KR20230036669A - Photosensitive resin composition, insulation pattern formed from the same and image display comprising the pattern - Google Patents

Abstract

A photosensitive resin composition according to an exemplary embodiment comprises: a first binder resin represented by chemical formula 1 and containing at least one repeating unit derived from a block isocyanate-based compound; a second binder resin containing an oxazoline group or a derivative thereof; a polymeric monomer; a photopolymerization initiator; and a solvent. The pattern formed from the photosensitive resin composition provides excellent visibility, heat resistance, moisture resistance, alkali resistance, chemical resistance, and storage stability.

Description

Photosensitive resin composition, insulating pattern formed therefrom, and image display device including the same

The present invention relates to a photosensitive resin composition, an insulating pattern formed therefrom, and an image display device including the same. More specifically, it relates to a photosensitive resin composition containing a curable resin or compound, an insulating pattern formed therefrom, and an image display device including the same.

In the display field, photosensitive resin compositions are used to form various photocurable patterns such as photoresists, insulating films, protective films, black matrices, and column spacers. For example, a desired photocuring pattern may be formed by selectively exposing and developing the photosensitive resin composition through a photolithography process.

The photosensitive resin composition is classified into a positive type and a negative type according to the photocuring type. The photoresist formed by the positive-type composition is modified in the chemical structure of the exposed portion and dissolved by a developing solution, and the photoresist formed by the negative-type composition has an increased degree of polymerization in the exposed portion and is cured or remains undissolved during the development process. Positive and negative compositions may each contain different binder resins, crosslinking agents, and the like.

Recently, the use of touch screens with touch panels is increasing, and accordingly, display devices including flexible touch screens are being actively developed. Therefore, the need for a photosensitive resin composition having stability against various physical and chemical changes has increased.

Korean Patent Registration No. 10-1302508 discloses a negative photosensitive resin composition including a copolymer polymerized using a cyclohexenyl acrylate-based monomer.

However, Korean Patent Registration No. 10-1302508 fails to disclose a photosensitive resin composition having sufficient stability against various physical and chemical changes.

Korean Patent Registration No. 10-1302508

One object of the present invention is to provide a photosensitive resin composition having excellent curability and stability.

One object of the present invention is to provide an insulating pattern formed from the photosensitive resin composition and an image display device including the same.

1. A first binder resin comprising at least one repeating unit derived from a block isocyanate-based compound represented by Formula 1 below; A second binder resin containing an oxazoline group or a derivative thereof; polymerizable monomers; photopolymerization initiator; And a photosensitive resin composition containing a solvent:

[Formula 1]

In Formula 1, D is O or CH ₂ , Z is an acrylate group, methacrylate group or a vinyl group, L ¹ is a C1 to C20 straight chain or C3 to C20 branched chain, and BL is a thermally dissociable blocking agent. It is a residue derived from

2, the photosensitive resin composition according to 1 above, wherein the second binder resin includes at least one oxazoline moiety represented by Formula 2 or Formula 3 below:

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3, R ₁ is an acyclic hydrocarbon group having at least one unsaturated bond and having C1 to C12, and R ₂ , R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom or a halogen atom. , A C1 to C12 straight chain or C3 to C12 branched chain alkyl group, a C6 to C12 aryl group, a C7 to C12 arylalkyl group, or a C7 to C12 alkylaryl group.

3. The photosensitive resin composition according to 1 above, wherein the second binder resin is an oxazoline-containing copolymer including at least one oxazoline moiety.

4. The photosensitive resin composition according to 3 above, wherein the oxazoline-containing copolymer is a terpolymer, and at least one of the oxazoline moieties is a pendant group of the terpolymer.

5. The heat dissociable blocking agent according to 1 above, wherein the thermally dissociable blocking agent is a phenol-based blocking agent, a lactam-based blocking agent, an active methylene-based blocking agent, an alcohol-based blocking agent, an oxime-based blocking agent, a mercaptan-based blocking agent, an acid amide-based blocking agent, A photosensitive resin composition comprising at least one selected from imide-based blocking agents, amine-based blocking agents, imidazole-based blocking agents, imine-based blocking agents, and pyrazole-based blocking agents;

6. The photosensitive resin composition according to 1 above, further comprising at least one of the cardo-based photopolymerizable compounds represented by the following Chemical Formulas 4 to 6:

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6, R ₆ and R ₇ are each independently hydrogen, a halogen atom, a hydroxyl group, a thiol group, an amino group, a nitro group, or a halogen atom, an ester group, a hydroxyl group, and at least one of a carbon-carbon double bond It is a C1 to C20 straight chain or C3 to C20 branched chain alkyl group including.

7. In the above 1, of the total weight of the solid content of the photosensitive resin composition, 10 to 80% by weight of the first binder resin, 5 to 80% by weight of the second binder resin, and 10 to 60% by weight of the polymerizable monomer To do, photosensitive resin composition.

8. An insulating pattern formed from the photosensitive resin composition according to 1 above.

9. An image display device comprising the insulating pattern according to 8 above.

According to exemplary embodiments of the present invention, the first binder resin included in the photosensitive resin composition and the second binder resin including an oxazoline group or a derivative thereof have excellent compatibility, and the first binder resin and the second binder resin have excellent compatibility. A crosslinking reaction between the binder resins may proceed densely at a low temperature of 100° C. or less. Accordingly, it is possible to provide a cured product having excellent mechanical/chemical durability and thermal stability even in a low-temperature curing process.

In addition, according to exemplary embodiments of the present invention, the pattern obtained by the crosslinking reaction between the first binder resin and the second binder resin included in the photosensitive resin composition has excellent water resistance, heat resistance, alkali resistance, and chemical resistance, Destruction of the pattern in the manufacturing process can be suppressed, and process cost can be reduced. Furthermore, since the adhesion of the pattern to the substrate layer is excellent, it is easy to reproduce the manufacturing process.

The photosensitive resin composition according to embodiments of the present invention is represented by Chemical Formula 1 and includes a first binder resin containing at least one repeating unit derived from a block isocyanate-based compound, and a second binder resin containing an oxazoline group or a derivative thereof. , a polymerizable monomer, a photopolymerization initiator, and a solvent. Hereinafter, each compound is described in detail.

<First binder resin>

The first binder resin according to example embodiments may include a block isocyanate group. The first binder resin may be a component that imparts solubility to an alkaline developing solution used in a developing process in forming a pattern. For example, the first binder resin may be an alkali-soluble resin.

The first binder resin according to an exemplary embodiment may include at least one repeating unit derived from a block isocyanate-based compound represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1, D is O or CH ₂ , Z is an acrylate group, methacrylate group or a vinyl group, L ¹ is a C1 to C20 straight chain or C3 to C20 branched chain, and BL is a thermally dissociable blocking agent. It is a residue derived from

In exemplary embodiments, the blocked isocyanate-based compound may be obtained by a reaction between a compound containing an isocyanate group and a thermally dissociable blocking agent.

For example, the blocked isocyanate group may be a group in which the isocyanate group is temporarily inactivated by being protected by a reaction with a thermally dissociable blocking agent. In this case, the thermally dissociable blocking agent may be dissociated by heating the blocked isocyanate group to a predetermined temperature, thereby generating an isocyanate group. The term "thermal dissociation" as used herein means dissociation of a thermally dissociable blocking agent bonded to an isocyanate group by heating.

For example, the reaction between an isocyanate-based compound and a thermally dissociable blocking agent can be summarized as shown in Scheme 1 below. In the following Reaction Scheme 1, D is O or CH- ₂ , Z is an acrylate group, methacrylate group or a vinyl group, L ¹ is a C1 to C20 straight chain or C3 to C20 branched chain, and H-BL is thermal dissociation It is a sex blocking agent, and BL is a residue derived from a thermally dissociable blocking agent.

[Scheme 1]

For example, a nucleophilic functional group included in a thermally dissociable blocking agent may undergo a nucleophilic addition reaction with an isocyanate group included in an isocyanate-based compound, and as a result, a chemical bond is formed between a carbon atom of the isocyanate group and the thermally dissociable blocking agent. can be formed

In addition, in the photosensitive resin composition according to an exemplary embodiment, the moiety derived from the thermally dissociable blocking agent is a conventional isocyanate group in a blocked isocyanate-based compound obtained after a series of synthetic reactions including a nucleophilic addition reaction are completed. It is bonded to the carbon atom of and may refer to the entire moiety derived from the thermally dissociable blocking agent.

In the photosensitive resin composition according to some exemplary embodiments, the thermally dissociable blocking agent may include a compound capable of chemically bonding with an isocyanate-based compound. For example, the heat dissociable blocking agent may include a phenol-based blocking agent containing at least one phenol group, a lactam-based blocking agent containing at least one lactam group, an active methylene-based blocking agent containing at least one active methylene group, and at least one alcohol group. Alcohol-based blocking agent containing, oxime-based blocking agent containing at least one oxime group, mercaptan-based blocking agent containing at least one mercapto group, acid amide-based blocking agent containing at least one acid amide group, containing at least one imide group Imide-based blocking agents, amine-based blocking agents containing at least one amine group, imidazole-based blocking agents containing at least one imidazole group, imine-based blocking agents containing at least one imine group, and pyrazole-based blocking agents containing at least one pyrazole group Blocking agents and the like may be included. These may be used alone or in combination of two or more.

Examples of the phenolic blocking agent include phenol, cresol, xylenol, chlorophenol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoic acid ester.

Examples of the lactam-based blocking agent include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam.

Examples of the active methylene-based blocking agent include methyl acetoacetate, ethyl acetoacetate, acetylacetone, dimethyl malonate and diethyl malonate.

As examples of the alcohol-based blocking agent, methanol, ethanol, propanol, butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, amyl alcohol, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate, etc. can be heard

Examples of the oxime-based blocking agent include formaldehyde, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexanone oxime.

Examples of the mercaptan-based blocking agent include butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol and ethylthiophenol.

Examples of the acid amide blocking agent include acetic acid amide and benzamide.

Examples of the imide-based blocking agent include succinic acid imide and maleic acid imide.

Examples of the amines include xylidine, aniline, butylamine, dibutylamine, diphenylamine, carbazole, di-n-propylamine, diisopropylamine and isopropylethylamine.

Examples of the imidazole-based blocking agent include imidazole and 2-ethylimidazole.

Examples of the imine-based blocking agent include methyleneimine and propyleneimine.

Examples of the pyrazole-based blocking agent include pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.

In addition, as an example of a residue derived from an active methylene-based blocking agent, a substituent shown in partial structural formula 1 below may be considered. In addition, as an example of a residue derived from a pyrazole-based blocking agent, a substituent shown in partial structural formula 2 below may be considered. Waves shown in partial structural formula 1 and partial structural formula 2 below mean the bonding position between the isocyanate-based compound and each substituent.

[Partial structural formula 1]

[Partial structural formula 2]

In addition, in the photosensitive resin composition according to some exemplary embodiments, a C-C, C-O, C-N, or C-S bond is formed between a carbon atom of a conventional isocyanate group and a moiety derived from the thermally dissociable blocking agent by changing the thermally dissociable blocking agent. can be formed In addition, the dissociation temperature of the C-C, C-O, C-N, or C-S bond may be varied by changing the residue derived from the thermal dissociation blocking agent.

In the photosensitive resin composition according to some exemplary embodiments, the dissociation temperature of the residue derived from the thermal dissociation blocking agent may be 40°C to 300°C, preferably 60°C to 200°C.

In addition, in an exemplary embodiment, the first binder resin may have reactivity to light or heat and may have solubility in an alkaline solution. In addition, reactivity and alkali solubility may be controlled by changing the repeating unit included in the first binder resin.

In some exemplary embodiments, the first binder resin is a polymerized polymer further including at least one of an ethylenically unsaturated compound having a carboxyl group, an ethylenically unsaturated compound having a hydroxyl group, and a compound having a glycidyl group. can

For example, the first binder resin is a repeating unit derived from a compound containing a carboxyl group and an unsaturated bond, a repeating unit derived from a compound containing a hydroxyl group and an unsaturated bond, and a repeating unit derived from a compound containing a glycidyl group. It may be a copolymer containing at least one of the units.

Alkali solubility of the first binder resin may be improved by including a repeating unit derived from a compound including the carboxyl group and an unsaturated bond.

Examples of the compound containing the carboxyl group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and α-chloroacrylic acid; dicarboxylic acids such as maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid and their anhydrides; and mono(meth)acrylate-based compounds of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate. These may be used alone or in combination of two or more. Preferably, acrylic acid or methacrylic acid may be included as a compound containing a carboxyl group and an unsaturated bond.

As used herein, the term "(meth)acrylate" is a term encompassing acrylates and methacrylates.

Furthermore, the carboxylic acid moiety or the carboxylic acid anion moiety included in the first binder resin may undergo a crosslinking reaction with a second binder resin including an oxazoline group or a derivative thereof described later. By a crosslinking reaction between the carboxylic acid moiety or the carboxylic acid anion moiety and the second binder resin including an oxazoline group or a derivative thereof, low-temperature curability of the photosensitive resin composition may be further secured, and the photosensitive resin composition Physical properties such as moisture resistance, heat resistance, alkali resistance, and chemical resistance of the pattern formed therefrom can be improved.

Alkali solubility of the first binder resin may be improved by including a repeating unit derived from a compound including the hydroxyl group and an unsaturated bond.

Examples of the compound containing the hydroxyl group and an unsaturated bond include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, Hydroxy-3-phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, etc. are mentioned. These may be used alone or in combination of two or more. Preferably, hydroxyethyl (meth)acrylate may be included as the compound including the hydroxyl group and an unsaturated bond.

By including the repeating unit derived from the compound containing the glycidyl group, photocurability of the first binder resin may be further improved.

Examples of the compound containing the glycidyl group include glycidyl methyl ether, glycidyl propyl ether, glycidyl butyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether. , glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 3-methyl -3,4-epoxybutyl (meth)acrylate, 3-ethyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate α-ethyl acrylate glycy Dill etc. are mentioned. These may be used alone or in combination of two or more. Preferably, the glycidyl group-containing compound may include glycidyl butyl ether, allyl glycidyl ether and/or glycidyl (meth)acrylate.

In addition, as a non-limiting example of a compound containing an unsaturated bond capable of copolymerization with the precursor of each repeating unit included in the exemplary first binder resin, a substituted or unsubstituted alkyl ester compound, an alicyclic or aromatic ring is included. A carboxylic acid ester-based compound having at least one alkene bond, an unsaturated carboxylic acid ester-based compound containing at least one alkene bond, an aromatic vinyl compound, and a vinyl cyanide compound may be additionally considered.

In some exemplary embodiments, the first binder resin may be a copolymer polymerized by further including an unsaturated polymerizable compound capable of copolymerizing with the aforementioned compounds. For example, the first binder resin may include a repeating unit derived from a compound having an unsaturated bond copolymerizable with the above compounds.

The unsaturated polymerizable compound may not include a carboxyl group, a hydroxyl group, and a glycidyl group. Examples of the unsaturated polymerizable compound include aromatic vinyl compounds, N-substituted maleimide compounds, non-polar hydrocarbon group-containing (meth)acrylate compounds, and oxetane compounds. These may be used alone or in combination of two or more.

Examples of the aromatic vinyl compound include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m- Vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, etc. are mentioned.

Examples of the N-substituted maleimide-based compound include N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o -Methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N-p-methoxyphenyl maleimide, etc. are mentioned.

Examples of the non-polar hydrocarbon group-containing (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, and n-butyl Alkyl (meth)acrylate compounds, such as (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate; Cyclopentyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-methylcyclohexyl(meth)acrylate, tricyclo[5.2.1.0 2,6]decan-8-yl(meth)acrylate, dicyclo alicyclic (meth)acrylate compounds such as fentanyl (meth)acrylate, 2-dicyclopentanyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate; Aryl (meth)acrylate compounds, such as phenyl (meth)acrylate and benzyl (meth)acrylate, etc. are mentioned.

Examples of the oxetane compound include (3-ethyloxetan-3-yl)methyl methacrylate, 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3- Ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl )Oxetane compounds having unsaturated bonds such as oxetane and 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane.

In addition, in the photosensitive resin composition according to some exemplary embodiments, in view of improving the developability of the photosensitive resin composition, the acid value of the first binder resin may be 10 to 200 mgKOH/g, preferably. 10 to 150 mgKOH/g. When the acid value of the first binder resin satisfies the above range, the photosensitive resin composition may secure a sufficient developing rate, and adhesion to the substrate may be improved, thereby preventing occurrence of a pattern short circuit.

Also, in the photosensitive resin composition according to some exemplary embodiments, the weight average molecular weight (Mw) of the first binder resin may be 3,000 to 30,000.

In addition, in the photosensitive resin composition according to some exemplary embodiments, the molecular weight distribution of the first binder resin of the present invention, that is, the weight average molecular weight relative to the number average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) may be 1.5 to 6.0. When the first binder resin satisfies the weight average molecular weight and molecular weight distribution ranges, there is an advantage of excellent developability.

In the photosensitive resin composition according to an exemplary embodiment, the content of the first binder resin may be 10 to 80% by weight, preferably 10 to 70% by weight, more preferably 20 to 80% by weight of the total solid weight of the photosensitive resin composition. to 50% by weight. Within the above range, pattern formation may be facilitated due to excellent solubility in a developing solution, and film reduction in the pixel portion of the exposed portion may be suppressed during development, and omission of non-pixel portions may be improved.

<Second binder resin>

The photosensitive resin composition according to an exemplary embodiment includes a second binder resin including an oxazoline group or a derivative thereof. The second binder resin may be an oxazoline-containing copolymer including repeating units derived from oxazoline monomers.

For example, the second binder resin may include two or more repeating units derived from different compounds in a structure, and at least one of the repeating units may include an oxazoline group.

In the photosensitive resin composition according to some exemplary embodiments, the second binder resin may include at least one oxazoline moiety represented by Chemical Formula 2 or Chemical Formula 3 below.

[Formula 2]

In Formula 2, R ₁ may be a C1 to C12 acyclic hydrocarbon group containing one or more unsaturated bonds.

In Formula 2, R ₂ , R ₃ , R ₄ , and R ₅ are independently hydrogen, a halogen atom, a C1 to C12 straight or branched chain alkyl group, a C3 to C12 aryl group, or a C3 to C12 arylalkyl group. , or a C3 to C12 alkylaryl group.

[Formula 3]

In Formula 3, R ₁ may be a C1 to C12 acyclic hydrocarbon group containing one or more unsaturated bonds.

Further, in Formula 3, R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen, a halogen atom, a C1 to C12 straight chain or C3 to C12 branched chain alkyl group, a C6 to C12 aryl group, or a C7 to C12 arylalkyl group, or C7 to C12 alkylaryl group.

Further, in Formulas 2 and 3, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may each be one of an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group substituted with at least one hetero atom. By being substituted with one or more hetero atoms, an alcohol group, an ether group, an amine group, a sulfide group, a thiol group in an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group , or a halo group may be included.

In the photosensitive resin composition according to some exemplary embodiments, preferred examples of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in Formula 2 or Formula 3 include the oxazoline group or a derivative thereof. Substituents capable of further promoting the formation of a crosslink between the second binder resin and the first binder resin may be considered. When crosslinking with the first binder resin is promoted, physical properties of a pattern derived from the photosensitive resin composition may be further improved even under low temperature conditions.

For example, R ₁ in Formula 2 or Formula 3 is a C1 to C12 acyclic hydrocarbon group containing one or more unsaturated bonds. The C1 to C12 acyclic hydrocarbon group includes a C1 to C12 straight chain alkyl group and a C3 to C12 branched chain alkyl group. In addition, the unsaturated bond included in the R ₁ moiety may be a double bond or a triple bond between carbons. Furthermore, a conjugated bond may be formed between the unsaturated bond included in the R ₁ moiety and the imine moiety included in the oxazoline moiety.

In Formula 2, R ₂ and R ₃ are preferably functional groups capable of promoting dissociation of the CO bond by donating electrons to adjacent CO bonds. For example, hydrogen, a halogen atom, a straight-chain or branched-chain alkyl group of C1 to C12, or an aryl group of C6 to C12 may promote dissociation of adjacent CO bonds through superconjugated bonds.

In Formula 2, R ₄ and R ₅ are preferably functional groups capable of stabilizing the cation at the 5th carbon site to which R ₄ and R ₅ are bonded. For example, when R ₄ and R ₅ are C1 to C12 straight-chain or C3 to C12 branched-chain alkyl groups, or C7 to C12 arylalkyl groups, the cation at the 5th carbon site is stabilized by a superconjugated bond or a covalent bond. Therefore, dissociation of the CO bond included in the oxazoline moiety of Chemical Formula 2 may be promoted.

In addition, when R ₄ and R ₅ are an aryl group of C6 to C12 or an alkylaryl group of C7 to C12, the cation at the 5th carbon site can be stabilized due to the formation of a conjugation bond. Dissociation of the CO bond involved in the sleepy moiety may be promoted.

Also, in the photosensitive resin composition according to some exemplary embodiments, the second binder resin may be an oxazoline-containing copolymer including at least one oxazoline moiety. In terms of excellent miscibility with the first binder resin, the copolymer may include one or more oxazoline moieties and may further include one or more carboxylic acid groups or carboxylic acid anions.

Also, in the photosensitive resin composition according to some exemplary embodiments, the oxazoline-containing copolymer may be a terpolymer, and the oxazoline moiety may be a pendant group of the terpolymer.

By including the oxazoline moiety as a pendant group in the terpolymer, accessibility to the oxazoline moiety may be increased, and a crosslinking reaction between the oxazoline moiety and the first binder resin may be promoted.

In addition, in some exemplary embodiments, the terpolymer may include a repeating unit derived from a compound including a carboxylic acid group and an unsaturated bond. Alkali solubility of the second binder resin may be improved by including a repeating unit derived from a compound containing a carboxylic acid group and an unsaturated bond.

In addition, since a repeating unit including a carboxylic acid group or a carboxylic acid anion is included in the second binder resin, a hydrogen bond may be formed between the first binder resin and the second binder resin, and the first binder resin And the compatibility of the second binder resin can be increased.

Furthermore, the carboxylic acid group or the carboxylic acid anion included in the terpolymer may undergo a crosslinking reaction with the isocyanate moiety included in the first binder resin, and a photosensitive property including the first binder resin and the second binder resin. The compactness of the resin composition can be further improved.

Examples of compounds containing a carboxylic acid group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and α-chloroacrylic acid; dicarboxylic acids such as maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid and their anhydrides; Polyvalent carboxylic acids such as ω-carboxypolycaprolactone mono(meth)acrylate and the like can be considered.

In addition, in an exemplary embodiment, the second binder resin may have reactivity to light or heat and may have solubility in an alkaline solution. In addition, reactivity and alkali solubility may be controlled by changing the repeating unit included in the second binder resin.

In some exemplary embodiments, the second binder resin further includes at least one of a repeating unit derived from a compound containing a hydroxyl group and an unsaturated bond, or a repeating unit derived from a compound containing an epoxy group and an unsaturated bond. can do.

In addition, alkali solubility of the second binder resin may be improved by including a repeating unit derived from a compound containing a hydroxyl group and an unsaturated bond. As a non-limiting example of a compound containing a hydroxyl group and an unsaturated bond, hydroxyl such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate ( meth)acrylate, caprolactone adduct of hydroxy(meth)acrylate, alkylene oxide adduct of hydroxy(meth)acrylate, glycerin mono(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol Tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, methylolpropane mono(meth)acrylate, ditrimethylolpropane tri(meth)acrylate and polyhydric alcohols such as (meth)acrylic acid Ester compounds and the like can be considered.

In addition, photocurability of the first binder resin may be further improved by including a repeating unit derived from a compound including an epoxy group and an unsaturated bond. As non-limiting examples of compounds containing an epoxy group and an unsaturated bond, glycidyl methyl ether, glycidyl propyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, glycidyl Dill (meth)acrylate, methylglycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 3-methyl-3, 4-epoxybutyl (meth)acrylate, 3-ethyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, α-ethyl glycidyl acrylate, etc. can be considered

In some exemplary embodiments, the second binder resin may be a copolymer polymerized by further including an unsaturated polymerizable compound capable of copolymerizing with the aforementioned compound. For example, the second binder resin may further include a repeating unit derived from an unsaturated polymerizable compound copolymerizable with the aforementioned compounds.

The unsaturated polymerizable compound may not include a carboxyl group, a hydroxyl group, and an epoxy group. Examples of the unsaturated polymerizable compound include aromatic vinyl compounds, N-substituted maleimide compounds, non-polar hydrocarbon group-containing (meth)acrylate compounds and/or oxetane compounds. These may be used alone or in combination of two or more.

As non-limiting examples of the aromatic vinyl compound, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m - Vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, etc. are mentioned.

As non-limiting examples of the N-substituted maleimide-based compound, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide Mead, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N-p-methoxyphenyl maleimide, etc. are mentioned.

As non-limiting examples of the non-polar hydrocarbon group-containing (meth)acrylate compound, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, Alkyl (meth)acrylate compounds, such as n-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate; Cyclopentyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-methylcyclohexyl(meth)acrylate, tricyclo[5.2.1.0 2,6]decan-8-yl(meth)acrylate, dicyclo alicyclic (meth)acrylate compounds such as fentanyl (meth)acrylate, 2-dicyclopentanyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate; Aryl (meth)acrylate compounds, such as phenyl (meth)acrylate and benzyl (meth)acrylate, etc. are mentioned.

As non-limiting examples of the oxetane compound, (3-ethyloxetan-3-yl)methyl methacrylate, 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl) -3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl) Iloxymethyl) oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyl oxetane, etc. are mentioned.

In the photosensitive resin composition according to an exemplary embodiment, the acid value of the solid content of the second binder resin included in the photosensitive resin composition may be 10 mgKOH/g to 200 mgKOH/g, preferably 10 mgKOH/g. g to 150 mgKOH/g.

When the acid value of the second binder resin satisfies the aforementioned numerical range, the alkali solubility of the photosensitive resin composition including the second binder resin may be improved while the denseness of the insulating pattern obtained from the photosensitive resin composition is secured.

In the photosensitive resin composition according to an exemplary embodiment, the weight average molecular weight of the second binder resin included in the photosensitive resin composition may be 3,000 to 30,000.

When the weight average molecular weight of the second binder resin satisfies the aforementioned numerical range, the density of the insulating pattern obtained from the photosensitive resin composition is increased, and moisture resistance, heat resistance, alkali resistance, and chemical resistance of the insulating pattern may be improved.

In the photosensitive resin composition according to some exemplary embodiments, the molecular weight distribution of the second binder resin may be 1.5 to 6.0. For example, the molecular weight distribution may be the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight (Mw)/number average molecular weight (Mn)). When the molecular weight distribution of the second binder resin satisfies the aforementioned numerical range, durability and stability of the insulating pattern may be improved while coating properties and coating properties of the photosensitive resin composition may be improved.

In the photosensitive resin composition according to exemplary embodiments, the content of the second binder resin may be 5 to 80% by weight, preferably 5 to 70% by weight, more preferably 5 to 70% by weight based on the total solid weight of the photosensitive resin composition. 10 to 50% by weight.

When the second binder resin is included in the photosensitive resin composition to satisfy the above-described numerical range, the density of the insulating pattern formed from the photosensitive resin composition is increased, and the moisture resistance, heat resistance, alkali resistance, and chemical resistance of the insulating pattern are improved. can

<Polymerizable monomer>

A photosensitive resin composition according to an exemplary embodiment includes a polymerizable monomer. A polymerizable monomer means a monomer containing at least one polymerizable unsaturated bond. The polymerizable monomer included in the photosensitive resin composition of the exemplary embodiment undergoes a polymerization or copolymerization reaction, so that the density of an insulating pattern formed from the photosensitive resin composition is further improved, and heat resistance and the like can be further improved.

In some exemplary embodiments, the polymerizable monomer may include a monofunctional monomer, a difunctional monomer, or a trifunctional or multifunctional monomer. These may be used alone or in combination of two or more.

As non-limiting examples of the monofunctional monomer, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, hydroxy Propyl (meth)acrylate, hydroxybutyl (meth)acrylate, N-vinylpyrrolidone, etc. are mentioned.

As non-limiting examples of the bifunctional monomer, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Acrylates, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like are exemplified.

As non-limiting examples of the trifunctional or higher functional monomer, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate Latex, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxyl Rated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate tripentaerythritol hexa(meth)acrylate, tetrapentaerythritol hexa(meth)acrylate, polypentaerythritol poly acrylates and urethane acrylates; and the like.

Preferably, the polymerizable monomer may include a bifunctional, trifunctional or more multifunctional monomer.

In the photosensitive resin composition according to an exemplary embodiment, the content of the polymerizable monomer may be 10 to 60% by weight, preferably 20 to 50% by weight, based on the total solid weight of the photosensitive resin composition.

When the polymerizable monomer is included in the photosensitive resin composition to satisfy the above numerical range, the density of the insulating pattern formed from the photosensitive resin composition is increased, and the moisture resistance, heat resistance, alkali resistance, and chemical resistance of the insulating pattern can be improved. there is.

<Cardo-based photopolymerizable compound>

The photosensitive resin composition according to an exemplary embodiment may further include a cardo-based photopolymerizable compound. For example, the cardo-based photopolymerizable compound may be a cardo-based monomer or a cardo-based resin that can undergo a polymerization reaction by light irradiation and/or a photopolymerization agent.

According to some exemplary embodiments, moisture resistance, heat resistance, alkali resistance, and storage stability of the photosensitive resin composition may be further improved by including the cardo-based photopolymerizable compound in the photosensitive resin composition.

For example, the cardo-based monomer included in the photosensitive resin composition imparts additional steric hindrance to the photosensitive resin composition, dissociation of residues derived from the thermally decomposable blocking agent, and a first binder resin containing an oxazoline group or a derivative thereof. It may contribute to promoting cross-linking between the second binder resins.

In the photosensitive resin composition according to some exemplary embodiments, at least one of the cardo-based photopolymerizable compounds represented by Chemical Formulas 4 to 6 may be further included.

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6, R ₆ and R ₇ are each independently hydrogen, a halogen atom, a hydroxyl group, a thiol group, an amino group, a nitro group, or a halogen atom, an ester group, a hydroxyl group, and at least one of a carbon-carbon double bond It may be a C1 to C20 straight chain or C3 to C20 branched chain alkyl group including.

In some exemplary embodiments, in Chemical Formulas 3 to 5, at least one of R ₆ and R ₇ may be a C1 to C20 straight chain or C3 to C20 branched chain alkyl group including a carbon-carbon double bond. .

For example, R ₆ or R ₇ may be a functional group represented by Formula 7 below.

[Formula 7]

In Formula 7, R17 may be a C1 to C4 alkylene group. In one embodiment, the alkylene group may include an ester group, a C6 to C14 cycloalkylene group, or a C6 to C14 arylene group in at least one carbon bond. R18 may be a hydrogen atom or a methyl group.

According to some exemplary embodiments, the cardo-based photopolymerizable compound may include at least one of compounds represented by Chemical Formulas 8 to 12 below.

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

In the photosensitive resin composition according to an exemplary embodiment, when a cardo-based photopolymerizable compound is included, the content of the cardo-based photopolymerizable compound may be 30% by weight or less based on the total solid weight of the photosensitive resin composition. For example, the content of the cardo-based photopolymerizable compound may be 5 to 30% by weight, preferably 5 to 20% by weight, based on the total solid weight of the photosensitive resin composition.

By including the cardo-based photopolymerizable compound in the photosensitive resin composition to satisfy the above-mentioned numerical range, the uniformity of the insulating pattern formed from the photosensitive resin composition is increased, and the moisture resistance, heat resistance, alkali resistance, and chemical resistance of the insulating pattern are improved. can be improved

<Photoinitiator>

The photosensitive resin composition according to an exemplary embodiment includes a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as a compound for initiating polymerization of the photosensitive resin composition described above. As examples of the photopolymerization initiator, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, anthracene-based, anthraquinone-based, and biimidazole-based compounds may be considered. Alternatively, two or more kinds may be mixed and used.

As a non-limiting example, the benzophenone-based compound includes benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzo phenone, 4,4'-bis(diethyl amino) benzophenone, and the like can be considered.

As another example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylclioxylate, titanocene compounds, etc. this can be considered.

As a non-limiting example, the content of the photopolymerization initiator may be 1 to 15% by weight, preferably 3 to 10% by weight, based on the total weight of the solid content of the photosensitive resin composition.

When the content of the photopolymerization initiator is within the above range, an insulating pattern may be densely formed from the photosensitive resin composition, and physical properties of the insulating pattern may be uniformly improved.

<Solvent>

The photosensitive resin composition according to an exemplary embodiment includes a solvent.

In the photosensitive resin composition according to exemplary embodiments, the solvent is a material capable of dissolving or dispersing the compound included in the photosensitive resin composition, and the type thereof is not limited.

As examples of representative solvents, alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, cyclic esters and the like can be considered.

More specific examples of the solvent include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Ryu; Aromatic hydrocarbons, such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

Among the above solvents, it is preferable that the boiling point of the solvent is between 100 and 200 ° C. from the viewpoint of securing coating properties and drying properties. As examples thereof, alkylene glycols, alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, Esters such as methyl 3-methoxypropionate and the like can be considered.

The amount of the solvent may be determined in consideration of the solubility of the above components or the above components and other additives to be described later. For example, the type and content of the solvent may be determined in consideration of dispersion stability of the solute and processability (eg, coatability) in the manufacturing process.

<Other additives>

The photosensitive resin composition according to some exemplary embodiments may further include other additives.

Examples of other additives include antioxidants such as 2,2'-thiobis(4-methyl-6-t-butylphenol) or 2,6-di-t-butyl-4-methylphenol; curing agents such as epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, or oxetane compounds; curing aids such as polyvalent carboxylic acids or polyvalent carboxylic acid anhydrides; Surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, or amphoteric surfactants, vinyltrialkoxysilane, haloalkyltrialkoxysilane, isocyanatealkyltrialkoxysilane, or mercaptoalkyltrialkoxysilane, etc. Adhesion promoters, aggregation inhibitors such as sodium polyacrylate, and the like can be considered.

The content of the other additives may be 0.01 to 10% by weight, preferably 0.01 to 5% by weight, more preferably 0.01 to 3% by weight, based on the total weight of the solid content of the photosensitive resin composition.

When the other additives are included in an amount of 0.01 to 10 parts by weight, physical properties of the insulating pattern formed from the photosensitive resin composition may not deteriorate, and each predetermined function may be provided.

<Insulation pattern>

In addition, the present specification additionally discloses an insulating pattern formed from the photosensitive resin composition according to each exemplary embodiment.

An insulating pattern according to example embodiments may be a photocurable pattern formed from a photosensitive resin composition.

In addition, as an example of a photocurable pattern formed from the photosensitive resin composition according to each exemplary embodiment, a color filter further containing a colorant, an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and A spacer pattern or the like may be considered.

The photocuring pattern may be formed by applying the photosensitive resin composition according to each exemplary embodiment on a substrate, photocuring, and developing.

For example, a smooth coating film may be obtained by applying the photosensitive resin composition according to each exemplary embodiment to a substrate and then drying the composition.

As examples of the coating method, spin coating, casting coating, roll coating, slit and spin coating, or slit coating may be considered. In addition, drying of the solvent may be performed through heat drying (pre-bake) or reduced pressure drying. The heating temperature may be usually 70 to 150 °C, preferably 80 to 130 °C.

A mask is placed on one surface of the coating film, and ultraviolet rays are irradiated to form a target insulating pattern. A device such as a mask aligner or a stepper may be installed prior to irradiation with ultraviolet rays. Curing of the irradiated area may be achieved by irradiation of ultraviolet rays.

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 by a person skilled in the art as needed.

When the cured coating film is exposed to an alkaline developer, uncured portions may be dissolved, and an insulating pattern may be developed by dissolution.

As examples of the developing method, a liquid addition method, a dipping method, a spray method, and the like can be considered, and the substrate may be tilted at an arbitrary angle during development.

An alkaline developer used for developing an insulating pattern according to an exemplary embodiment may include an alkaline compound and a surfactant. As non-limiting examples of the alkaline compound, inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate and the like and organic alkaline compounds such as triethylamine, tetramethylammonium hydroxide, ethanolamine and the like can be considered.

As non-limiting examples of the surfactant, known nonionic surfactants, anionic surfactants, or cationic surfactants may be considered.

<Image Display Device>

Also, according to exemplary embodiments, an image display device including the above-described insulating pattern is provided.

In the image display device according to example embodiments, the insulating pattern may include a color filter further containing a colorant, an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and/or a spacer pattern. can be included

In addition, as an example of the image display device, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, a digital camera A display device such as a display device for car navigation and a display device for car navigation may be considered.

In addition, the image display device may include other components that may be included in a conventional image display device, such as a light emitting device such as a light source, a light guide plate, and a liquid crystal display including a color filter.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but these embodiments are only illustrative of the present invention and do not limit the scope of the appended claims, and embodiments within the scope and spirit of the present invention It is obvious to those skilled in the art that various changes and modifications to the are possible, and it is natural that these variations and modifications fall within the scope of the appended claims.

Examples and Comparative Examples

Synthesis Example 1: 1st Binder Resin A-1

400 parts by weight of propylene glycol monomethyl ether acetate, 7 parts by weight of AIBN, 15 parts by weight of tricyclodecane methacrylate, 30 parts by weight of methacrylate in a 1000 ml flask equipped with a stirrer, thermometer reflux condenser, dropping funnel and nitrogen inlet pipe , 20 parts by weight of methacrylic acid, ethyl 3-ethoxy-2-({2-[(2-methylacryloyl)oxy]ethyl}carbamoyl)but-3-enoate (represented by the following formula 1-1 Compound) 20 parts by weight and 15 parts by weight of hydroxyl methacrylate were added and a nitrogen atmosphere was formed.

Thereafter, the temperature of the reaction solution was raised to 70° C. while stirring, and the reaction proceeded for 10 hours to synthesize a first binder resin containing a block isocyanate group. The final solid content of the synthesized first binder resin was 30.0%, the solid acid value was 95 mgKOH/g, and the weight average molecular weight measured by GPC was 7600.

[Formula 1-1]

Synthesis Example 2: First Binder Resin A-2

400 parts by weight of propylene glycol monomethyl ether acetate, 7 parts by weight of AIBN, 15 parts by weight of tricyclodecane methacrylate, 30 parts by weight of methacrylate in a 1000 ml flask equipped with a stirrer, thermometer reflux condenser, dropping funnel and nitrogen inlet pipe , 20 parts by weight of methacrylic acid, 2-{[1-(3,5-dimethyl-4,5-dihydro-1H-pyrazol-1-yl)ethenyl]amino}ethyl 2-methylprop- 20 parts by weight of 2-NOate (a compound represented by Formula 1-2 below) and 15 parts by weight of hydroxyl methacrylate were added, and a nitrogen nitrogen atmosphere was formed.

Thereafter, the temperature of the reaction solution was raised to 70° C. while stirring, and the reaction was conducted for 10 hours to synthesize a first binder resin containing a block isocyanate group. The final solid content of the synthesized first binder resin was 32.0%, the solid acid value was 90 mgKOH/g, and the weight average molecular weight measured by GPC was 7100.

[Formula 1-2]

Synthesis Example 3: Second Binder Resin B-1

Using a dropping lot, 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 55.57 g (0.50 mol) of 2-isopropenyl-2-oxazoline, t-butylperoxy-2-ethyl A precursor mixture was prepared by adding 4 g of hexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA), followed by stirring and mixing. In addition, a chain transfer agent was prepared by stirring and mixing 6 g of n-dodecanethiol and 24 g of PGMEA.

Thereafter, after introducing 395 g of PGMEA into the flask and creating a nitrogen atmosphere in the flask, the temperature of the flask was raised to 90° C. while stirring.

The precursor mixture and chain transfer agent were then loaded from the loading lot. The starting temperature condition at the time of dropping was 90°C, and the dropping time was 2 hours. After 1 hour had elapsed from the end of the dropping, the temperature was raised to 110°C, and the temperature condition was maintained for 3 hours. After 3 hours had elapsed, bubbling was started with a mixed gas of oxygen/nitrogen = 5/95 (v/v).

Then, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% relative to the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were added into the flask, and the reaction was carried out at 110 ° C. for 8 hours to obtain a second binder resin B-1.

The acid value of the finally obtained solid content was 70 mgKOH/g, the weight average molecular weight in terms of polystyrene measured by GPC was 14,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Synthesis Example 4: Second Binder Resin B-2

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet pipe, a nitrogen atmosphere was formed in the flask, and the temperature was raised to 100°C.

Benzyl methacrylate 70.5 g (0.40 mol), methacrylic acid 45.0 g (0.50 mol), 2-methyl-2-oxazoline 42.55 g (0.50 mol), 2- (2-methyl) adamantyl methacrylate 22.0 g (0.10 mole) and 136 g of propylene glycol monomethyl ether acetate were prepared.

A precursor solution was prepared by adding 3.6 g of azobisisobutyronitrile to the precursor mixture, and the precursor solution was added dropwise to the flask over 2 hours using a dropping funnel, and stirred for 5 hours at a temperature of 100 ° C. continued.

Next, an air atmosphere was created in the flask, and 30 g of glycidyl methacrylate [0.2 mol, (40 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were added. was added to the flask. Thereafter, the reaction was continued for 6 hours under a temperature condition of 110° C., thereby obtaining a second binder resin B-2.

The acid value of the finally obtained solid content was 99 mgKOH/g, the weight average molecular weight in terms of polystyrene measured by GPC was 26,000, and the molecular weight distribution (Mw/Mn) was 2.2.

Synthesis Example 5: Second Binder Resin B-3

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet pipe, a nitrogen atmosphere was formed in the flask, and the temperature was raised to 100°C.

Vinyltoluene 47.27 g (0.40 mol), methacrylic acid 45.0 g (0.50 mol), 2-isopropenyl-2-oxazoline 55.57 g (0.50 mol), 2-(2-methyl)adamantyl methacrylate 22.0 g (0.10 mole) and 136 g of propylene glycol monomethyl ether acetate were prepared.

A precursor solution was prepared by adding 3.6 g of azobisisobutyronitrile to the precursor mixture, and the precursor solution was added dropwise to the flask over 2 hours using a dropping funnel, and stirred for 5 hours at a temperature of 100 ° C. continued.

Next, an air atmosphere was created in the flask, and 30 g of glycidyl methacrylate [0.2 mol, (40 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were added. was put into the flask. Thereafter, the reaction was continued for 6 hours under a temperature condition of 110° C., whereby the second binder resin B-3 was obtained.

The acid value of the finally obtained solid content was 99 mgKOH/g, the weight average molecular weight in terms of polystyrene measured by GPC was 23,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Synthesis Example 6: Cardo-based photopolymerizable compound D-1

In a reactor, bisphenol epoxy compound 9,9'-bis(4-glyciloxyphenyl)fluorene (Hear chem) 138g, 2-carboxyethyl acrylate (2-Carboxyethyl acrylate) 54g, benzyltriethylammonium chloride (large Jeonghwageum Co.) 1.4g, triphenylphosphine (Aldrich Co.) 1g, propylene glycol methylethylacetate (Daicel Chemical Co.) 128g, and hydroquinone 0.5g were added, and the temperature was raised to 120° C. and maintained for 12 hours to obtain Formula 8 below. The indicated cardo-based photopolymerizable compound was synthesized.

[Formula 8]

A photosensitive resin composition according to Example and Comparative Example was prepared by mixing the synthesized first binder resin and the like. The composition and content ratio of each photosensitive resin composition according to exemplary embodiments and comparative examples are shown in Table 1 below. The total weight part of the photosensitive resin composition of Example Examples and Comparative Examples shown in Table 1 below is 10.

1st binder resin Second binder resin polymerizable monomer cardo-based photopolymerizable compound photoinitiator solvent additive A B C D E F G Example One A-1 B-1 0.89 - 0.23 7.50 0.04 0.67 0.67 2 A-1 B-2 0.89 0.67 0.67 3 A-1 B-3 0.89 0.67 0.67 4 A-2 B-1 0.89 0.67 0.67 5 A-2 B-2 0.89 0.67 0.67 6 A-2 B-3 0.89 0.67 0.67 7 A-1 B-1 0.89 0.45 0.89 8 A-1 B-1 0.89 0.89 0.45 9 A-1 B-1 0.44 D-1 0.67 0.67 0.43 comparative example One A-1 B-4 0.89 - 0.23 7.50 0.04 0.67 0.67 2 A-1 B-5 0.89 0.67 0.67 3 A-1 - 0.89 1.34 0.00 4 A-2 - 0.89 1.34 0.00 5 - B-1 0.89 0.00 1.34 6 - B-2 0.89 0.00 1.34 7 - B-3 0.89 0.00 1.34 8 - B-4 0.89 0.00 1.34 9 - B-5 0.89 0.00 1.34

The names and structural formulas of each compound listed in Table 1 are as follows.

A-1: First binder resin of Synthesis Example 1

A-2: First binder resin of Synthesis Example 2

B-1: Second binder resin of Synthesis Example 3

B-2: Second binder resin of Synthesis Example 4

B-3: Second binder resin of Synthesis Example 5

B-4: SPCY-1L (acrylic resin, manufactured by Showa Denko)

B-5: SPCY-2L (acrylic resin, manufactured by Showa Denko Co., Ltd.)

C: dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Explosive Co., Ltd.)

D-1: Cardo-based photopolymerizable compound of Synthesis Example 5

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

F: propylene glycol monomethyl ether acetate

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

Experimental example

A 5×5 cm glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with neutral detergent, water, and alcohol, and dried. The photosensitive resin composition according to the exemplary embodiment and the comparative example was spin-coated on one surface of the dried glass substrate, respectively, and pre-baked at 80° C. for about 120 seconds. The pre-baked substrate and the photosensitive resin composition were cooled to room temperature, and light was irradiated onto the photosensitive resin composition using an exposure machine (MA6, manufactured by Karl Suss Co., Ltd.). The exposure amount was 30 mJ/cm 2 (based on 365 nm), a quartz glass photomask was used, and the distance between the substrate and the photomask was 50 μm. Further, in the photomask, square openings (hole patterns) having one side of 30 μm were repeatedly formed on the same plane, and the interval between the openings was 100 μm.

After the exposure process, each cured photosensitive resin composition was developed for 60 seconds in a 2.38% by weight aqueous solution of tetramethyl ammonium hydroxide. Further, by washing with ultrapure water and drying under nitrogen, an insulating pattern could be formed on each photosensitive resin composition. Then, post-baking was performed at 85° C. for about 2 hours.

1. Residue evaluation

The formation of residues on each insulating pattern was evaluated with an optical microscope.

<Evaluation Criteria>

No residue: ○

Residue present: X

2. Moisture resistance evaluation

Moisture resistance was evaluated by measuring and comparing the thickness of each insulating pattern before and after storing it in a chamber at a temperature of 25 °C and a humidity of 85% for 24 hours.

<Evaluation Criteria>

◎: Less than 1% change in thickness

○: thickness change of 1% or more and less than 2%

△: thickness change of 2% or more and less than 5%

X: thickness change of 5% or more

3. Heat resistance evaluation

The thickness of each insulating pattern was measured and compared before and after being placed in an oven at a temperature of 85° C. for 1 hour to evaluate heat resistance.

<Evaluation Criteria>

◎: Less than 1% change in thickness

○: thickness change of 1% or more and less than 2%

△: thickness change of 2% or more and less than 5%

X: thickness change of 5% or more

4. Alkali resistance evaluation

Alkali resistance was evaluated by measuring and comparing the thickness of each insulating pattern before and after putting it in 2.38 wt% aqueous solution of tetramethyl ammonium hydroxide for 5 minutes.

<Evaluation Criteria>

◎: Less than 1% change in thickness

○: thickness change of 1% or more and less than 2%

△: thickness change of 2% or more and less than 5%

X: thickness change of 5% or more

5. Chemical resistance evaluation

The thickness of each insulating pattern was measured and compared before and after being immersed in NMP aqueous solution for 6 minutes, respectively, to evaluate chemical resistance.

6. Evaluation of preservation stability

The photosensitive resin compositions prepared according to Examples and Comparative Examples were placed in an oven at 40° C., and changes in viscosity after 24 hours were evaluated.

<Evaluation Criteria>

◎: Viscosity change less than 1%

○: Viscosity change 1% or more and less than 2%

△: Viscosity change of 2% or more and less than 5%

X: Viscosity change of 5% or more

For each insulating pattern formed from the photosensitive resin composition according to Examples and Comparative Examples, the evaluation results of 1 to 6 are shown in Table 2 below. Each evaluation result may be referred to as excellent (◎), excellent (○), poor (Δ), or poor (X).

residue moisture resistance heat resistance alkali resistance chemical resistance Storage stability Example One ○ ◎ ◎ ◎ 0.00 ◎ 2 ○ ◎ ◎ ◎ -0.01 ◎ 3 ○ ○ ○ ◎ -0.03 ◎ 4 ○ ◎ ◎ ○ -0.01 ○ 5 ○ ◎ ◎ ◎ 0.02 ○ 6 ○ ◎ ◎ ◎ 0.01 ◎ 7 ○ ◎ ◎ ◎ 0.00 ○ 8 ○ ○ ○ ○ 0.01 ○ 9 ○ ◎ ◎ ◎ 0.02 ◎ comparison example One X X △ △ -0.57 ○ 2 X X △ △ -0.60 ○ 3 X X △ X -0.65 △ 4 X △ X X -0.50 X 5 X ○ ○ X -0.45 △ 6 ○ △ ○ ○ -0.30 X 7 X ○ △ △ -0.59 ○ 8 X X X X -0.81 X 9 X X X X -0.95 X

Referring to Table 2, it was confirmed that residue patterns were not formed on each pattern formed from the photosensitive resin composition according to the example and visibility was excellent. Furthermore, according to the chemical resistance evaluation results, even when exposed to the NMP aqueous solution, the thickness of each pattern formed from the photosensitive resin composition according to each example was changed in the range of ±0.03 mm, and it was confirmed that it was not substantially etched by the NMP aqueous solution. .

In addition, each pattern formed from the photosensitive resin composition according to the examples was evaluated as excellent or better in moisture resistance, heat resistance, alkali resistance, and storage stability. In the case of each pattern formed from the photosensitive resin compositions of Examples 1, 2, 5 to 7, and 9, moisture resistance, heat resistance, alkali resistance, and storage stability were all evaluated to be excellent.

It was confirmed that residue patterns were formed on each pattern formed from the photosensitive resin composition according to the comparative example. In addition, each pattern formed from the photosensitive resin composition according to Comparative Example was evaluated to be less than insufficient in at least one of moisture resistance, heat resistance, alkali resistance, and storage stability.

Furthermore, when exposed to the NMP aqueous solution, it was found that the thickness of each pattern formed from the photosensitive resin composition according to Comparative Example decreased by at least 0.3 μm. For example, in the case of Comparative Example 8, it was evaluated that the thickness of the pattern decreased by 0.95 μm.

Claims (9)

A first binder resin comprising at least one repeating unit derived from a block isocyanate-based compound represented by Formula 1 below; A second binder resin containing an oxazoline group or a derivative thereof; polymerizable monomers; photopolymerization initiator; And a photosensitive resin composition containing a solvent:
[Formula 1]

(In Formula 1,
D is O or CH- ₂ ;
Z is an acrylate group, a methacrylate group or a vinyl group,
L ¹ is a C1 to C20 straight chain or C3 to C20 branched chain alkylene group;
BL is a residue derived from a thermally dissociable blocking agent).
The photosensitive resin composition of claim 1, wherein the second binder resin includes at least one oxazoline moiety represented by Formula 2 or Formula 3 below:
[Formula 2]

[Formula 3]

(In Formula 2 and Formula 3,
R ₁ is a C1 to C12 acyclic hydrocarbon group each containing at least one unsaturated bond;
R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen, a halogen atom, a C1 to C12 straight chain or C3 to C12 branched chain alkyl group, a C6 to C12 aryl group, a C7 to C12 arylalkyl group, or a C7 to C12 alkylaryl group).
The photosensitive resin composition of claim 1, wherein the second binder resin is an oxazoline-containing copolymer including at least one oxazoline moiety.
The photosensitive resin composition according to claim 3, wherein the oxazoline-containing copolymer is a terpolymer, and at least one of the oxazoline moieties is a pendant group of the terpolymer.
The method according to claim 1, wherein the heat dissociable blocking agent is a phenol-based blocking agent, a lactam-based blocking agent, an active methylene-based blocking agent, an alcohol-based blocking agent, an oxime-based blocking agent, a mercaptan-based blocking agent, an acid amide-based blocking agent, or an imide-based blocking agent. A photosensitive resin composition comprising at least one selected from a blocking agent, an amine-based blocking agent, an imidazole-based blocking agent, an imine-based blocking agent, and a pyrazole-based blocking agent.
The photosensitive resin composition according to claim 1, further comprising at least one of the cardo-based photopolymerizable compounds represented by the following Chemical Formulas 4 to 6:
[Formula 4]

[Formula 5]

[Formula 6]

(In Formulas 4 to 6, R ₆ and R ₇ are each independently hydrogen, a halogen atom, a hydroxyl group, a thiol group, an amino group, a nitro group, or a halogen atom, an ester group, a hydroxyl group, and at least one of a carbon-carbon double bond It is a C1 to C20 straight chain or C3 to C20 branched chain alkyl group including one).
The method according to claim 1, of the total solid weight of the photosensitive resin composition,
10 to 80% by weight of the first binder resin;
5 to 80% by weight of the second binder resin; and
A photosensitive resin composition comprising 10 to 60% by weight of the polymerizable monomer.
An insulating pattern formed from the photosensitive resin composition according to claim 1 .
An image display device comprising the insulating pattern according to claim 8 .