KR20230030466A - 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 protruding pattern and an image display device using the same. The photosensitive resin composition according to the present invention can form a pattern showing a high refractive index without using inorganic particles, and thus has excellent pattern characteristics and chemical resistance even when cured at a low temperature.

Description

Photosensitive resin composition, protrusion pattern and image display device using the same {Photosensitive Resin Composition, Protrusion Pattern and Display Device Using the Same}

The present invention relates to a photosensitive resin composition, a protruding pattern and an image display device using the same, and more particularly, a pattern exhibiting a high refractive index can be formed without using inorganic particles, and the pattern characteristics and durability even when cured at a low temperature It relates to a photosensitive resin composition with excellent chemical properties, a protruding pattern and an image display device using the same.

An organic light emitting diode (OLED) is expected to be a next-generation display and lighting device due to its advantages such as fast response speed, wide viewing angle, and low voltage driving.

In general, in an OLED, an organic material layer made of a light emitting material or a charge transfer material is positioned between an upper electrode and a lower electrode. The OLED has a structure in which materials having different refractive indices are stacked, and since reflection occurs at the interface of these materials, the light extraction efficiency to the outside is low.

Specifically, the refractive index of the organic light emitting layer constituting the OLED is approximately 1.7, the refractive index of ITO used as a transparent electrode is 2.0, and the refractive index of the glass substrate is 1.5. In this case, the ratio of unextractable guided light trapped in the transparent electrode or organic layer is about 45%, and the ratio of substrate guided light trapped in the substrate and unextractable is about 35%. Therefore, only about 20% of the light emitted from the OLED is extracted to the outside.

Various studies are being conducted to solve this problem, and a representative example is a micro lens array. The microlens array serves to increase the light extraction efficiency by changing the angle incident on the interface between the glass substrate and the air surface of the OLED device.

The micro lens array must exhibit a high refractive index higher than that of the glass substrate. In general, inorganic particles have a higher refractive index than organic particles, but 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 poor, resulting in a flexible image. Difficult to apply to display devices.

Therefore, it is necessary to develop a photosensitive resin composition capable of forming a pattern having a refractive index higher than that of a glass substrate without using inorganic particles.

In addition, in order to apply to a flexible image display device, it is required to develop a photosensitive resin composition having excellent chemical resistance that exhibits excellent pattern characteristics even when cured at a low temperature and has no change in film thickness even during post-processing.

Republic of Korea Patent Publication No. 10-2021-0052452

One object of the present invention is to provide a photosensitive resin composition capable of forming a pattern showing a high refractive index without using inorganic particles, and having excellent pattern characteristics and chemical resistance even when cured at a low temperature.

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

Another object of the present invention is to provide an image display device including the protruding pattern.

On the other hand, the present invention provides a photosensitive resin composition comprising an alkali-soluble resin containing at least one repeating unit of Formulas 1 to 6, a cardo-based photopolymerizable compound, a multifunctional acrylate photopolymerizable compound, a photopolymerization initiator, and a solvent. do.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In the above formula,

,

,

,

,

,

,

,

,

,

,

,

또는

이고,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

ego,

Y is an acid anhydride residue,

Z is an acid dianhydride moiety;

R' is a hydrogen atom, an ethyl group, a phenyl group, -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 each independently a C ₁ -C ₆ alkylene group, and the alkylene group is interposed with or without at least one of an ester bond, a C ₆ -C ₁₄ cycloalkylene group and an arylene group, ,

R9, R9', R10, R10', R11, R11', R12 and R12' are each independently a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,

m and n are each independently an integer from 1 to 30;

t and u are each independently an integer from 0 to 1,

,

,

,

또는

이고,P is each independently

,

,

,

or

ego,

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 moiety;

A is O, S, NR', Si(R') ₂ or Se;

a and b are each independently an integer from 1 to 6,

p and q are each independently an integer of 1 to 30;

In the photosensitive resin composition according to an embodiment of the present invention, a cured coating film may exhibit a refractive index of 1.60 or more at a wavelength of 550 nm.

In one embodiment of the present invention, the acid anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride and methyl anhydride. It may be selected from the group consisting of tetrahydrophthalic acid.

In one embodiment of the present invention, the acid dianhydride may be selected from the group consisting of pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenylethertetracarboxylic dianhydride.

In one embodiment of the present invention, the cardo-based photopolymerizable compound may include a compound represented by any one of Chemical Formulas 7 to 9 below.

[Formula 7]

[Formula 8]

[Formula 9]

In the above formula,

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 a polymerizable functional group having 2 to 20 carbon atoms having an unsaturated double bond, and at least one of R15 or R16 has an unsaturated double bond It is a polymerizable functional group having 2 to 20 carbon atoms.

이고, R15 또는 R16 중 적어도 하나는

이며, In one embodiment of the present invention, 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 or R16

is,

R17 is a C ₁ -C ₆ alkylene group, and the alkylene group is interposed with or without at least one of an ester bond, a C ₆ -C ₁₄ cycloalkylene group, and an arylene group;

R18 may be a hydrogen atom or a methyl group.

In one embodiment of the present invention, the cardo-based photopolymerizable compound may be included in an amount of 30 to 70 parts by weight based on 100 parts by weight of the alkali-soluble resin.

In one embodiment of the present invention, the multifunctional acrylate photopolymerizable compound may be included in an amount of 30 to 120 parts by weight based on 100 parts by weight of the alkali-soluble resin.

The photosensitive resin composition according to an embodiment of the present invention may further include a multifunctional thiol compound.

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

On the other hand, the present invention provides a protruding pattern formed using the photosensitive resin composition.

On the other hand, the present invention provides an image display device including the protruding pattern.

The photosensitive resin composition according to the present invention uses a cardo-based alkali-soluble resin, a cardo-based photopolymerizable compound, and a multifunctional acrylate photopolymerizable compound including a repeating unit having a specific structure, and thus has a photopolymerizable value of 1.60 or more at a wavelength of 550 nm without using inorganic particles. It can form a pattern showing a high refractive index, and has excellent pattern characteristics such as development speed, residue, adhesion, and surface hardness characteristics even when cured at a low temperature, and has excellent chemical resistance to developers and monomers.

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention is a photosensitive resin composition comprising an alkali-soluble resin (A), a cardo-based photopolymerizable compound (B), a multifunctional acrylate photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E). It is about.

The photosensitive resin composition according to an embodiment of the present invention uses a cardo-based alkali-soluble resin, a cardo-based photopolymerizable compound, and a multifunctional acrylate photopolymerizable compound including a repeating unit having a specific structure, so that a 550 nm photopolymerizable compound can be obtained without using inorganic particles. A pattern exhibiting a high refractive index of 1.60 or more at a wavelength, for example, 1.60 to 1.7 may be formed. Therefore, the insulating film patterned through the photolithography process using the photosensitive resin composition according to an embodiment of the present invention can be used as a light extraction material for a self-light emitting device, and thus the light extraction efficiency of light emitted from the self-light emitting device. and the luminance of light emission can be greatly improved.

In addition, the photosensitive resin composition according to an embodiment of the present invention exhibits a ratio of development rates so that an exposed portion and an unexposed portion are clear even when cured at a low temperature, has excellent pattern characteristics such as residue, adhesion, surface hardness characteristics, and excellent curing degree. As a result, it has excellent chemical resistance to developers and/or monomers used in the post-process.

Alkali-soluble resin (A)

In one embodiment of the present invention, the alkali-soluble resin (A) is a component that usually has reactivity by the action of light or heat and imparts solubility to an alkali developing solution used in the developing process when forming a pattern.

The alkali-soluble resin (A) includes a cardo-based alkali-soluble resin. The cardo-based alkali-soluble resin includes at least one repeating unit of Formulas 1 to 6 below.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In the above formula,

,

,

,

,

,

,

,

,

,

,

,

또는

이고,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

ego,

Y is an acid anhydride residue,

Z is an acid dianhydride moiety;

R' is a hydrogen atom, an ethyl group, a phenyl group, -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 each independently a C ₁ -C ₆ alkylene group, and the alkylene group is interposed with or without at least one of an ester bond, a C ₆ -C ₁₄ cycloalkylene group and an arylene group, ,

R9, R9', R10, R10', R11, R11', R12 and R12' are each independently a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,

m and n are each independently an integer from 1 to 30;

t and u are each independently an integer from 0 to 1,

,

,

,

또는

이고,P is each independently

,

,

,

or

ego,

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 moiety;

A is O, S, NR', Si(R') ₂ or Se;

a and b are each independently an integer from 1 to 6,

p and q are each independently an integer of 1 to 30;

As used herein, the C ₁ -C ₆ alkylene group refers to a straight-chain or branched divalent hydrocarbon having 1 to 6 carbon atoms, and includes, for example, methylene, ethylene, propylene, butylene, etc., but is limited thereto. it is not going to be

As used herein, the C ₆ -C ₁₄ cycloalkylene group refers to a simple or fused cyclic divalent hydrocarbon having 6 to 14 carbon atoms, and examples thereof include cyclohexylene, cycloheptylene, and cyclooctylene. but is not limited thereto.

The arylene group used herein includes both divalent aromatic groups, heteroaromatic groups, and partially reduced derivatives thereof. The aromatic group is a 5- to 15-membered simple or fused ring, and the heteroaromatic group refers to an aromatic group containing at least one oxygen, sulfur, or nitrogen. Examples of representative arylene groups include phenylene, naphthylene, pyridinylene, furanylene, thiophenylene, indolylene, quinolinylene, imidazolinylene ( imidazolinylene), oxazolylene, thiazolylene, tetrahydronaphthylene, etc., but are not limited thereto.

As used herein, the C ₁ -C ₆ alkyl group refers to a straight-chain or branched monovalent hydrocarbon having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, i-propyl, and n-butyl. , i-butyl, t-butyl, n-pentyl, n-hexyl, and the like, but are not limited thereto.

The aryl group used herein includes both monovalent aromatic groups, heteroaromatic groups, and partially reduced derivatives thereof. The aromatic group is a 5- to 15-membered simple or fused ring, and the heteroaromatic group refers to an aromatic group containing at least one oxygen, sulfur, or nitrogen. Representative examples of aryl groups include phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, oxazolyl, thiazolyl, tetrahydronaphthyl, etc., but are not limited thereto.

The acid anhydride residue used herein can be obtained by reacting the synthetic intermediate of the cardo-based resin of the present invention with an acid anhydride. The acid anhydride into which the acid anhydride residue can be introduced is not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylendomethylenetetrahydrophthalic anhydride. , chlorendic acid anhydride, methyltetrahydrophthalic anhydride, and the like. These acid anhydrides may be used alone or in combination of two or more.

The acid dianhydride residue used herein can be obtained by reacting the synthetic intermediate of the cardo-based resin of the present invention with acid dianhydride. The acid dianhydride capable of introducing an acid dianhydride residue is not particularly limited, and examples thereof include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenylethertetracar. A boxylic acid dianhydride etc. are mentioned. These acid dianhydrides may be used alone or in combination of two or more.

In the present specification, the acid dianhydride refers to a compound containing two acid anhydride groups in a molecule.

The photosensitive resin composition according to the present invention can form a pattern showing a high refractive index of 1.60 or more at a wavelength of 550 nm by including a cardo-based alkali-soluble resin containing at least one repeating unit of Formulas 1 to 6, even when cured at a low temperature. It has excellent pattern characteristics and excellent chemical resistance to developers and/or monomers used in post-processing.

The method for producing the cardo-based alkali-soluble resin is not particularly limited. For example, the cardo-based alkali-soluble resin is synthesized by reacting a bisphenol compound and an epoxy compound to synthesize a bisphenol epoxy compound, reacting the synthesized bisphenol epoxy compound with an acrylate compound to synthesize a bisphenol epoxy acrylate compound, and then synthesizing a bisphenol epoxy acrylic It can be prepared by reacting a rate compound with an acid anhydride, an acid dianhydride, or a mixture thereof.

The cardo-based alkali-soluble resin may have an acid value of 20 to 200 (KOH mg/g). When the acid value is in the above range, the solubility in the developing solution is improved, so that the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, a pattern of the exposed portion remains during development to improve the film remaining ratio, which is preferable. The acid value here is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the polymer, and can usually be obtained by titrating using an aqueous potassium hydroxide solution.

The weight average molecular weight in terms of polystyrene (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) of the cardo-based alkali-soluble resin is 1,000 g/mol to 30,000 It is preferably g/mol. When the weight average molecular weight is within the above range, the sensitivity of the non-exposed part to be dissolved in the developing solution is increased, and excellent chemical resistance can be exhibited in a post-process that proceeds after thermal curing, which is preferable.

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the cardo-based 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 reliability is excellent.

The alkali-soluble resin (A) may be included in an amount of 10 to 70% by weight, preferably 20 to 50% by weight, based on 100% by weight of the total solid content in the photosensitive resin composition. When the content of the alkali-soluble resin is less than 10% by weight, the sensitivity of the non-exposed part to be dissolved in the developing solution is lowered, and residue may be generated. there is.

In the present invention, the solid content in the photosensitive resin composition means the total of components from which the solvent has been removed.

Cardo-based photopolymerizable compound (B)

In one embodiment of the present invention, the cardo-based photopolymerizable compound (B) is a cardo-based compound that can be polymerized by the action of light and a photopolymerization initiator to be described later, and serves to increase the refractive index.

The cardo-based photopolymerizable compound may include a compound represented by any one of Chemical Formulas 7 to 9 below.

[Formula 7]

[Formula 8]

[Formula 9]

In the above formula,

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 a polymerizable functional group having 2 to 20 carbon atoms having an unsaturated double bond, and at least one of R15 or R16 has an unsaturated double bond It is a polymerizable functional group having 2 to 20 carbon atoms.

이고, R15 또는 R16 중 적어도 하나는

이며, In one embodiment of the present invention, 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 or R16

is,

R17 is a C ₁ -C ₆ alkylene group, and the alkylene group is interposed with or without at least one of an ester bond, a C ₆ -C ₁₄ cycloalkylene group, and an arylene group;

R18 may be a hydrogen atom or a methyl group.

Specifically, the cardo-based photopolymerizable compound may include a compound represented by any one of Chemical Formulas 10 to 14 below.

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

In one embodiment of the present invention, the cardo-based photopolymerizable compound may be included in an amount of 30 to 70 parts by weight, preferably 30 to 60 parts by weight, based on 100 parts by weight of the alkali-soluble resin. If the cardo-based photopolymerizable compound is included in an amount of less than 30 parts by weight based on 100 parts by weight of the alkali-soluble resin, the refractive index may not be improved, and if it is included in an amount of more than 70 parts by weight, the sensitivity of the non-exposed part to be dissolved in the developing solution is reduced and residues may occur.

The cardo-based photopolymerizable compound (B) may be included in an amount of 5 to 50% by weight, preferably 10 to 30% by weight, based on 100% by weight of the total solid content in the photosensitive resin composition. When the content of the cardo-based photopolymerizable compound is less than 5% by weight, the refractive index may not be improved, and when it is greater than 50% by weight, the sensitivity of the non-exposed portion to be dissolved in the developing solution is lowered, and residue may be generated.

Multifunctional acrylate photopolymerizable compound (C)

In one embodiment of the present invention, the multifunctional acrylate photopolymerizable compound (C) is a compound that can be polymerized by the action of light and a photopolymerization initiator to be described later, and is polymerized by an exposure process to improve mechanical properties such as hardness and adhesion of a pattern. It serves to improve the properties or supplement the developability of the alkali-soluble resin.

The multifunctional acrylate photopolymerizable compound is a compound having 2 or more, preferably 3 or more, more preferably 4 or more (meth)acryloyloxy groups in a molecule.

Examples of the multifunctional acrylate photopolymerizable compound include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triethylene glycol di( bifunctional acrylate photopolymerizable compounds such as meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate; Trifunctional such as trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate acrylate photopolymerizable compounds; tetrafunctional acrylate photopolymerizable compounds such as ditrimethylolpropanetetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate; Penta-functional acrylate photopolymerizable compounds, such as dipentaerythritol penta (meth)acrylate; and hexafunctional acrylate photopolymerizable compounds such as ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, or dipentaerythritol hexa(meth)acrylate. .

The polyfunctional acrylate photopolymerizable compounds exemplified above may be used alone or in combination of two or more.

In one embodiment of the present invention, the multifunctional acrylate photopolymerizable compound may be included in an amount of 30 to 120 parts by weight, preferably 40 to 110 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the polyfunctional acrylate photopolymerizable compound is included in an amount of less than 30 parts by weight based on 100 parts by weight of the alkali-soluble resin, the photocuring degree is lowered so that the exposed part can be dissolved in the developer, and when it is included in an amount of more than 120 parts by weight, the lower portion Residues may be generated on the substrate or the refractive index may be lowered.

The multifunctional acrylate photopolymerizable compound (C) may be included in an amount of 5 to 80% by weight, preferably 10 to 60% by weight, based on 100% by weight of the total solid content in the photosensitive resin composition. When the content of the polyfunctional acrylate photopolymerizable compound is less than 5% by weight, the photocuring degree is lowered and the exposed portion may be dissolved in the developer, and when it is greater than 80% by weight, residue may be generated on the lower substrate or the refractive index may be lowered. can

Photopolymerization initiator (D)

In one embodiment of the present invention, the photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the cardo-based photopolymerizable compound (B) and the multifunctional acrylate photopolymerizable compound (C). . In particular, the photopolymerization initiator (D) is acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, oxime-based compounds and It is preferred to use at least one compound selected from the group consisting of thioxanthone-based compounds, and particularly preferred are acetophenone-based compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyl) Roxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1 -one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra ( tert-butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine; and the like.

Specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4 , 4',5,5'-tetraphenyl-1,2'-biimidazole or a biimidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group; and the like there is. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferred. used

Specific examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octadione, -1-(4-phenylthio)phenyl, -2- (o-benzoyloxime), ethanone, -1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-,1-(o-acetyloxime), etc., commercially available as CGI -124 (Ciba Geigy Co.), CGI-224 (Ciba Gei Co.), Irgacure OXE-01 (BASF Co.), Irgacure OXE-02 (BASF Co.), N-1919 (Adecas Co.), NCI-831 (Adecas Co.) etc. can be mentioned.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. there is

Further, a photopolymerization initiator other than the above may be further used in combination within a range not impairing the effects of the present invention. Examples thereof include benzoin-based compounds and anthracene-based compounds, which may 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, and benzoin isobutyl ether.

Examples of the anthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. there is.

In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenyl cyclooxylate or A titanocene compound or the like can be further used in combination as a photopolymerization initiator.

The photopolymerization initiator (D) may be included in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, based on 100% by weight of the total solid content in the photosensitive resin composition. The above content range takes into consideration the photopolymerization rate and the physical properties of the finally obtained coating film. If it is less than the above range, the polymerization rate is low and the overall process time may be lengthened. Since this may rather deteriorate, it is appropriately used within the above range.

In addition, a photopolymerization initiation auxiliary agent may be used together with the photopolymerization initiator. When the photopolymerization initiation auxiliary agent is used together with the photopolymerization initiator, the photosensitive resin composition becomes more sensitive and productivity is improved, so it is preferable. As the photopolymerization initiation aid, one or more compounds selected from the group consisting of amines and carboxylic acid compounds may be preferably used.

It is preferable to use such a photopolymerization initiation aid within the range of usually 10 moles or less, preferably 0.01 to 5 moles, per mole of the photopolymerization initiator. When the photopolymerization initiation aid is used within the above range, an effect of improving productivity can be expected by increasing the polymerization efficiency.

Solvent (E)

In one embodiment of the present invention, the solvent contained in the photosensitive resin composition is not particularly limited, and various organic 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, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol. Diethylene glycol dialkyl ethers such as dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Alkylene glycol alkyl ether acetates such as ethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone, Ketones such as methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Cyclic esters, such as esters, such as methyl, and (gamma)-butyrolactone, etc. are mentioned.

Among the above solvents, organic solvents having a boiling point of 100 ° C to 200 ° C are preferably used in terms of coating properties and drying properties, and more preferably, alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate or , esters such as 3-methoxymethylpropionate may be used, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxyethylpropionate, 3-methoxypropionic acid methyl and the like can be used. These solvents can be used individually or in mixture of two or more types, respectively.

The solvent (E) may be included in an amount of usually 60 to 90% by weight, preferably 70 to 85% by weight, based on 100% by weight of the entire photosensitive resin composition. When the above range is satisfied, coating properties tend to be good when applied with a coating device such as a roll coater, spin coater, slit-and-spin coater, slit coater (sometimes referred to as a die coater), or inkjet, which is preferable. .

Multifunctional thiol compound (F)

The photosensitive resin composition according to an embodiment of the present invention may further include a multifunctional thiol compound (F).

The multifunctional thiol compound (F) is a component that serves to improve the degree of curing and increase the refractive index of the pattern, and is a compound having two or more, preferably three or more thiol groups in a molecule.

For example, the Multifunctional thiol compounds include butane-1,4-diyl bis(mercaptoacetate), ethoxylated pentaerythritol tetra(3-mercaptopropionate), trimethylolpropanetri(3-mercaptopropionate), trimethyl All-propane tri(3-mercaptoacetate), glycol di-(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), glycol dimercapto acetate, ethoxylated glycol dimercapto Acetate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, 1,3,5-tris(3-mercapto Butyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), 1,6-hexanedithiol, 1,3-propane It may be dithiol, 1,2-ethanedithiol, polyethylene glycol dithiol containing 1 to 10 ethylene glycol repeating units, or a combination thereof.

The multifunctional thiol compound (F) may be included in an amount of 20% by weight or less, for example, 0.5 to 20% by weight, preferably 1 to 10% by weight, based on 100% by weight of the total solid content in the photosensitive resin composition. When the content of the polyfunctional thiol compound is greater than 20% by weight, the non-exposed portion may not be developed in a developing solution.

Additive (G)

The photosensitive resin composition according to an embodiment of the present invention may further include additives such as a surfactant, an adhesion promoter, and an antioxidant in addition to the above components, if necessary.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethylene. In addition to this, there are products such as KP (manufactured by Shin-Etsu Chemical High School Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), and Mega Pack. (MEGAFAC) (manufactured by Dainippon Ink Kagaku Kogyo Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (SOLSPERSE) (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by Ajinomoto Co., Ltd.), and DISPER BYK (manufactured by BYK).

As said adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-8-aminooctyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. are mentioned.

Specific examples of antioxidants include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

The additive may be included in an amount of 10% by weight or less, for example, 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on 100% by weight of the total solid content in the photosensitive resin composition, but is not limited thereto.

The photosensitive resin composition according to an embodiment of the present invention may not include inorganic particles. That is, the photosensitive resin composition according to an embodiment of the present invention may not include scattering particles such as metal oxide particles, eg, inorganic particles such as fillers such as glass, silica, and alumina.

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

One embodiment of the present invention relates to a protruding pattern formed using the photosensitive resin composition described above.

The protruding pattern may be used in a microlens array used to increase light extraction efficiency of a self-luminous device.

The protruding pattern may have a hemispherical shape, a trapezoidal shape, or a conical shape.

The protruding pattern may be formed by applying the above-described photosensitive resin composition on a substrate, exposing and developing in a predetermined pattern, and then post-baking.

First, the photosensitive resin composition of the present invention is applied to a substrate and then heated and dried to remove volatile components such as a solvent to obtain a smooth coating film.

Examples of the coating method include inkjet printing, spin coating, casting coating, roll coating, slit and spin coating, and slit coating.

After application, heat drying (pre-bake) or reduced pressure drying is followed by heating to volatilize volatile components such as a solvent. At this time, the heating temperature is relatively low, 70 to 100 ° C.

The coating film obtained in this way is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated to the entire exposure area and accurate positioning of the mask and the substrate is performed. When irradiated with ultraviolet rays, the portion irradiated with ultraviolet rays is cured.

As the ultraviolet rays, g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), and the like may be used. The irradiation amount of ultraviolet rays can be appropriately selected as needed.

Thereafter, a process of developing by dissolving the unexposed portion by contacting the cured coating film with a developing solution is performed.

The developing method may be any of a liquid addition method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development.

After development, it is washed with water, and post-bake is performed at a relatively low temperature of 70 to 100° C. for 10 to 60 minutes.

One embodiment of the present invention relates to an image display device including the above-described protruding pattern. The image display device may include, but is not limited to, a liquid crystal display (LCD), an organic light emitting diode (OLED), and the like, and may include all image display devices known in the art that can be applied. In particular, the image display device may be a flexible display.

Hereinafter, the present invention will be described in more detail by Examples, Comparative Examples and Experimental Examples. These Examples, Comparative Examples and Experimental Examples are only for explaining 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: Cardo-based alkali-soluble resin (A-1)

In a reactor, bisphenol epoxy compound 9,9'-bis(4-glycidyloxyphenyl)fluorene (Hear chem) 138g, 2-carboxyethyl acrylate (2-carboxyethyl acrylate) 54g, benzyltriethylammonium chloride ( Daejeong Chemical Co.) 1.4 g, triphenylphosphine (Aldrich Co.) 1 g, propylene glycol methylethyl acetate (Daicel Chemical Co.) 128 g, and hydroquinone 0.5 g were heated to 120 ° C and maintained for 12 hours to obtain the following chemical formula 11 The compound represented by was synthesized.

In a reactor, 60 g of the compound represented by Formula 11, 11 g of biphenyltetracarboxylic di-anhydride (Mitsubishi Gas Co.), 3 g of tetrahydrophthalic anhydride (Aldrich Co.), 20 g of propylene glycol methylethyl acetate (Daicel Chemical Co.), and N After adding 0.1 g of N'-tetramethylammonium chloride, the temperature was raised to 120°C and maintained for 2 hours to synthesize a resin represented by Formula 15 below. The weight average molecular weight of the obtained resin was 5,400 g/mol.

[Formula 11]

[Formula 15]

Synthesis Example 2: Cardo-based alkali-soluble resin (A-2)

138g of bisphenol epoxy compound 9,9'-bis(4-glycidyloxyphenyl)fluorene (Hear chem), 54g of mono-2-acryloyloxyethyl succinate in a reactor , 1.4 g of benzyltriethylammonium chloride (Daejeong Chemical Co.), 1 g of triphenylphosphine (Aldrich Co.), 128 g of propyl glycol methyl ethyl acetate (Daicel Chemical Co.), and 0.5 g of hydroquinone were added, and the temperature was raised to 120° C. After holding the time, a compound represented by Formula 12 was synthesized.

In a reactor, 60 g of the compound represented by Chemical Formula 12, 11 g of biphenyltetracarboxylic di-anhydride (Mitsubishi Gas Co.), 3 g of tetrahydrophthalic anhydride (Aldrich Co.), 20 g of propyl glycol methylethyl acetate (Daicel Chemical Co.), and N After adding 0.1 g of N'-tetramethylammonium chlorite, the temperature was raised to 120°C and maintained for 2 hours to synthesize a resin represented by Formula 16 below. The weight average molecular weight of the obtained resin was 5,400 g/mol.

[Formula 12]

[Formula 16]

Synthesis Example 3: Cardo-based alkali-soluble resin (A-3)

In a 3000 ml three-neck round flask, 364.4 g of 3′,6′-dihydroxyspiro (fluorene-9,9-xanthene) and t-butylammonium bromide 0.4159g was mixed, and 2359g of epichlorohydrin was added and reacted by heating to 90 ° C. 3',6'-dihydroxyspiro (fluorene-9,9-xanthene) was completely consumed by liquid chromatography analysis. After cooling to 30 ° C, 50% NaOH aqueous solution (3 equivalents) was slowly added After analysis by liquid chromatography, epichlorohydrin was completely consumed, extracted with dichloromethane, washed with water three times, and dried with magnesium sulfate. After that, dichloromethane was distilled under reduced pressure and recrystallized using a mixed solvent of dichloromethane and methanol (50:50, v/v).

After mixing 1 equivalent of the epoxy compound thus synthesized with 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid, 24.89 g of the solvent propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was heated and dissolved at a temperature of 90 to 100° C. while blowing air at 25 ml/min. In a cloudy state, the reaction solution was completely dissolved by heating to 120°C. When the solution became clear and the viscosity increased, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH/g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of Formula 13 below.

[Formula 13]

After adding and dissolving 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Formula 13, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and the temperature was gradually raised to 110 to 115 ° C. for 4 hours. reacted After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to obtain a resin. Disappearance of anhydride was confirmed by IR spectrum.

Synthesis Example 4: Cardo-based alkali-soluble resin (A-4)

364.4g of 4,4′-(9H-xanthene-9,9-diyl)diphenol and t-butylammonium bromide in a 3000ml three-necked round flask 0.4159g was mixed, and 2359g of epichlorohydrin was added and heated to 90°C to react. When 4,4′-(9H-xanthene-9,9-diyl)diphenol (4,4′-(9H-xanthene-9,9-diyl)diphenol) is completely consumed by analyzing by liquid chromatography, After cooling, 50% NaOH aqueous solution (3 equivalents) was slowly added. When epichlorohydrin was completely consumed by liquid chromatography, it was extracted with dichloromethane, washed with water three times, and the organic layer was dried with magnesium sulfate, dichloromethane was distilled under reduced pressure, and a mixed solvent of dichloromethane and methanol (50:50 , v/v) was used to recrystallize.

After mixing 1 equivalent of the epoxy compound thus synthesized with 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid, 24.89 g of the solvent propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was heated and dissolved at a temperature of 90 to 100° C. while blowing air at 25 ml/min. In a cloudy state, the reaction solution was completely dissolved by heating to 120°C. When the solution became clear and the viscosity increased, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH/g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of Formula 14 below.

[Formula 14]

After adding and dissolving 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Formula 14, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and the temperature was gradually raised to 110 to 115° C. for 4 hours. reacted After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to obtain a resin. Disappearance of anhydride was confirmed by IR spectrum.

Synthesis Example 5: Cardo-based alkali-soluble resin (A-5)

Level 1

[Scheme 1]

After installing a reflux condenser and a thermometer in a three-necked flask, 42.5 g of 9,9-bisphenolfluorene was added and 220 mL of 2-(chloromethyl)oxirane was quantified. and then injected. After adding 100 mg of tetrabutylammonium bromide, the temperature was raised to 90° C. while stirring was started. After confirming that the unreacted material content was less than 0.3%, it was distilled under reduced pressure.

After lowering the temperature to 30° C., dichloromethane was injected, and NaOH was slowly added. After confirming that the product was 96% or more by high performance liquid chromatography (HPLC), the reaction was terminated by adding 5% HCl dropwise. After the reactants were extracted and layer separated, the organic layer was washed with water and washed to become neutral. The organic layer was dried with MgSO ₄ and concentrated by distillation under reduced pressure using a rotary evaporator. After adding dichloromethane to the concentrated product and stirring while raising the temperature to 40 ° C., methanol was added, and then the solution temperature was lowered and stirred. After filtering the produced solid, it was vacuum-dried at room temperature to obtain 52.7 g of a white solid powder (yield: 94%). The structure thereof was confirmed by ¹ H NMR.

¹ H NMR in CDCl ₃ : 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

[Scheme 2]

After installing a reflux condenser and a thermometer in a three-necked flask, the first step reactant (1000 g), thiophenol 524 g, and ethanol 617 g were added and stirred. 328 g of triethylamine was slowly added dropwise to the reaction solution. After confirming that the starting material disappeared by high-performance liquid chromatography (HPLC), the reaction was terminated. After completion of the reaction, ethanol was removed by distillation under reduced pressure. The organic matter was dissolved in dichloromethane, washed with water, and dichloromethane was removed by distillation under reduced pressure. After dissolving the concentrated organic matter in ethyl acetate, ether solvent was added dropwise and stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 945 g (yield: 64%) of pale yellow oil. Its structure was confirmed by ¹ H NMR.

¹ H NMR in CDCl ₃ : 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 reflux condenser and a thermometer in a three-necked flask, 3,3'-(((9H-fluorene-9,9-diyl)bis(4,1 -phenylene))bis(oxy))bis(1-phenylthio)propan-2-ol)(3,3'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene) 200 g of bis(oxy))bis(1-(phenylthio)propan-2-ol)) monomer was added and the temperature was raised to 115°C. After dropping 31.1 g of 3,3,'4,4'-biphenyltetracarboxylic dianhydride at 115 ° C, while maintaining 115 ° C for 6 hours stirred. After adding 7.35 g of phthalic anhydride and stirring for another 2 hours, the reaction was terminated. After cooling, a resin having a weight average molecular weight of 3,500 g/mol was obtained.

Synthesis Example 6: Cardo-based alkali-soluble resin (A-6)

After installing a reflux condenser and a thermometer in a three-necked flask, 3,3'-(((9H-fluorene-9,9-diyl)bis((9H-fluorene-9,9-diyl)bis( 4,1-phenylene))bis(oxy))bis(1-(phenylthio)propan-2-ol)(3,3'-(((9H-fluorene-9,9-diyl)bis(4, 200 g of 1-phenylene))bis(oxy))bis(1-(phenylthio)propan-2-ol)) monomer was added and the temperature was raised to 115°C. After dropping 21.1 g of pyromellitic dianhydride at 115°C, the mixture was stirred while maintaining 115°C for 6 hours. After adding 7.35 g of phthalic anhydride and stirring for another 2 hours, the reaction was terminated. After cooling, a resin having a weight average molecular weight of 4,500 g/mol was obtained.

Synthesis Example 7: Acrylic alkali-soluble resin (A-7)

In a three-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet tube, 100 parts by weight of propylene glycol monomethyl ether acetate, 100 parts by weight of propylene glycol monomethyl ether, 5 parts by weight of AIBN, 23.0 parts by weight of vinyl toluene, 4- 1.6 parts by weight of methyl styrene, 46.0 parts by weight of glycidyl methacrylate, and 3 parts by weight of n-dodecyl mercapto were added, followed by nitrogen substitution. Thereafter, while stirring, the temperature of the reaction solution was raised to 80° C. and reacted for 4 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and the atmosphere of the flask was changed from nitrogen to air. Then, 0.2 parts by weight of triethylamine, 0.1 part by weight of 4-methoxy phenol, and 23.3 parts by weight of acrylic acid were introduced and reacted at 100 ° C. for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 parts by weight of succinic anhydride was added, and the mixture was reacted at 80° C. for 6 hours.

The weight average molecular weight of the alkali-soluble resin thus synthesized was 3,350 g/mol.

Synthesis Example 8: Acrylic alkali-soluble resin (A-8)

120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 13.0 parts by weight of acrylic acid, benzyl methacrylic 10 parts by weight of latex, 57.0 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercapto were added, followed by nitrogen substitution. Thereafter, while stirring, the temperature of the reaction solution was raised to 80° C. and reacted for 8 hours.

The weight average molecular weight of the alkali-soluble resin thus synthesized was 14,950 g/mol.

Synthesis Example 9: Acrylic alkali-soluble resin (A-9)

In a 3-necked flask equipped with a reflux condenser, thermometer, dropping funnel, and nitrogen inlet tube, nitrogen was flowed at 0.02 L/min to create a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70° C. while stirring. Subsequently, 132.2 g (0.60 mol) of the compound represented by Formula 17, 55.3 g (0.30 mol) of 3-ethyl-3-oxetanyl methacrylate, and 8.6 g (0.10 mol) of methacrylic acid were mixed with diethylene glycol methylethyl A solution was prepared by dissolving in 150 g of ether. After the prepared solution was added dropwise into the flask using a dropping funnel, 27.9 g (0.11 mol) of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methyl ethyl ether. The dissolved solution was added dropwise into the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the solution of the polymerization initiator was completed, the temperature was maintained at 70°C for 4 hours, and then cooled to room temperature. The weight average molecular weight of the alkali-soluble resin thus synthesized was 4,700 g/mol.

[Formula 17]

Synthesis Example 10: Acrylic alkali-soluble resin (A-10)

After the dropwise addition of the solution of the polymerization initiator was completed, the same procedure as in Synthesis Example 9 was performed except that the temperature was maintained at 70° C. for 8 hours.

The alkali-soluble resin thus synthesized had a weight average molecular weight of 12,300 g/mol.

Examples and Comparative Examples: Preparation of photosensitive resin composition

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

Example alkali soluble resin cardo-based photopolymerizable compound Multifunctional acrylate photopolymerizable compound multifunctional thiol compounds photopolymerization initiator solvent additive Sum A B C F D E G One A-1 B-1 0.89 0 0.23 7.5 0.04 10 0.89 0.45 2 A-2 B-1 0.89 0 0.23 7.5 0.04 10 0.89 0.45 3 A-3 B-1 0.89 0 0.23 7.5 0.04 10 0.89 0.45 4 A-4 B-1 0.89 0 0.23 7.5 0.04 10 0.89 0.45 5 A-5 B-1 0.89 0 0.23 7.5 0.04 10 0.89 0.45 6 A-6 B-1 0.89 0 0.23 7.5 0.04 10 0.89 0.45 7 A-1 B-2 0.89 0 0.23 7.5 0.04 10 0.89 0.45 8 A-1 B-3 0.89 0 0.23 7.5 0.04 10 0.89 0.45 9 A-1 B-4 0.89 0 0.23 7.5 0.04 10 0.89 0.45 10 A-1 B-5 0.89 0 0.23 7.5 0.04 10 0.89 0.45 11 A-1 B-1 0.87 0.07 0.22 7.5 0.04 10 0.87 0.43 12 A-1 B-1 0.85 0.12 0.22 7.5 0.04 10 0.85 0.42 13 A-5 B-1 0.89 0 0.23 7.5 0.04 10 1.03 0.31 14 A-5 B-1 0.89 0 0.23 7.5 0.04 10 0.79 0.55 15 A-5 B-1 0.4 0 0.23 7.5 0.04 10 1.2 0.63 16 A-5 B-1 0.98 0 0.23 7.5 0.04 10 0.82 0.43

comparative example alkali soluble resin cardo-based photopolymerizable compound Multifunctional acrylate photopolymerizable compound multifunctional thiol compounds photopolymerization initiator solvent additive Sum A B C F D E G One A-7 B-1 0.89 0 0.23 7.5 0.04 10 0.89 0.45 2 A-8 B-1 0.89 0 0.23 7.5 0.04 10 0.89 0.45 3 A-9 B-1 0.89 0 0.23 7.5 0.04 10 0.89 0.45 4 A-10 B-1 0.89 0 0.23 7.5 0.04 10 0.89 0.45 5 A-7 B-5 0.89 0 0.23 7.5 0.04 10 0.89 0.45 6 A-6 - 1.12 0 0.22 7.5 0.04 10 1.12 0 7 A-6 - 1.09 0.06 0.22 7.5 0.04 10 1.09 0 8 A-7 B-1 0 0.07 0.22 7.5 0.04 10 1.3 0.87 9 A-7 - 0 0.07 0.22 7.5 0.04 10 2.17 0 10 A-7 - 0 0 0.23 7.5 0.04 10 2.23 0 11 A-6 B-1 0 0 0.23 7.5 0.04 10 1.32 0.91

A-1: Cardo-based alkali-soluble resin of Synthesis Example 1

A-2: Cardo-based alkali-soluble resin of Synthesis Example 2

A-3: Cardo-based alkali-soluble resin of Synthesis Example 3

A-4: Cardo-based alkali-soluble resin of Synthesis Example 4

A-5: Cardo-based alkali-soluble resin of Synthesis Example 5

A-6: Cardo-based alkali-soluble resin of Synthesis Example 6

A-7: Acrylic alkali-soluble resin of Synthesis Example 7

A-8: Acrylic alkali-soluble resin of Synthesis Example 8

A-9: Acrylic alkali-soluble resin of Synthesis Example 9

A-10: Acrylic alkali-soluble resin of Synthesis Example 10

B-1: Compound represented by Formula 10

B-2: Compound represented by Formula 11

B-3: Compound represented by Formula 12

B-4: Compound represented by Formula 13

B-5: Compound represented by Formula 14

C: dipentaerythritol hexaacrylate (manufactured by Nippon Explosive)

D: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369), manufactured by Ciba Specialty Chemical

E: propylene glycol monomethyl ether acetate

F: dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by SC Organic Chemical)

G: N-2-(aminoethyl)-8-aminooctyltrimethoxysilane (KBM-6803, manufactured by Shin-Etsu)

Experimental Example 1: Evaluation of physical properties of the pattern

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

Regarding the pattern, refractive index, development speed, residue, adhesion, surface hardness, and chemical resistance to TMAH and DPHA were evaluated as follows, and the results are shown in Table 3 below.

<How to manufacture a pattern>

A 5×5 cm glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with neutral detergent, water and alcohol, and then dried. The photosensitive resin composition prepared in Examples and Comparative Examples was spin-coated on the glass substrate, respectively, and then pre-baked at 80° C. for 120 seconds using a hot plate. After cooling the pre-baked substrate to room temperature, using an exposure machine (MA6; manufactured by Karl Suss Co., Ltd.) at a distance of 50 μm from a quartz glass photomask, using an exposure amount of 30 mJ / cm 2 (based on 365 nm). was investigated.

At this time, the photomask had circular openings (dot patterns) having diameters of 5, 10, 20, and 30 μm, and a pattern having a mutual interval of 30 μm was formed on the same plane. After light irradiation, it was developed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, washed with ultrapure water, and then dried under nitrogen to form a pattern on the photosensitive resin composition film. In an oven, post-bake was performed at 85° C. for 2 hours.

(1) Measurement of refractive index

Conditions of 25° C. and 50% RH using an ellipsometer (J. A. Woollam Co., M-2000) for the cured film formed by exposure in the same way as in the pattern manufacturing method except for not using a mask. In, incident angles of 65, 70, and 75° were applied and linearly polarized light was measured in the wavelength range of 200 nm to 1000 nm. Optimizing the measured linear polarization measurement data (Ellipsometry data (Ψ, Δ)) so that the MSE is 70 or less with the Cauchy model of Equation 1 below using Complete EASE software Thus, the refractive index at a wavelength of 550 nm was calculated.

[Equation 1]

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

(2) Development speed of unexposed areas

As in the pattern manufacturing method, the substrate progressed to pre-baking was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution to measure the time required for the photosensitive resin composition to completely dissolve, and the development speed was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

Developing speed: Stated by rounding the time to the nearest 10 seconds

Non-development within 120 seconds: indicated as ×

(3) residue

The presence or absence of residue around the dot pattern obtained in the pattern manufacturing method was observed with an optical microscope and evaluated according to the following evaluation criteria.

<Evaluation Criteria>

No residue: ○

Residue present: ×

(4) Adhesion

The minimum mask size in which the dot pattern obtained in the pattern manufacturing method is closely adhered to the lower substrate by 90% or more was measured and evaluated according to the following evaluation criteria.

<Evaluation Criteria>

90% or more adhesion of 5 ㎛ dot pattern: 5

90% or more adhesion of 10 ㎛ dot pattern: 10

90% or more adhesion of 20 ㎛ dot pattern: 20

90% or more adhesion of 30 ㎛ dot pattern: 30

Undeveloped or missing pattern: ×

(5) surface hardness

Except for not using a mask, the curing degree of the cured film formed by exposure in the same way as in the pattern manufacturing method was measured using a durometer (HM500, Fischer Co.). At this time, the surface hardness was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

◎: surface hardness of 40 or more

○: surface hardness of 30 or more and less than 40

△: surface hardness of 10 or more and less than 30

×: less than 10 surface hardness

(6) 2.38% TMAH chemical resistance

Except for not using a mask, the cured film formed in the same way as the pattern manufacturing method was immersed in 2.38% tetraammonium hydroxide aqueous solution for 2 minutes, and the film thickness change (unit: μm) was measured.

(7) DPHA chemical resistance

Except for not using a mask, dipentaerythritol hexaacrylate (DPHA) was added dropwise to the cured film formed in the same way as in the pattern manufacturing method, left for 2 minutes, washed with ultrapure water, and then dried under nitrogen to obtain a film thickness. The change (unit: μm) was measured.

refractive index developing speed residue adhesion surface hardness 2.38% TMAH chemical resistance DPHA chemical resistance Example One 1.62 30 ○ 5 ○ -0.03 0.02 2 1.62 30 ○ 5 ○ -0.02 0.02 3 1.62 40 ○ 5 ○ -0.01 0.02 4 1.62 50 ○ 5 ○ -0.02 0.03 5 1.64 20 ○ 5 ◎ -0.01 0.01 6 1.64 20 ○ 5 ◎ -0.01 0.01 7 1.62 30 ○ 5 ○ -0.03 0.02 8 1.62 30 ○ 5 ○ -0.04 0.03 9 1.62 30 ○ 5 ○ -0.03 0.02 10 1.62 30 ○ 5 ○ -0.04 0.02 11 1.64 40 ○ 5 ○ 0 0.01 12 1.64 50 ○ 5 ○ 0 0 13 1.64 10 ○ 5 ◎ -0.01 0.02 14 1.64 30 ○ 5 ◎ 0 0.01 15 1.65 30 ○ 5 ◎ -0.01 0.02 16 1.64 10 ○ 5 ◎ -0.02 0 comparative example One 1.53 20 ○ 5 △ -0.17 0.31 2 1.54 × × 5 △ -0.1 0.2 3 1.53 30 ○ 5 △ -0.13 0.29 4 1.53 × × 5 △ -0.11 0.22 5 1.53 20 ○ 5 △ -0.07 0.17 6 1.51 20 ○ 10 △ -0.09 0.23 7 1.54 30 ○ 5 △ -0.23 0.17 8 1.56 × × 5 △ -0.35 0.46 9 1.54 × × × × × × 10 1.51 × × × × × × 11 1.56 × × 30 × × ×

As shown in Table 3, the photosensitive resin compositions of Examples 1 to 16 including a cardo-based alkali-soluble resin, a cardo-based photopolymerizable compound, and a multifunctional acrylate photopolymerizable compound including a repeating unit having a specific structure are inorganic particles Even without using, the refractive index of the pattern formed therefrom shows a high refractive index of 1.60 or more at a wavelength of 550 nm, and even when cured at a low temperature of 100 ° C or less, pattern characteristics such as development speed, residue, adhesion, and surface hardness characteristics are excellent, It can be confirmed that the chemical resistance to the developing solution and the monomer is excellent.

On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 8 and 11 that do not include any one of the cardo-based alkali-soluble resin, the cardo-based photopolymerizable compound, and the multifunctional acrylate photopolymerizable compound including a repeating unit having a specific structure have a wavelength of 550 nm showed a refractive index of less than 1.60, and it was found that any one or more physical properties of developing rate, residue, adhesion, and surface hardness were poor. In addition, the photosensitive resin compositions of Comparative Examples 1 to 8 and 11 have poor chemical resistance to a developer used in the development process and chemical resistance to a monomer used in a post-process to form another pattern, resulting in film loss and film loss. It was confirmed that swelling was severe.

In addition, the photosensitive resin compositions of Comparative Examples 9 and 10 containing neither the cardo-based photopolymerizable compound nor the polyfunctional acrylate photopolymerizable compound were dissolved in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) on the exposed portion, so that a coating film was not formed. It turned out that the characterization could not be confirmed.

Having described specific parts of the present invention in detail above, it is clear that these specific techniques are only preferred embodiments for those skilled in the art to which the present invention belongs, and the scope of the present invention is not limited thereto. do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above information.

Accordingly, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (12)

A photosensitive resin composition comprising an alkali-soluble resin containing at least one repeating unit of Formulas 1 to 6, a cardo-based photopolymerizable compound, a polyfunctional acrylate photopolymerizable compound, a photopolymerization initiator, and a solvent:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In the above formula,
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

ego,
Y is an acid anhydride residue,
Z is an acid dianhydride moiety;
R' is a hydrogen atom, an ethyl group, a phenyl group, -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 each independently a C ₁ -C ₆ alkylene group, and the alkylene group is interposed with or without at least one of an ester bond, a C ₆ -C ₁₄ cycloalkylene group and an arylene group, ,
R9, R9', R10, R10', R11, R11', R12 and R12' are each independently a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,
m and n are each independently an integer from 1 to 30;
t and u are each independently an integer from 0 to 1,
P is each independently

,

,

,

or

ego,
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 moiety;
A is O, S, NR', Si(R') ₂ or Se;
a and b are each independently an integer from 1 to 6,
p and q are each independently an integer of 1 to 30; The photosensitive resin composition according to claim 1, wherein the cured coating film exhibits a refractive index of 1.60 or more at a wavelength of 550 nm. The acid anhydride of claim 1, wherein the acid anhydride is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic acid anhydride and methyltetrahydrophthalic anhydride. A photosensitive resin composition selected from the group consisting of phthalic acid. The photosensitive resin composition according to claim 1, wherein the acid dianhydride is selected from the group consisting of pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride and biphenylethertetracarboxylic dianhydride. The photosensitive resin composition according to claim 1, wherein the cardo-based photopolymerizable compound includes a compound represented by any one of the following Chemical Formulas 7 to 9:
[Formula 7]

[Formula 8]

[Formula 9]

In the above formula,
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 a polymerizable functional group having 2 to 20 carbon atoms having an unsaturated double bond, and at least one of R15 or R16 has an unsaturated double bond It is a polymerizable functional group having 2 to 20 carbon atoms. The method of claim 5, 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 or R16

is,
R17 is a C ₁ -C ₆ alkylene group, and the alkylene group is interposed with or without at least one of an ester bond, a C ₆ -C ₁₄ cycloalkylene group, and an arylene group;
The photosensitive resin composition in which R18 is a hydrogen atom or a methyl group. The photosensitive resin composition according to claim 1, wherein the cardo-based photopolymerizable compound is included in an amount of 30 to 70 parts by weight based on 100 parts by weight of the alkali-soluble resin. The photosensitive resin composition according to claim 1, wherein the multifunctional acrylate photopolymerizable compound is included in an amount of 30 to 120 parts by weight based on 100 parts by weight of the alkali-soluble resin. The photosensitive resin composition according to claim 1, further comprising a multifunctional thiol compound. The photosensitive resin composition according to claim 1, which does not contain inorganic particles. A protruding pattern formed using the photosensitive resin composition according to any one of claims 1 to 10. An image display device comprising the protruding pattern according to claim 11.