,

,

,

,

,

,

,

or

; Y is the residue of an acid anhydride; Z is the residue of an acid dianhydride; R' is a hydrogen atom, ethyl, phenyl, -C ₂ H ₄ Cl, -C ₂ H ₄ OH or -CH ₂ CH=CH ₂ , R1, R1', R2, R2', R3, R3', R4, R4', R5, R5', R6 and R6' are each independently a hydrogen atom or a methyl group; R7, R7', R8 and R8' are independently C ₁ to C ₆ alkylene group, wherein the alkylene group is inserted with an ester bond, C ₆ to C ₁₄ cycloalkylene group, at least one of aryl group or no insertion; R9, R9', R10 , R10', R11, R11', R12 and R12' are each independently a hydrogen atom, a halogen atom or a C ₁ to C ₆ alkyl group; m and n are each independently an integer from 1 to 30; t and u are each independently 0 Integers from to 1; P are each independently

,

,

,

or

; R13 and R14 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogen atom; Ar1 is each independently an aryl group; Y' is an acid anhydride residue; Z' is an acid dianhydride residue; A is O, S, NR', Si(R') ₂ or Se; a and b are each independently an integer of 1 to 6; and p and q are each independently an integer of 1 to 30.

Herein, the C ₁ to C ₆ alkylene group refers to a linear or branched divalent hydrocarbon having 1 to 6 carbon atoms, and includes, for example, methylene, ethylidene, propylidene, butylene base, but not limited to.

Herein, C ₆ to C ₁₄ cycloalkylene refers to a monocyclic or condensed ring divalent hydrocarbon having 6 to 14 carbon atoms, and includes, for example, cyclohexylene, cycloheptylene, cyclooctylene, etc. , but not limited to this.

As used herein, aryl includes divalent aryl and heteroaryl groups and some of their reduced derivatives. Aryl is a 5 to 15 membered monocyclic or condensed ring group, and heteroaryl refers to an aryl group containing at least one of oxygen, sulfur or nitrogen. Examples of representative arylenyl groups include phenylene, naphthylene, pyridylene, furylene, thiophenylene, indolylene, quinolinyl, imidazolinyl, oxazolylene, Thiazolyl, tetrahydronaphthyl, etc., but not limited thereto.

Herein, a C1 _{to C6} alkyl refers to a linear or branched monovalent hydrocarbon having 1 to 6 carbon atoms, and includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl group, isobutyl group, tertiary butyl group, n-pentyl group, n-hexyl group, etc., but not limited thereto.

As used herein, aryl includes monovalent aryl and heteroaryl as well as some of their reduced derivatives. Aryl is a 5 to 15 membered monocyclic or condensed ring group, and heteroaryl refers to an aryl group containing at least one of oxygen, sulfur or nitrogen. Examples of representative aryl groups include phenyl, naphthyl, pyridyl, furyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, oxazolyl, thiazolyl, tetralinyl, and the like, but not limited to this.

The residue of the acid anhydride herein can be obtained by reacting the synthesis intermediate product of the cardole-based resin of the present invention with an acid anhydride. The acid anhydride that can be introduced into the acid anhydride residue is not particularly limited, and includes, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Inner methylene tetrahydrophthalic anhydride (methylendomethylenetetrahydrophthalic anhydride), chlorine bridge anhydride and methyl tetrahydrophthalic anhydride, etc. These acid anhydrides can be used alone or in combination of two or more.

The residue of the acid dianhydride herein can be obtained by reacting the synthesis intermediate product of the cardole-based resin of the present invention with the acid dianhydride. The acid dianhydride that can be introduced into the acid dianhydride residue is not particularly limited, and includes, for example, pyromelteric dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride And biphenyl ether tetracarboxylic dianhydride (biphenylethertetracarboxylic dianhydride) and so on. These acid anhydrides can be used alone or in combination of two or more.

The acid dianhydride herein refers to a compound containing two acid anhydride groups in the molecule.

The photosensitive resin composition according to the present invention can further increase the refractive index and further improve the Pattern properties and chemical resistance under low temperature curing.

The method for preparing the cardole-based alkali-soluble resin is not particularly limited. For example, a carbadole-based alkali-soluble resin can be prepared by reacting a bisphenol compound with an epoxy compound to synthesize a bisphenol epoxy compound, and subjecting the synthesized bisphenol epoxy compound to an acrylate compound. react to synthesize a bisphenol epoxy acrylate compound, and then react the bisphenol epoxy acrylate compound with an acid anhydride, an acid dianhydride or a mixture thereof.

The photosensitive resin composition according to the present invention may further contain an acrylic alkali-soluble resin in addition to the cardole-based alkali-soluble resin as the alkali-soluble resin.

The acrylic alkali-soluble resin includes, for example, a copolymer of a carboxyl group-containing monomer and other monomers copolymerizable therewith.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids, for example, unsaturated monocarboxylic acids and unsaturated polycarboxylic acids having two or more carboxyl groups in the molecule, such as unsaturated dicarboxylic acids and unsaturated tricarboxylic acid. Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid and the like. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid may be an acid anhydride and specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. In addition, the unsaturated polycarboxylic acids may be mono(2-methacryloxyalkyl)esters thereof, including for example mono(2-acryloxyethyl)succinate, mono(2-methacryloxyethyl)succinate, mono(2-methacryloxy ethyl) succinate, mono(2-acryloxyethyl) phthalate, mono(2-methacryloxyethyl) phthalate, etc. The unsaturated polycarboxylic acid may be a mono(meth)acrylate having a dicarboxylic polymer at both ends, including, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. . These carboxyl group-containing monomers can be used alone or in combination of two or more.

Other monomers copolymerizable with carboxyl-containing monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxy Styrene, m-methoxystyrene, p-methoxystyrene, o-styrene methyl ether, m-styrene methyl ether, p-styrene methyl ether, o-styrene glycidyl ether, m-styrene epoxy Propyl ether, p-styrene glycidyl ether, indene, etc.; unsaturated carboxylic acid esters, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, methyl n-propyl acrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, secondary butyl acrylate, methacrylic acid Secondary butyl ester, tertiary butyl acrylate, tertiary butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate , 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, acrylic acid 4-Hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, acrylic acid Phenyl ester, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate , Methoxydiethylene glycol acrylate, Methoxydiethylene glycol methacrylate, Methoxytriethylene glycol acrylate, Methoxytriethylene glycol methacrylate, Methoxypropylene glycol acrylate ester, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, Dicyclopentadienyl methacrylate, Adamantyl (meth)acrylate, Norbornyl (meth)acrylate, 2-Hydroxy-3-phenoxypropyl acrylate, 2-Hydroxy-3-methacrylate - Phenoxypropyl, glyceryl monoacrylate, glycerol methacrylate, etc.; aminoalkyl unsaturated carboxylates, such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminoethyl acrylate -Dimethylaminoethyl methacrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, methyl 2-dimethylaminopropyl acrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc. ; Unsaturated carboxylic acid glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; vinyl carboxylates, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Esters, etc.; unsaturated ethers, such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, etc.; vinyl cyanide (vinyl cyanide) compounds, such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, Vinylidene dicyanide, etc.; unsaturated amides, such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide Amides, etc.; unsaturated imides, such as maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide imines, etc.; aliphatic conjugated dienes, such as 1,3-butadiene, isoprene, chloroprene, etc.; Acyl-based macromonomers, such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. These monomers may be used alone or in combination of two or more.

The alkali-soluble resin may have an acid value (KOH mg/g) of 20 to 200. When the acid value is within the above range, the solubility in the developer is improved. Therefore, the non-exposed portion is easily dissolved and the sensitivity is increased. Therefore, the pattern of the exposed portion continues to exist at the time of development, thereby improving the residual ratio of the film, which is preferable. The acid value herein is a value measuring the amount (mg) of potassium hydroxide required to neutralize 1 g of polymer, and can be determined by titration using an aqueous potassium hydroxide solution.

The polystyrene-based weight average molecular weight of the alkali-soluble resin measured by gel permeation chromatography (GPC; using tetrahydrofuran as a dike fluid) (hereinafter referred to as the weight average molecular weight) is preferably 1,000 g/mol Up to 30,000 g/mol. When the weight average molecular weight is within the above range, the sensitivity of the non-exposed portion to dissolve in the developer increases, and exhibits excellent chemical resistance during post-processing after thermal curing, which is preferable.

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.5 to 6.0. A molecular weight distribution of 1.5 to 6.0 is preferable because of excellent reliability .

Based on 100% by weight of the total solid content in the photosensitive resin composition, the content of the alkali-soluble resin (B) is 20 to 80% by weight, preferably 30 to 70% by weight. When the content of the alkali-soluble resin (B) is less than 20% by weight, the sensitivity of the non-exposed portion to dissolve in the developer decreases and thus residue may be generated. When the content of the alkali-soluble resin (B) is more than 80% by weight, photocurability may decrease and thus exposed portions may be dissolved in the developer.

Multifunctional acrylate photopolymerizable compound ( C )

In one embodiment of the present invention, the polyfunctional acrylate photopolymerizable compound (C) is a component that can be polymerized by the action of light on the following photopolymerization initiator. It is polymerized through the exposure process to improve the mechanical properties of the pattern, such as hardness, adhesive properties, etc., or to increase the developability of the alkali-soluble resin.

The polyfunctional acrylate photopolymerizable compound is a compound having two or more (meth)acryloxy groups in the molecule, preferably having three or more (meth)acryloxy groups, and more preferably having Four or more (meth)acryloyloxy groups.

The polyfunctional acrylate photopolymerizable compound includes, for example, a difunctional (meth)acrylate photopolymerizable compound such as 1,6-hexanediol di(meth)acrylate, ethylene glycol di( Meth)acrylate, Neopentyl glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, Bis(acryloxyethyl)ether of bisphenol A, 3-Methylpentyl Diol di(meth)acrylate, etc.; trifunctional (meth)acrylate photopolymerizable compounds such as trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(methyl) ) acrylate, propoxylated trimethylolpropane tri(meth)acrylate, neopentylthritol tri(meth)acrylate, etc.; tetrafunctional (meth)acrylate photopolymerizable compounds such as Hydroxymethylpropane tetra(meth)acrylate, neopentylitol tetra(meth)acrylate, ethoxylated neopentylitol tetra(meth)acrylate, etc.; pentafunctional (meth)acrylate light Polymerizable compounds such as dipenteoerythritol penta(meth)acrylate, etc.; and hexafunctional (meth)acrylate photopolymerizable compounds such as ethoxylated dipenteoerythritol hexa(meth)acrylate ester, propoxylated diperythritol hexa(meth)acrylate, dipenteoerythritol hexa(meth)acrylate, etc.

The illustrated polyfunctional acrylate photopolymerizable compounds can be used alone or in combination of two or more.

Based on 100% by weight of the total solid content in the photosensitive resin composition, the content of the polyfunctional acrylate photopolymerizable compound (C) is 10 to 60% by weight, preferably 20 to 50% by weight. When the content of the polyfunctional acrylate photopolymerizable compound (C) is less than 10% by weight, photocurability decreases and thus exposed portions may be dissolved in a developer. When the content of the polyfunctional acrylate photopolymerizable compound (C) is more than 50% by weight, residue may be generated on the lower substrate or the refractive index may be lowered.

Photopolymerization initiator ( D. )

In one embodiment of the present invention, as long as the polyfunctional acrylate photopolymerizable compound (C) and the following cardole-based photopolymerizable compound (F) can be polymerized, the use of the photopolymerization initiator (D) There are no particular restrictions. Specifically, it is preferable to use at least one selected from the following groups: acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, bis-imidazole-based compounds, oxime-based compounds, and thioxanthone (thioxanthone) ) is a compound (according to polymerization characteristics, initial efficiency, absorption wavelength, availability, price, etc.). In particular, acetophenone-based compounds are preferred.

Specific examples of acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[ 4-(2-Hydroxyethoxy)benzene]-2-methylpropan-1-one, 1-hydroxycyclohexylbenzophenone, 2-methyl-1-(4-methylbenzenethio)-2-morphol Linpropan-1-one, 2-benzyl-2-dimethylamine-1-(4-morpholinobenzene)butan-1-one, 2-hydroxy-2-methyl-1-[4-(-1 -methylvinyl)benzene]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamine)-1-(4-morpholinbenzene)butan-1-one, etc.

Examples of benzophenone-based compounds include benzophenone, methyl phthalate, 4-benzobenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3, 3',4,4'-Tetrakis(tertiary butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Specific examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(-4-methoxybenzene)-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxynaphthalene)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine (2,4 -bis(trichloromethyl)-6-piperonyl-1,3,5-triazine), 2,4-bis(trichloromethyl)-6-(4-methoxystyrene)-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloro Methyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-di Methylamino-2-toluene)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxybenzene)ethenyl ]-1,3,5-triazine etc.

Specific examples of bisimidazole-based compounds include 2,2'-bis(2-chlorobenzene)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorobenzene )-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorobenzene)-4,4',5,5'-tetra(alkoxybenzene)bisimidazole, 2,2'-bis(2-chlorobenzene)-4,4',5,5'-tetrakis(trialkoxybenzene)biimidazole, 2,2'-bis(2,6-dichlorobenzene)- 4,4',5,5'-tetraphenyl-1,2'-biimidazole and bisimidazole compounds in which the phenyl groups at the 4,4',5,5' positions are substituted by carboalkoxy groups. Preferably, 2,2'-bis(2-chlorobenzene)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorobenzene)-4, 4',5,5'-tetraphenylbisimidazole or 2,2'-bis(2,6-dichlorobenzene)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole.

Specific examples of oxime compounds include o-ethoxycarbonyl-α-oxyimine-1-phenylpropan-1-one, 1,2-octanedione-1-(4-phenylthio)benzene-2-(o-phenyl formyl oxime), ketene-1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-1-(o-acetyloxime), etc. Commercially available oxime compounds include CGI-124 (available from Ciba-Geigy), CGI-224 (available from Ciba-Geigy), Irgacure OXE-01 (available from BASF), Irgacure OXE-02 (purchased from BASF), N-1919 (purchased from Adeka), NCI-831 (purchased from Adeka), etc.

Examples of thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone wait.

In addition, other photopolymerization initiators other than the above may be additionally used together within the range not impairing the efficacy of the present invention. For example, a benzoin-based compound or an anthracene-based compound can be used alone or in combination of two or more.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

Examples of anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene Anthracene et al.

In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, formazan Methylphenylglyoxylate or a titanocene compound may additionally be used in combination as a photopolymerization initiator.

Based on 100% by weight of the total solid content in the photosensitive resin composition, the content of the photopolymerization initiator (D) is 1 to 15% by weight, preferably 3 to 10% by weight. This range takes into account the rate of polymerization and the physical properties of the resulting coating film. When the content of the photopolymerization initiator is lower than this range, the polymerization rate is low and thus the overall process time may become long. When the content of the photopolymerization photopolymerization initiator is higher than the range, the physical properties of the coating film may be deteriorated due to excessive reaction resulting in excessive crosslinking reaction. Therefore, it should be used appropriately within the above range.

In addition, a photopolymerization initiator adjuvant may be used together with the photopolymerization initiator. When the photopolymerization initiator auxiliary agent is used together with the photopolymerization initiator, the photosensitive resin composition becomes more sensitive and thus improves productivity. Preferably, at least one compound selected from the group consisting of amines and carboxylic acid compounds can be used as the photopolymerization initiator auxiliary agent.

Such a photopolymerization initiator auxiliary is preferably used in an amount of 10 mol or less, more preferably in the range of 0.01 to 5 mol, per 1 mol of the photopolymerization initiator. When the photopolymerization initiator adjuvant is used in the above range, the polymerization effect is increased and thus the yield is improved.

solvent ( E. )

In one embodiment of the present invention, the solvent used in the photosensitive resin composition is not particularly limited, and various solvents used in the field of photosensitive resin compositions can be used.

Specific examples include ethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc.; diethylene glycol dialkyl ethers, such as Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc.; glycol alkyl ether acetates, such as methyl cellosolve acetate acetate), ethyl celluloid acetate, etc.; alkanediol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl Acetate, methoxypentyl acetate, etc.; aromatic hydrocarbons, such as benzene, toluene, xylene, mesitylene, etc.; ketones, such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl Isobutyl ketone, cyclohexanone, etc.; alcohols, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, etc.; esters, such as ethyl 3-ethoxypropionate, Methyl 3-methoxypropionate, etc.; cyclic esters, such as γ-butyrolactone, etc.

The solvent is preferably an organic solvent with a boiling point of 100°C to 200°C (in terms of coating and drying), more preferably alkanediol alkyl ether acetates, ketones, esters, such as 3-ethoxy Ethyl propionate, methyl 3-methoxypropionate, and even better, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. The above-mentioned solvents may be used alone or in combination of two or more.

Based on 100% by weight of the total solid content in the photosensitive resin composition, the content of the solvent (E) is 60 to 90% by weight, preferably 70 to 85% by weight. When the amount of the solvent is within the above range, when using a coating machine such as a roll coater (roll coater), a spin coater (spin coater), a slit and spin coater (slit and spin coater), a slit coater (slit Coater (also called die coater) and inkjet (inkjet) coating, the coating tendency is good.

Cardole photopolymerizable compound ( f )

The photosensitive resin composition according to one embodiment of the present invention may further include a cardole-based photopolymerizable compound (F).

The carbadole-based photopolymerizable compound (F) is a carbadole-based compound that can be polymerized by light and a photopolymerization initiator, and is used to increase the refractive index of the pattern.

（XV）

（XVI）

（XVII） 其中，R15及R16各自獨立為氫原子、羥基、硫醇基、胺基、硝基、鹵素原子或具有不飽和雙鍵的2至20個碳原子的聚合性官能基，並且R15及R16之至少一者係具有不飽和雙鍵的2至20個碳原子的聚合性官能基。 The cardole-based photopolymerizable compound may include a compound represented by any one of the following formula (XV) to formula (XVII):

(XV)

(XVI)

(XVII) wherein, R15 and R16 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a nitro group, a halogen atom, or a polymerizable functional group of 2 to 20 carbon atoms with an unsaturated double bond, and R15 and At least one of R16 is a polymerizable functional group of 2 to 20 carbon atoms having an unsaturated double bond.

，並且R15及R16之至少一者係

； R17係C ₁至C ₆的伸烷基，並且該伸烷基係插入有酯鍵、C ₆至C ₁₄的伸環烷基、伸芳基之至少一者或沒有插入；以及 R18係氫原子或甲基。 In one embodiment of the present invention, R15 and R16 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a nitro group, a halogen atom or

, and at least one of R15 and R16 is

; R17 is C ₁ to C ₆ alkylene group, and the alkylene system is inserted with an ester bond, C ₆ to C ₁₄ cycloalkylene group, at least one of arylene group or no insertion; and R18 is hydrogen atom or methyl.

（XVIII）

（XIX）

（XX）

（XXI）

（XXII） In particular, the carbadole-based photopolymerizable compound may further include a compound represented by any one of the following formulas (XVIII) to formula (XXII):

(XVIII)

(XIX)

(XX)

(XXI)

(XXII)

Based on the total solid content of the photosensitive resin composition as 100% by weight, the content of the carbadole-based photopolymerizable compound (F) may be 30% by weight or less, for example, the carbadole-based photopolymerizable compound The content of is 5 to 30% by weight, preferably 5 to 20% by weight. When the content of the cardole-based photopolymerizable compound is more than 30% by weight, the sensitivity of the non-exposed portion to dissolve in the developer may decrease.

additive( G )

The photosensitive resin composition according to one embodiment of the present invention may further include additives such as surfactants, adhesion promoters, and antioxidants, in addition to the above components, as needed.

Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitol fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethylene imine etc. In addition, examples may include, for example, the following products: KP (available from Shinyue Chemical Industry Co., Ltd.), POLYFLOW (available from Kyoeisha Chemical Company), EFTOP (available from Tochem Products), MEGAFAC (available from Dainippon Ink & Chemicals Company), Flourad ( Sumitomo 3M), Asahi guard (Asahi Glass), Surflon (Asahi Glass), SOLSPERSE (Lubrizol), EFKA (EFKA Chemicals), PB 821 (Ajinomoto) , and DISPER BYK (purchased from BYK Company).

Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-8-aminooctyltrimethoxysilane, 3-aminopropyltrimethoxysilane Ethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane, 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane , 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-hydrogenthiopropyltrimethoxysilane, etc.

Examples of antioxidants include 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

Based on the total solid content of the photosensitive resin composition as 100% by weight, the content of the additive (G) is 10% by weight or less than 10% by weight, for example, the content of the additive is 0.1 to 10% by weight, which is relatively Jia is 0.1 to 5% by weight, but not limited thereto.

The photosensitive resin composition according to one embodiment of the present invention may not contain inorganic particles. Therefore, the photosensitive resin composition according to one embodiment of the present invention may not contain scattering particles (scattering particles), such as metal oxide particles, for example, inorganic particles such as fillers, such as glass, silicon dioxide, alumina, etc. .

Therefore, the photosensitive resin composition according to an embodiment of the present invention may have low pattern surface roughness, prevent cracks, and have sufficient bending resistance to be applied to a flexible display device.

One embodiment of the present invention relates to a protrusion pattern formed by using the above-mentioned photosensitive resin composition.

The protruding pattern can be used in the microlens array to increase the light extraction effect of the self-luminous device.

The protrusion pattern may have a hemispherical shape, a trapezoidal shape, a conical shape, or the like.

The protruding pattern can be formed by coating the above-mentioned photosensitive resin composition on a substrate, exposing and dissolving the photosensitive resin composition in a predetermined pattern, and then performing post-baking.

First, the photosensitive resin composition of the present invention is coated on a substrate and dried by heating to remove volatile components such as solvents to obtain a smooth coating film.

Coating methods include, for example, inkjet printing, spin coating, flexible coating, roll coating, spin and slit coating, slit coating, and the like.

After the composition is applied, it is dried by heating (pre-baking) or dried under reduced pressure, and heated to remove hair-glowing ingredients such as solvents. In this case, the heating temperature is a relatively low temperature of 70 to 100°C.

The obtained film is irradiated with ultraviolet light passing through a mask to form a target pattern. In this case, it is preferable to use equipment such as a mask aligner or a stepper to uniformly irradiate the parallel light to the entire exposed portion and align the mask and the substrate precisely. When ultraviolet rays are irradiated, the part irradiated with ultraviolet rays is cured.

G-rays (wavelength 436 nm), h-rays, i-rays (wavelength 365 nm), etc. can be used as the ultraviolet rays. The amount of radiation of ultraviolet rays can be appropriately selected as required.

After that, a developing process is performed by bringing the cured coating film into contact with a developer to dissolve unexposed portions.

The image development method may be any of a liquid addition method, a dipping method, and a spray method. At the same time, the substrate can be tilted at any angle during the developing process.

After development, the substrate is rinsed with water and post-baked at a relatively low temperature of 70 to 100° C. for 10 to 60 minutes.

An embodiment of the present invention relates to a display device including the above-mentioned protruding pattern. Examples of the display device include, but are not limited to, a liquid crystal display device (LCD), an organic light emitting diode (OLED), etc., and include any display device known in the art and applicable. In particular, the display device may be a flexible display.

Hereinafter, the present invention will be described in detail through examples, comparative examples and experimental examples. These examples, comparative examples and experimental examples are only used to illustrate the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.

Synthesis example 1 : Cardole-based alkali-soluble resin ( B-1 )

Add 138 grams of 9,9'-bis(4-epoxypropoxyphenyl) stilbene (which is a bisphenol epoxy compound) (purchased from Hear Chem) and 54 grams of 2-carboxyethylpropionic acid to the reactor ester, 1.4 grams of benzyltriethylammonium chloride (purchased from Daejeong Chemicals & Metals), 1 gram of triphenylphosphine (purchased from Aldrich), 128 grams of propylene glycol methyl ethyl acetate (purchased from Daicel company) and 0.5 g of hydroquinone, and the temperature was raised to 120°C for 12 hours to synthesize the compound represented by the following formula (XIX).

（XIX）

（XXIII） In the reactor, add 60 grams of compounds represented by the following formula (XIX), 11 grams of biphenyl tetracarboxylic dianhydride (purchased from Mitsubishi Gas Chemical Company), 3 grams of tetrahydrophthalic anhydride (purchased from Aldrich) , 20 grams of propylene glycol methyl ethyl acetate (purchased from Daicel) and 0.1 grams of N,N'-tetramethylammonium chloride, and the temperature was raised to 120 ° C for 2 hours to synthesize the following formula ( Compounds represented by XXIII). The weight average molecular weight of the obtained resin was 5,400 g/mol.

(XIX)

(XXIII)

Synthesis example 2 : Cardole-based alkali-soluble resin ( B-2 )

Add 138 grams of 9,9'-bis(4-epoxypropoxyphenyl) stilbene (a bisphenol epoxy compound) (purchased from Hear Chem), 54 grams of mono-2-acryloxy Ethyl ethyl succinate, 1.4 g of benzyltriethylammonium chloride (purchased from Daejeong Chemicals & Metals), 1 g of triphenylphosphine (purchased from Aldrich), 128 g of propylene glycol methyl ethyl acetate (purchased from Daicel) and 0.5 g of hydroquinone, and the temperature was raised to 120° C. for 12 hours to synthesize a compound represented by the following formula (XX).

（XX）

（XXIV） In the reactor, add 60 grams of compounds represented by the following formula (XX), 11 grams of biphenyl tetracarboxylic dianhydride (purchased from Mitsubishi Gas Chemical Company), 3 grams of tetrahydrophthalic anhydride (purchased from Aldrich) , 20 grams of propylene glycol methyl ethyl acetate (purchased from Daicel) and 0.1 grams of N,N'-tetramethylammonium chloride, and the temperature was raised to 120 ° C for 2 hours to synthesize the following formula ( XXIV) compounds represented. The weight average molecular weight of the obtained resin was 5,400 g/mol.

(XX)

(XXIV)

Synthesis example 3 : Cardole-based alkali-soluble resin ( B-3 )

Mix 364.4 grams of 3',6'-dihydroxyspiro(fen-9,9-dibenzopyran) and 0.4159 grams of tertiary butylammonium bromide in a 3000-ml three-necked round-bottom bottle, and then add 2359 grams of epichlorohydrin and heated to 90 ° C for reaction. When analysis by liquid chromatography confirmed that 3',6'-dihydroxyspiro(terpine-9,9-dibenzopyran) was completely consumed, the reaction was cooled to 30°C and 50% hydroxide was added slowly Aqueous sodium solution (3 eq.). When analysis by liquid chromatography confirmed that the epichlorohydrin was completely consumed, extraction was performed with dichloromethane. Next, washing with water was performed three times, and the organic layer was dried over magnesium sulfate. Then, dichloromethane was distilled under reduced pressure, and recrystallization was performed using a mixed solvent of dichloromethane and methanol (50:50, v/v).

（XXI） Mix 1 equivalent of the synthesized epoxy compound, 0.004 equivalent of tertiary butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid, then add 24.89 grams of propylene glycol monomethyl as solvent ether acetate and mix. The reaction solution was dissolved by heating at a temperature of 90 to 100° C. while blowing air into the solution at a rate of 25 ml/min. The reaction solution in a cloudy state was heated to 120° C. to completely dissolve it. When the solution became clear and the viscosity increased, the acid value was measured and the solution was stirred until the acid value became less than 1.0 mg KOH/g. Stirring is required for 11 hours until the acid value reaches the target value (0.8). After completing the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of the following formula (XXI).

(XXI)

600 g of propylene glycol monomethyl ether acetate was added to 307.0 g of the compound of formula (XXI) and dissolved. Next, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added, and the mixture was gradually heated to 110 to 115° C. for 4 hours. After confirming that the anhydride group disappeared, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was added and brought to 90° C. for 6 hours to obtain a resin. The disappearance of the anhydride group was confirmed by IR spectrum.

Synthesis example 4 : Cardole-based alkali-soluble resin ( B-4 )

Mix 364.4 grams of 4,4'-(9H-dibenzopyran-9,9-diyl)diphenol and 0.4159 grams of tertiary butylammonium bromide in a 3000 ml three-neck round bottom bottle, and then Add 2359 grams of epichlorohydrin and heat to 90°C for reaction. When the analysis by liquid chromatography confirmed that 4,4'-(9H-dibenzopyran-9,9-diyl)diphenol was completely consumed, the reaction solution was cooled to 30°C and 50% Aqueous sodium hydroxide solution (3 equivalents). When analysis by liquid chromatography confirmed that the epichlorohydrin was completely consumed, extraction was performed with dichloromethane. Next, washing with water was performed three times and the organic layer was dried over magnesium sulfate. Then, dichloromethane was distilled under reduced pressure, and recrystallization was performed using a mixed solvent of dichloromethane and methanol (50:50, v/v).

（XXII） Mix 1 equivalent of the synthesized epoxy compound, 0.004 equivalent of tertiary butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid, then add 24.89 grams of propylene glycol monomethyl as solvent ether acetate and mix. The reaction solution was dissolved by heating at a temperature of 90 to 100° C. while blowing air into the solution at a rate of 25 ml/min. The reaction solution in a cloudy state was heated to 120° C. to completely dissolve it. When the reaction solution became transparent and the viscosity increased, the acid value was measured and the solution was stirred until the acid value became less than 1.0 mgKOH/g. Stirring is required for 11 hours until the acid value reaches the target value (0.8). After completing the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of the following formula (XXII).

(XXII)

600 g of propylene glycol monomethyl ether acetate was added to 307.0 g of the compound of formula (XXII) and dissolved. Next, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added, and the mixture was gradually heated to a temperature of 110 to 115° C. for 4 hours. After confirming that the anhydride group disappeared, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was added and the temperature was brought to 90° C. for 6 hours to obtain a resin. The disappearance of the anhydride group was confirmed by infrared spectroscopy.

Synthesis example 5 : Cardole-based alkali-soluble resin ( B-5 )

step 1

[response mechanism 1]

After installing a condensing reflux device and a thermometer in the three-necked bottle, add 42.5 grams of 9,9-bisphenol oxirane and measure 220 milliliters of 2-(chloromethyl)oxirane and inject. After adding 100 mg of tetrabutylammonium bromide, the temperature was raised to 90°C while stirring was started. After confirming that the unreacted component was less than 0.3%, vacuum distillation was carried out.

After the temperature dropped to 30°C, dichloromethane was injected, and sodium hydroxide was slowly added. After confirming that the product was more than 96% by high performance liquid chromatography (HPLC), 5% hydrochloric acid (HCl) was added dropwise to terminate the reaction. After extracting the reaction product and separating the layers, the organic layer was washed with water until it became neutral. The organic layer was dried with methoxysulfate and concentrated by distillation under reduced pressure using a rotary evaporator. Dichloromethane was added to the concentrated product, and methanol was added while the temperature was raised to 40°C and stirred. Then, the solution was cooled and stirred. After filtering the obtained solid, vacuum drying was performed at room temperature to obtain 52.7 g of white solid powder (yield 94%). Its structure was confirmed by ¹ H NMR.

^1H NMR in _CDCl3 : 7.75(2H), 7.35-7.254(6H), 7.08(4H), 6.74(4H), 4.13(2H), 3.89(2H), 3.30(2H), 2.87(2H) 2.71 (2H).

step 2

[Reaction Mechanism 2]

After installing a condensing reflux device and a thermometer in the three-necked flask, add 1000 grams of the reaction product of step 1, 524 grams of thiophenol and 617 grams of ethanol and stir. Slowly add 328 g of triethylamine dropwise into the reaction solution. After confirming the disappearance of the starting material by high performance liquid chromatography (HPLC), the reaction was terminated. After completing the reaction, ethanol was removed by distillation under reduced pressure. The organic material was dissolved in dichloromethane, washed with water, and the dichloromethane was removed by distillation under reduced pressure. After dissolving the concentrated organic matter in ethyl acetate, an ether solvent was added dropwise and stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 945 g of light yellow oil (64% yield). Its structure was confirmed by ¹ H NMR.

^1H NMR in _CDCl3 : 7.82(2H), 7.38-6.72(20H), 6.51(4H), 4.00(2H), 3.97(2H), 3.89(2H), 3.20(2H), 3.01(2H) , 2.64 (2H).

step 3

After installing a condensing reflux device and a thermometer in the three-necked flask, add 200 grams of 3,3'-(((9H-oxa-9,9-diyl)bis(4,1-phenylene) synthesized in step 2 )bis(oxy))bis(1-(phenylthio)propan-2-ol) monomer dissolved in 50% propylene glycol methyl ether acetate (PGMEA) and warmed to 115°C. 31.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was added dropwise at a temperature of 115°C, followed by stirring for 6 hours while maintaining the temperature at 115°C. After adding 7.35 g of phthalic anhydride and stirring for an additional 2 hours, the reaction was terminated. A resin having a weight average molecular weight of 3,500 g/mole was obtained after cooling.

Synthesis example 6 : Cardole-based alkali-soluble resin ( B-6 )

After installing a condensing reflux device and a thermometer in the three-necked flask, add 200 grams of 3,3'-(((9H-oxa-9,9-diyl)bis(4,1- phenylene))bis(oxyl))bis(1-(phenylthio)propan-2-ol) monomer dissolved in 50% propylene glycol methyl ether acetate (PGMEA) and heated to 115 ℃. At a temperature of 115°C, 21.1 g of pyromelteric dianhydride was added dropwise, followed by stirring for 6 hours while maintaining the temperature at 115°C. After adding 7.35 g of phthalic anhydride and stirring for an additional 2 hours, the reaction was terminated. A resin having a weight average molecular weight of 4,500 g/mole was obtained after cooling.

Embodiment and comparative example: the preparation of photosensitive resin composition

A photosensitive resin composition was prepared by mixing the components (% by weight) in the compositions shown in Table 1 and Table 2 below.

Table 1 Example polythiol compound Alkali soluble resin Multifunctional acrylate photopolymerizable compound Cardole photopolymerizable compound Photopolymerization initiator solvent additive total A B C f D. E. G 1 A-1 B-1 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 2 A-2 B-1 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 3 A-3 B-1 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 4 A-4 B-1 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 5 A-5 B-1 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 6 A-1 B-1 0.65 F-1 0.22 7.5 0.04 10 0.07 1.09 0.43 7 A-1 B-1 0.65 F-2 0.22 7.5 0.04 10 0.07 1.09 0.43 8 A-1 B-1 0.65 F-3 0.22 7.5 0.04 10 0.07 1.09 0.43 9 A-1 B-1 0.81 - 0.22 7.5 0.04 10 0.13 1.3 0 10 A-1 B-1 0.75 - 0.21 7.5 0.04 10 0.2 1.3 0 11 A-1 B-1 0.6 F-1 0.22 7.5 0.04 10 0.13 1.09 0.42 12 A-1 B-1 0.6 F-1 0.21 7.5 0.04 10 0.2 1.04 0.41 13 A-1 B-2 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 14 A-1 B-3 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 15 A-1 B-4 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 16 A-1 B-5 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 17 A-1 B-6 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0

（a） B-1：合成例1的咔哚系鹼溶性樹脂 B-2：合成例2的咔哚系鹼溶性樹脂 B-3：合成例3的咔哚系鹼溶性樹脂 B-4：合成例4的咔哚系鹼溶性樹脂 B-5：合成例5的咔哚系鹼溶性樹脂 B-6：合成例6的咔哚系鹼溶性樹脂 C：二新戊四醇六丙烯酸酯（購自Nippon Kayaku公司） F-1：由式（XVIII）所表示的化合物 F-2：由式（XXI）所表示的化合物 F-3：由式（XXII）所表示的化合物 D： 2-苄-2-二甲胺-1-（4- N-嗎福林苯）丁-1-酮（Irgacure 369，購自汽巴精化） E：丙二醇單甲醚乙酸酯 G：N-2-（胺乙基）-8-胺辛三甲氧矽烷（KBM-6803，購自信越化學工業） Table 2 comparative example polythiol compound Alkali soluble resin Multifunctional acrylate photopolymerizable compound Cardole photopolymerizable compound Photopolymerization initiator solvent additive total A B C f D. E. G 1 - B-1 0.83 - 0.23 7.5 0.04 10 0 1.4 0 2 A-6 B-1 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 3 A-7 B-1 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 4 A-8 B-1 0.87 - 0.22 7.5 0.04 10 0.07 1.3 0 5 A-1 B-1 0.79 - 0.2 7.5 0.04 10 0.29 1.18 0 6 A-1 B-1 0.00 F-1 0.22 7.5 0.04 10 0.07 1.30 0.87 A-1: Polythiol compound represented by formula (IV) A-2: Polythiol compound represented by formula (V) A-3: Polythiol compound represented by formula (VI) A- 4: Polythiol compound represented by formula (VII) A-5: Polythiol compound represented by formula (VIII) A-6: Tetraethylene glycol bis(3-hydrothiopropionate) (EGMP -4, available from SC Organic Chemical Company) A-7: 1,4-bis(3-hydrothiobutoxy)butane (available from Showa Denko) A-8: Acetylene represented by the following formula (a) Urea derivatives (TS-G, purchased from Shikoku Chemical Industries)

(a) B-1: Cardole-based alkali-soluble resin of Synthesis Example 1 B-2: Cardole-based alkali-soluble resin of Synthesis Example 2 B-3: Cardole-based alkali-soluble resin of Synthesis Example 3 B-4: Synthesis Cardole-based alkali-soluble resin B-5 of Example 4: cardole-based alkali-soluble resin B-6 of Synthesis Example 5: cardole-based alkali-soluble resin C of Synthesis Example 6: Dineopentaerythritol hexaacrylate (purchased from Nippon Kayaku Corporation) F-1: compound represented by formula (XVIII) F-2: compound represented by formula (XXI) F-3: compound represented by formula (XXII) D: 2-benzyl-2 -Dimethylamine-1-(4-N-morpholine benzene)butan-1-one (Irgacure 369, purchased from Ciba Specialty Chemicals) E: Propylene glycol monomethyl ether acetate G: N-2-(amine Ethyl)-8-aminooctyl trimethoxysilane (KBM-6803, purchased from Xinyue Chemical Industry)

Experimental example 1 : Evaluation of Pattern Physical Properties

Patterns were prepared as follows by using the photosensitive resin compositions prepared in Examples and Comparative Examples.

The patterns were evaluated for refractive index, developing speed, residue, adhesive properties, surface hardness, and chemical resistance to TMAH and DPHA as follows, and the results are shown in Table 3 below.

＜How to prepare the pattern＞

A 5 cm x 5 cm glass substrate (Eagle 2000, purchased from Corning Incorporated) was sequentially washed with neutral detergent, water and ethanol, and then dried. The photosensitive resin composition manufactured for each Example and the comparative example was spin-coated on the glass substrate, and it prebaked at 80 degreeC for 120 second on the hotplate after that. After the pre-baked glass substrate was cooled to room temperature, the substrate was irradiated with exposure equipment (MA6, purchased from Karl suss) at an exposure dose of 30 mJ/cm2 (based on 365 nm), and the quartz glass The reticle distance was set to 50 μm.

The mask had circular openings (dot patterns) with diameters of 5 µm, 10 µm, 20 µm, and 30 µm, with patterns formed at intervals of 30 µm on the same plane. After light irradiation, the substrate was developed for 60 seconds in an aqueous solution of 2.38% tetramethylammonium hydroxide (TMAH), washed with ultrapure water, and dried under nitrogen to form a pattern on the photosensitive resin composition. Post drying was performed in an oven at 85°C for 2 hours.

( 1 ) Refractive Index Measurement

In the same way as in the pattern preparation method, incident angles of 65°, 70° and 75° were applied to the cured film formed by exposure, but without using a photomask, an ellipsometer (M-2000, available from JA Woollam Co.) Linear polarization is measured in the wavelength range from 200nm to 1000nm at 25°C and 50% relative humidity. Using the Complete EASE software, use the Cauchy model of the following equation 1 to fit the measured data of linear polarization (ellipsometry data (Ψ, Δ)) to make the MSE equal to or less than 70, and calculate the refractive index at a wavelength of 550 nm. [Formula 1]

In Equation 1, n(λ) is the refractive index at λ wavelength, λ is in the range of 200 nm to 1000 nm, and A, B, and C are Cauchy parameters.

( 2 ) The developing speed of the non-exposed part

The substrate prebaked by the pattern preparation method was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution to measure the time for the photosensitive resin composition to completely dissolve, and the developing speed was evaluated according to the following evaluation criteria. ＜Evaluation criteria＞ Development Speed: Recording times rounded to 10 second increments No development within 120 seconds: ×

( 3 )the remains

The presence or absence of residue around the dot pattern obtained by the pattern preparation method was observed using an optical microscope, and evaluated according to the following evaluation criteria. ＜Evaluation criteria＞ No residue: O Residue observed: ×

( 4 ) Adhesive properties

The minimum mask size in which 90% or more of the dot patterns obtained by the pattern preparation method is adhered to the lower substrate was measured, and evaluated according to the following evaluation criteria. ＜Evaluation criteria＞ 5 micron dot pattern with 90% adhesion or better: 5 90% or better adhesion of 10 micron dot pattern: 10 20 micron dot pattern with 90% or more adhesion: 20 30 micron dot pattern with 90% or more adhesion: 30 Undeveloped or lost pattern: ×

( 5 )Surface hardness

A hardness meter (HM500, available from Fischer Co.) was used to measure the degree of curing of the cured film formed by exposure in the pattern preparation method (but without using a photomask). Surface hardness was evaluated by the following evaluation criteria. ＜Evaluation criteria＞ ◎: Surface hardness 40 or above ○: Surface hardness 30 or more and less than 40 △: Surface hardness 10 or more and less than 30 ×: surface hardness is less than 10

( 6 )right 2.38% TMAH chemical resistance

The cured film formed by the pattern preparation method (but without using a photomask) was immersed in 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 2 minutes to measure the change of film thickness (unit: μm).

( 7 )right DPHA chemical resistance

Dineopenylthritol hexaacrylate (DPHA) was added dropwise to the cured film formed by the pattern preparation method (but without using a photomask) and left for 2 minutes. The film was washed with ultrapure water and dried under nitrogen to measure the change in film thickness (unit: micron).

table 3 Refractive index Development speed the remains Adhesive properties Surface hardness Chemical resistance to 2.38% TMAH Chemoresistance to DPHA Example 1 1.63 20 ○ 20 ○ -0.09 0.02 2 1.62 20 ○ 20 ○ -0.09 0.03 3 1.62 20 ○ 20 ○ -0.09 0.03 4 1.63 20 ○ 20 ○ -0.1 0.05 5 1.63 20 ○ 20 ○ -0.12 0.07 6 1.65 30 ○ 10 ○ -0.07 0.03 7 1.66 30 ○ 10 ○ -0.08 0.02 8 1.65 30 ○ 10 ○ -0.08 0.02 9 1.66 30 ○ 10 ○ -0.05 0.03 10 1.66 30 ○ 10 ○ -0.03 0.02 11 1.67 30 ○ 5 ○ -0.01 0.01 12 1.67 30 ○ 5 ○ -0.01 0 13 1.63 30 ○ 10 ○ -0.1 0.03 14 1.63 30 ○ 10 ○ -0.09 0.03 15 1.63 30 ○ 10 ○ -0.1 0.04 16 1.69 20 ○ 10 ◎ -0.01 0 17 1.69 20 ○ 10 ◎ -0.02 0.01 comparative example 1 1.56 20 ○ 30 x -0.31 0.54 2 1.57 50 ○ 20 △ -0.15 0.32 3 1.57 50 ○ 20 △ -0.13 0.31 4 1.57 50 ○ 20 △ -0.14 0.27 5 1.6 x x 20 ○ -0.23 0.17 6 - - - - - - -

As shown in Table 3, from Examples 1 to 17, the photosensitive resin composition containing the polythiol compound of a specific structure without using inorganic particles can form a pattern exhibiting a high refractive index of 1.60 or more at a wavelength of 550 nm . In addition, the photosensitive resin compositions of Examples 1 to 17 exhibited excellent pattern properties, such as development speed, residue, adhesive properties, and surface hardness, even when cured below 100°C, and were resistant to developer And the monomer has excellent chemical resistance.

On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 4, which do not contain a polythiol compound of a specific structure, exhibited a refractive index of less than 1.60 at a wavelength of 550 nm, and exhibited a high performance in terms of developing speed, residue, and adhesion characteristics. Any one or more of surface hardness and surface hardness have poor physical properties. In addition, the photosensitive resin compositions of Comparative Examples 1 to 4 had poor chemical resistance to the developer used in the developing process and the monomer used to form another pattern in the post-processing process, resulting in severe film loss and film loss. swelling.

In addition, the photosensitive resin composition in Comparative Example 5, based on 100% by weight of the total solid content in the photosensitive resin composition, contained more than 10% by weight of the polythiol compound, and had poor developing speed, residue and Chemical resistance to developers and monomers.

In addition, the photosensitive resin composition in Comparative Example 6 did not contain a polyfunctional acrylate photopolymerizable compound, and the exposed portion was dissolved in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, so that no coating film was formed. Therefore, its characteristics cannot be confirmed.

Although specific embodiments of the present invention have been described and illustrated, those skilled in the art will understand that it is not intended to limit the invention to the preferred embodiments, and those skilled in the art It will be apparent that various changes and modifications can be made without departing from the spirit and scope of the invention.

The scope of the invention is defined by the appended claims and their equivalents.

:none.

:none.

:none.

Claims (12)

A photosensitive resin composition comprising a polythiol compound represented by the following formula (I), an alkali-soluble resin, a multifunctional acrylate photopolymerizable compound, a photopolymerization initiator, and a solvent:

(I) wherein, R is a k-valent aliphatic hydrocarbon group containing a sulfur atom, or a k-valent alicyclic hydrocarbon group containing a sulfur atom; and k is an integer of 2 to 6. The photosensitive resin composition according to claim 1, wherein the polythiol compound represented by the formula (I) includes a polythiol compound represented by the following formula (II) or formula (III):

(II)

(III) Among them, R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom or -CH ₂ -SH; ^Re , R ^f , R ^g and ^Rh are each independently a hydrogen atom or -CH ₂ -SH , and at least two of R ^e , R ^f , R ^g and ^Rh are —CH ₂ —SH; d is an integer of 1 to 2; and e is an integer of 0 to 2. The photosensitive resin composition according to claim 1, wherein the polythiol compound represented by the formula (I) comprises a polythiol represented by any one of the following formulas (IV) to (VIII) Compound:

(IV)

(V)

(VI)

(VII)

(VIII). The photosensitive resin composition according to claim 1, wherein, based on 100% by weight of the total solid content in the photosensitive resin composition, the content of the polythiol compound represented by formula (I) is 0.1 to 10% by weight. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin comprises at least one of the repeating units represented by the following formulas (IX) to (XIV):

(IX)

(X)

(XI)

(XII)

(XIII)

(XIV) Wherein, X and X' are each independently a single bond, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C( CH ₃ ) ₂ -, -O-,

,

,

,

,

,

,

,

,

,

,

,

or

; Y is the residue of an acid anhydride; Z is the residue of an acid dianhydride; R' is a hydrogen atom, ethyl, phenyl, -C ₂ H ₄ Cl, -C ₂ H ₄ OH or -CH ₂ CH=CH ₂ , R1, R1', R2, R2', R3, R3', R4, R4', R5, R5', R6 and R6' are each independently a hydrogen atom or a methyl group; R7, R7', R8 and R8' are independently C ₁ to C ₆ alkylene group, wherein the alkylene group is inserted with an ester bond, C ₆ to C ₁₄ cycloalkylene group, at least one of aryl group or no insertion; R9, R9', R10 , R10', R11, R11', R12 and R12' are each independently a hydrogen atom, a halogen atom or a C ₁ to C ₆ alkyl group; m and n are each independently an integer from 1 to 30; t and u are each independently 0 Integers from to 1; P are each independently

,

,

,

or

; R13 and R14 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogen atom; Ar1 is each independently an aryl group; Y' is an acid anhydride residue; Z' is an acid dianhydride residue; A is O, S, NR', Si(R') ₂ or Se; a and b are each independently an integer of 1 to 6; and p and q are each independently an integer of 1 to 30. The photosensitive resin composition as described in Claim 5, wherein the acid anhydride is selected from the following group: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, six Hydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorobridge anhydride, and methyltetrahydrophthalic anhydride. The photosensitive resin composition as described in Claim 5, wherein the acid dianhydride is selected from the following groups: pyromelteric dianhydride, benzophenonetetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, Carboxylic dianhydride and biphenylethertetracarboxylic dianhydride. The photosensitive resin composition according to Claim 1, further comprising a cardo-based photopolymerizable compound represented by any one of the following formulas (XV) to (XVII):

(XV)

(XVI)

(XVII) wherein, R15 and R16 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amine group, a nitro group, a halogen atom, or a polymerizable functional group of 2 to 20 carbons having an unsaturated double bond, and R15 and R16 At least one of them is a polymerizable functional group of 2 to 20 carbons having an unsaturated double bond. The photosensitive resin composition as described in Claim 8, wherein R15 and R16 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amino group, a nitro group, a halogen atom or

, and at least one of R15 and R16 is

; R17 is C ₁ to C ₆ alkylene group, and the alkylene system is inserted with an ester bond, C ₆ to C ₁₄ cycloalkylene group, at least one of arylene group or no insertion; and R18 is hydrogen atom or methyl. The photosensitive resin composition according to claim 1, which does not contain inorganic particles. A protrusion pattern formed by using the photosensitive resin composition described in any one of Claims 1 to 10. A display device comprising the protruding pattern as claimed in claim 11.