KR102252996B1 - Photosensitive resin composition, photosensitive resin layer using the same and electronic device - Google Patents

Abstract

(A) alkali-soluble resin; (B) photosensitive diazoquinone compound; (C) a crosslinking agent comprising a triazine core, a urethane linking group, and a substituted or unsubstituted C3 to C10 alkoxy group; And (D) a photosensitive resin composition containing a solvent, a photosensitive resin film prepared using the same, and an electronic device including the photosensitive resin film.

Description

A photosensitive resin composition, a photosensitive resin film and an electronic device using the same TECHNICAL FIELD [0001] PHOTOSENSITIVE RESIN LAYER USING THE SAME AND ELECTRONIC DEVICE

The present description relates to a photosensitive resin composition, a photosensitive resin film using the same, and an electronic device including the photosensitive resin film.

Conventionally, polyimide resins, polybenzoxazole resins, and the like, which have excellent heat resistance, electrical properties, mechanical properties, and the like, have been widely used as materials for display device panels and surface protective films and interlayer insulating films used in semiconductor devices. Since these resins have low solubility in various solvents, they are generally provided as a composition dissolved in a solvent in the form of a precursor in many cases.

However, due to the recent increase in environmental problems, countermeasures against organic solvents have been demanded, and similarly to photoresists, various proposals of heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution have been made.

Among them, a method of using an alkaline aqueous solution-soluble hydroxypolyamide resin which becomes a heat-resistant resin after heat curing is mixed with a photoacid generator such as a naphthoquinone diazide compound as a photosensitive resin composition has been proposed.

The developing mechanism of the photosensitive resin composition is by exposing the naphthoquinone diazide compound (i.e., photosensitive diazoquinone compound) and the polybenzoxazole (PBO) precursor to the unexposed portion, thereby exposing the photosensitive diazoquinone compound to indenecarboxylic acid. By transforming it into a compound, it takes advantage of the fact that the dissolution rate in an alkaline aqueous solution increases. By using the difference in dissolution rate for the developer between the exposed portion and the unexposed portion, it is possible to manufacture a relief pattern composed of an unexposed portion.

The photosensitive resin composition can form a positive relief pattern by exposure and development by an alkaline aqueous solution. Moreover, it has a thermosetting film characteristic by heating.

By the way, in the manufacturing process of a semiconductor, etc., as fine processing is in progress, the spacing between a pattern and a pattern is getting shorter. For this reason, when the film reduction during development is increased, contact with the developer occurs not only from the top of the film but also from the side surface during development, even if the dissolution rate of the unexposed portion is small in the unexposed portion adjacent to the opened exposed portion. Therefore, the pattern shape becomes too thin, and the reliability of the semiconductor package is lowered in the manufacturing process of a semiconductor device.

Therefore, it is necessary to develop almost without dissolving the unexposed portion (this phenomenon is said to have a high development residual film rate). However, in the case of increasing the development residual film rate, a high exposure amount is required for development of the exposed portion (this is referred to as a reduced degree).

Accordingly, a method of adding a phenolic compound to a heat-resistant resin precursor has been proposed as a method of forming a high residual film during development (adjusting development properties) and increasing sensitivity. However, conventionally used phenolic compounds have limitations in improving flexibility, and thus it is difficult to use them as circuit protection films in electronic devices such as semiconductors where elongation and elastic modulus are important.

Therefore, research to develop a photosensitive resin composition capable of solving the above problem is ongoing.

One embodiment is to provide a photosensitive resin composition capable of improving flexibility while maintaining heat resistance, strength, and the like at the same level as in the prior art.

Another embodiment is to provide a photosensitive resin film prepared by using the photosensitive resin composition.

Another embodiment is to provide an electronic device including the photosensitive resin film.

One embodiment is (A) an alkali-soluble resin; (B) photosensitive diazoquinone compound; (C) a crosslinking agent comprising a triazine core, a urethane linking group, and a substituted or unsubstituted C3 to C10 alkoxy group; And (D) It provides a photosensitive resin composition containing a solvent.

The crosslinking agent may be represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ³ are each independently a substituted or unsubstituted C3 to C10 alkoxy group,

R ⁴ to R ⁶ are each independently a hydrogen atom or *-C(=O)R ⁷ (R ⁷ is a C3 to C10 alkoxy group).

Each of R ⁴ to R ⁶ may independently be a hydrogen atom.

The crosslinking agent may be included in an amount of 3 parts by weight to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin.

The alkali-soluble resin may include a polybenzoxazole precursor, a polyimide precursor, a novolac resin, or a combination thereof.

The photosensitive resin composition may further include a dissolution control agent.

The photosensitive resin composition includes 5 parts by weight to 50 parts by weight of the photosensitive diazoquinone compound, 1 part by weight to 20 parts by weight of the crosslinking agent, and 100 parts by weight of the solvent based on 100 parts by weight of the alkali-soluble resin. It may contain from part to 500 parts by weight.

The photosensitive resin composition may further include an additive of malonic acid, 3-amino-1,2-propanediol, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.

Another embodiment provides a photosensitive resin film prepared by using the photosensitive resin composition.

Another embodiment provides an electronic device including the photosensitive resin film.

Other specifics of aspects of the present invention are included in the detailed description below.

The photosensitive resin composition according to an embodiment may improve not only strength, heat resistance, but also flexibility at the same time by including a crosslinking agent having a specific structure, and thus may be usefully used in manufacturing a circuit protective film used in electronic devices such as semiconductor devices.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified in the specification, "alkyl group" refers to a C1 to C20 alkyl group, "alkenyl group" refers to a C2 to C20 alkenyl group, and "cycloalkenyl group" refers to a C3 to C20 cycloalkenyl group, and , "Heterocycloalkenyl group" refers to a C3 to C20 heterocycloalkenyl group, "aryl group" refers to a C6 to C20 aryl group, and "arylalkyl group" refers to a C6 to C20 arylalkyl group, and "alkylene group" Means a C1 to C20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, and "heteroarylene group" refers to a C3 to C20 hetero It means an arylene group, and the "alkoxyl group" means a C1 to C20 alkoxyl group.

Unless otherwise specified in the specification, "substituted" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 To C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, C2 To C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a combination thereof.

In addition, unless otherwise specified in the specification, "hetero" means that at least one hetero atom of at least one of N, O, S, and P is included in the formula.

In addition, unless otherwise specified in the specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" refers to "acrylic acid" and "methacrylic acid. "It means both are possible.

In the present specification, unless otherwise defined, "combination" means mixing or copolymerization. In addition, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Unless otherwise specified in the specification, the unsaturated bond includes not only multiple bonds between carbon-carbon atoms, but also other molecules such as carbonyl bonds and azo bonds.

Unless otherwise defined in the chemical formula in the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.

In the present specification, unless otherwise defined, "*" means a moiety connected with the same or different atoms or chemical formulas.

The photosensitive resin composition according to an embodiment includes (A) an alkali-soluble resin; (B) photosensitive diazoquinone compound; (C) a crosslinking agent comprising a triazine core, a urethane linking group, and a substituted or unsubstituted C3 to C10 alkoxy group; And (D) a solvent.

In the case of a semiconductor circuit protective film, among the mechanical properties, stress-relaxation capability is required for the internal/external environment.One embodiment is a photosensitive resin containing a multifunctional crosslinking agent to improve heat resistance, elasticity, and stress relaxation. It relates to a composition, and more specifically relates to a photosensitive resin composition comprising a polyfunctional triazine-based crosslinking agent that reacts with a hydroxy group of an alkali-soluble resin to form a urethane bond.

Alkali-soluble resin is included as a key element of the photosensitive resin composition used as a semiconductor circuit protective film, typically polyimide (PI) or polyhydroxyamide based on polyamic acid (PAA) or polyamic acetate (PAE). (PHA)-based polybenzoxazole (PBO) resin is widely used. The photosensitive resin composition containing the resin is used together with other photosensitizers, dissolution control agents, etc. to realize excellent photosensitive characteristics and pattern characteristics without residues.In particular, durability such as heat resistance and etch resistance is required, and in particular, semiconductor circuits In the case of a protective film, mechanical properties such as strength, elongation, and elastic modulus are essentially required.

Polyimide and polybenzoxazole compositions generally have excellent heat resistance, chemical resistance, mechanical strength, and electrical properties, and have a low coefficient of thermal expansion, so they are applied to various fields of semiconductors and display devices. It is suitable to protect the device from mechanical/thermal stress and moisture (moisture absorption) applied during the assembly process.

Since the thermosetting film formed from the polyimide and polybenzoxazole precursor composition continuously remains in the semiconductor device and acts as a surface protection film, mechanical properties of the film such as tensile strength, elongation, and Young's modulus are very important. Polybenzoxazole resins often have the mechanical properties as described above, specifically elongation below an appropriate level, and to solve this, various additives are used, or a precursor compound having a structure capable of crosslinking during thermal curing is used. Examples were reported in advance.

On the other hand, the above polyimide and polybenzoxazole resins have excellent heat resistance, dimensional stability, and storage stability as known, and are easy to manufacture industrially, but they remain hydroxy groups even after the curing process, so when applied as a material for electronic devices such as semiconductors, they have hygroscopic resistance. There is a disadvantage in that it is vulnerable to, and it is advantageous to have a low molecular weight of the resin in order to realize high-sensitivity pattern characteristics, but the mechanical properties become more fragile and act as a disadvantage. Therefore, in order to compensate for the above disadvantages, a crosslinking agent capable of reacting with the hydroxy group of the resin can be additionally used, and when a flexible urethane bond is introduced into the polyimide and polybenzoxazole backbone having a relatively rigid structure, the mechanical Since it is possible to improve physical properties and stress relaxation, it is possible to reinforce the function of protecting the circuit from various stresses generated during the process.

Hereinafter, each component will be described in detail.

(C) crosslinking agent

In general, polyfunctional triazine-based crosslinking agents (melamine crosslinking agents) have relatively high reactivity and crosslinking efficiency, so they can be applied as crosslinking agents to various materials, but there are limitations in improving Young's modulus, elongation, and residual stress, so there is a problem in applying them for electronic materials. . However, according to one embodiment, by applying a triazine-based crosslinking agent having a more limited structure, a photosensitive resin composition having enhanced circuit protection film functions such as heat resistance and mechanical properties is provided.

Specifically, the structure-limited triazine-based crosslinking agent has a substituted or unsubstituted alkoxy group at the terminal, and the alkoxy group is composed of 3 to 10 carbon atoms. When the number of carbon atoms constituting the alkoxy group is 1 or 2, that is, when the alkoxy group is a methoxy group or an ethoxy group, the terminal length is too short to improve flexibility, and when the number of carbon atoms constituting the alkoxy group is 11 or more, the terminal length The crosslinking efficiency is deteriorated due to steric hindrance due to too long, and the function as a crosslinking agent may be lost.

For example, a triazine-based crosslinking agent having a limited structure may be a multifunctional crosslinking agent. For example, the substituted or unsubstituted alkoxy group located at the terminal may be 3 to 6, such as 3.

For example, the crosslinking agent may be represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ³ are each independently a substituted or unsubstituted C3 to C10 alkoxy group,

R ⁴ to R ⁶ are each independently a hydrogen atom or *-C(=O)R ⁷ (R ⁷ is a C3 to C10 alkoxy group).

The crosslinking agent reacts with a hydroxyl group of an alkali-soluble resin to be described later to form a crosslinked structure, thereby improving flexibility through mitigation of thermal and mechanical stress generated during the process, and ultimately effectively protecting electronic devices such as semiconductor circuits.

For example, R ⁴ to R ⁶ may each independently be a hydrogen atom.

The crosslinking agent may be included in an amount of 3 parts by weight to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the crosslinking agent is included in an amount of less than 3 parts by weight relative to 100 parts by weight of the alkali-soluble resin, the content is too small, and the cross-linking efficiency is deteriorated. It may cause a decrease in device reliability, such as a decrease in the elongation of the coating film.

(A) alkali-soluble resin

The alkali-soluble resin may be a resin containing a hydroxy group, such as a polybenzoxazole precursor, a polyimide precursor, a novolac resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, or a combination thereof.

The polybenzoxazole precursor may include a structural unit represented by Formula 2 below, and the polyimide precursor may include a structural unit represented by Formula 3 below.

[Formula 2]

In Chemical Formula 2,

X ⁰ and X ¹ are each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

Y ⁰ and Y ¹ are each independently a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted divalent to hexavalent C3 to C30 is an alicyclic organic group,

R ⁹ and R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a metal ion or an ammonium ion. ,

m1 and m2 are each independently an integer of 0 to 100000, and m1 + m2 is an integer of 2 or more.

[Formula 3]

In Chemical Formula 3,

X ² is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group ,

Y ² is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted tetravalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted tetravalent to hexavalent C3 to C30 alicyclic organic group .

In Formula 2, X ¹ may be a residue derived from an aromatic diamine as an aromatic organic group.

Examples of the aromatic diamine include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino- 4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-5-trifluoromethylphenyl)hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-6-trifluoromethylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-2-trifluoromethylphenyl)hexafluoropropane, 2 ,2-bis(4-amino-3-hydroxy-5-trifluoromethylphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxy-6-trifluoromethylphenyl)hexafluoro Lopropane, 2,2-bis(4-amino-3-hydroxy-2-trifluoromethylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-5-pentafluoro Ethylphenyl)hexafluoropropane, 2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-amino-4-hydroxy-5-pentafluoroethylphenyl)hexafluoro Lopropane, 2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-5-trifluoromethylphenyl)hexafluoropropane, 2-( 3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-6-trifluoromethylphenyl)hexafluoropropane, 2-(3-amino-4- Hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-2-trifluoromethylphenyl)hexafluoropropane, 2-(3-amino-4-hydroxy-2-tri Fluoromethylphenyl)-2-(3-hydroxy-4-amino-5-trifluoromethylphenyl)hexafluoropropane and 2-(3-amino-4-hydroxy-6-trifluoromethylphenyl)-2 At least one selected from -(3-hydroxy-4-amino-5-trifluoromethylphenyl)hexafluoropropane may be used. However, it is not limited thereto.

Examples of X ⁰ and X ¹ include functional groups represented by the following Formulas 4 and 5, but are not limited thereto.

[Formula 4]

[Formula 5]

In Chemical Formula 4 and Chemical Formula 5,

A ¹ may be a single bond, O, CO, CR ⁴⁷ R ⁴⁸ , SO ₂ or S, and R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, specifically C1 to C30 fluoroalkyl group,

R ⁵⁰ to R ⁵² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxy group or a thiol group,

n10 is an integer of 0 to 2, and n11 and n12 are each independently an integer of 0 to 3.

In Formula 2, Y ⁰ and Y ¹ are each independently an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent alicyclic organic group, and may be a residue of a dicarboxylic acid or a residue of a dicarboxylic acid derivative. have. Specifically, Y ⁰ and Y ¹ may each independently be an aromatic organic group or a divalent to hexavalent alicyclic organic group.

Specific examples of the dicarboxylic acid derivative include 4,4'-oxydibenzoyl chloride, diphenyloxydicarbonyldichloride, bis (phenylcarbonyl chloride) sulfone, bis (phenylcarbonyl chloride) ether, bis (phenylcarbonyl chloride) ) Phenone, phthaloyl dichloride, terephthaloyl dichloride, isophthaloyl dichloride, dicarbonyldichloride, diphenyloxydicarboxylate dibenzotriazole, or combinations thereof, but are not limited thereto.

Examples of Y ⁰ and Y ¹ include functional groups represented by the following Chemical Formulas 6 to 8, but are not limited thereto.

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 6 to 8,

R ⁵³ to R ⁵⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group,

n13 and n14 are each independently an integer of 0 to 4, n15 and n16 are each independently an integer of 0 to 3,

A ² may be a single bond, O, CR ⁴⁷ R ⁴⁸ , CO, CONH, S or SO ₂ , and R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, specifically Examples are C1 to C30 fluoroalkyl groups.

In Formula 3, X ² is an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent alicyclic organic group. Specifically, X ² is an aromatic organic group or a divalent to hexavalent alicyclic organic group.

Specifically, X ² may be a residue derived from an aromatic diamine, an alicyclic diamine, or a silicone diamine. In this case, the aromatic diamine, alicyclic diamine, and silicone diamine may be used alone or in combination of one or more of them.

Examples of the aromatic diamine include 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine , Bis[4-(4-aminophenoxy)phenyl]sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl ]Ether, 1,4-bis(4-aminophenoxy)benzene, compounds in which an alkyl group or a halogen atom is substituted in their aromatic ring, or a combination thereof, but are not limited thereto.

Examples of the alicyclic diamine include 1,2-cyclohexyl diamine, 1,3-cyclohexyl diamine, or a combination thereof, but is not limited thereto.

Examples of the silicone diamine include bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)tetramethylsiloxane, bis(p-aminophenyl)tetramethyldisiloxane, bis(γγ-aminopropyl)tetramethyldisiloxane , 1,4-bis(γγ-aminopropyldimethylsilyl)benzene, bis(4-aminobutyl)tetramethyldisiloxane, bis(γγ-aminopropyl)tetraphenyldisiloxane, 1,3-bis(aminopropyl)tetra Methyldisiloxane or a combination thereof may be mentioned, but the present invention is not limited thereto.

In Formula 3, Y ² is an aromatic organic group, a tetravalent to hexavalent aliphatic organic group, or a tetravalent to hexavalent alicyclic organic group. Specifically, Y ² is an aromatic organic group or a tetravalent to hexavalent alicyclic organic group.

The Y ² may be a residue derived from an aromatic acid dianhydride or an alicyclic acid dianhydride. In this case, the aromatic acid dianhydride and the alicyclic acid dianhydride may be used alone or in combination of one or more of them.

Examples of the aromatic acid dianhydride include pyromellitic dianhydride; Benzophenone tetracarboxylic dianhydride such as benzophenone-3,3',4,4'-tetracarboxylic dianhydride ; Oxydiphthalic dianhydride such as 4,4'-oxydiphthalic dianhydride; Biphthalic dianhydride such as 3,3',4,4'-biphthalic dianhydride; (Hexafluoroisopropylidene)diphthalic dianhydride, such as 4,4'-(hexafluoroisopropyledene)diphthalic dianhydride (4,4'-(hexafluoroisopropyledene)diphthalic dianhydride) ; Naphthalene-1,4,5,8-tetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic dianhydride (3,4,9,10-perylenetetracarboxylic dianhydride), and the like, but are not limited thereto.

Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1,2,3,4-cyclobutanetetracarboxylic dianhydride), 1,2,3,4-cyclopentanetetracarboxyl Acid dianhydride (1,2,3,4-cyclopentanetetracarboxylic dianhydride), 5-(2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexane-1,2-dicarboxylic dianhydride (5- (2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexane-1,2-dicarboxylic anhydride), 4-(2,5-dioxotetrahydrofuran-3-yl)-tetraline-1,2-dicar Acid dianhydride (4-(2,5-dioxotetrahydrofuran-3-yl)-tetralin-1,2-dicarboxylic anhydride), 　bicyclooctene-2,3,5,6-tetracarboxylic dianhydride (bicyclooctene- 2,3,5,6-tetracarboxylic dianhydride), bicyclooctene-1,2,4,5-tetracarboxylic dianhydride, and the like, It is not limited thereto.

For example, the alkali-soluble resin may include a polybenzoxazole precursor, a polyimide precursor, a novolac resin, or a combination thereof.

For example, the alkali-soluble resin may include a polybenzoxazole precursor and a novolac resin. When both the polybenzoxazole precursor and the novolac resin are included, it may be advantageous for controlling the development speed and forming a fine pattern.

The alkali-soluble resin may have a weight average molecular weight (M _w ) of 3,000 g/mol to 300,000 g/mol, specifically 5,000 g/mol to 30,000 g/mol of a weight average molecular weight (M _w ). have. When it has a weight average molecular weight (M _w ) in the above range, a sufficient residual film rate can be obtained in the non-exposed portion when developing with an aqueous alkali solution, and patterning can be performed efficiently.

(B) photosensitive diazoquinone compound

As the photosensitive diazoquinone compound, a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure may be preferably used.

Representative examples of the photosensitive diazoquinone compound include compounds represented by Chemical Formula 21 and Chemical Formula 23 to Chemical Formula 25, but are not limited thereto.

[Formula 21]

In Chemical Formula 21,

R ³¹ to R ³³ may each independently be a hydrogen atom or a substituted or unsubstituted alkyl group, specifically CH ₃ ,

D ¹ to D ³ may each independently be OQ, and Q may be a hydrogen atom, a functional group represented by the following formula 22a, or a functional group represented by the following formula 22b, wherein Q may not be a hydrogen atom at the same time,

Each of n31 to n33 may independently be an integer of 1 to 5.

[Formula 22a]

[Formula 22b]

[Formula 23]

In Chemical Formula 23,

R ³⁴ may be a hydrogen atom or a substituted or unsubstituted alkyl group,

D ⁴ to D ⁶ may each independently be OQ, and Q is the same as defined in Formula 16,

Each of n34 to n36 may independently be an integer of 1 to 5.

[Formula 24]

In Chemical Formula 24,

A ³ may be CO or CR ⁵⁰⁰ R ⁵⁰¹ , and R ⁵⁰⁰ and R ⁵⁰¹ may each independently be a substituted or unsubstituted alkyl group,

D ⁷ to D ¹⁰ may each independently be a hydrogen atom, a substituted or unsubstituted alkyl group, OQ or NHQ, and Q is the same as defined in Formula 21,

n37, n38, n39 and n40 may each independently be an integer of 1 to 4,

n37+n38 and n39+n40 may each independently be an integer of 5 or less,

However, ^{at least one of D 7} to D ¹⁰ is OQ, one aromatic ring may contain 1 to 3 OQ, and the other aromatic ring may contain 1 to 4 OQ.

[Formula 25]

In Chemical Formula 25,

R ₃₅ to R ₄₂ may each independently be a hydrogen atom or a substituted or unsubstituted alkyl group,

n41 and n42 may each independently be an integer of 1 to 5, specifically, may be an integer of 2 to 4,

Q is the same as defined in Chemical Formula 21.

The photosensitive diazoquinone compound is preferably contained in an amount of 5 parts by weight to 50 parts by weight, such as 10 parts by weight to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the content of the photosensitive diazoquinone compound is within the above range, the pattern is well formed without residue by exposure, there is no loss of film thickness during development, and a good pattern can be obtained.

(D) solvent

The photosensitive resin composition may include a solvent capable of easily dissolving each component such as the alkali-soluble resin, the photosensitive diazoquinone compound, and the crosslinking agent.

The solvent is an organic solvent, specifically N-methyl-2-pyrrolidone, gamma-butyrolactone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol di Ethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate (methyl lactate), ethyl lactate (ethyl lactate), butyl lactate (butyl Lactate), methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate (methylpyruvate), ethyl pyruvate (ethylpyruvate), methyl-3-me It may be used, such as oxy propionate or a combination thereof, but is not limited thereto.

The solvent may be appropriately selected and used according to a process of forming a photosensitive resin film such as spin coating or slit die coating.

The solvent is preferably used in an amount of 100 parts by weight to 500 parts by weight, for example, 100 parts by weight to 300 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the solvent is within the above range, a film having a sufficient thickness can be coated, and solubility and coating properties are excellent.

(E) dissolution regulator

The photosensitive resin composition according to an embodiment may further include a dissolution control agent.

For example, the dissolution control agent may be represented by the following formula (9).

[Formula 9]

In Chemical Formula 9,

R ⁷ to R ¹⁶ are each independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted Is a C6 to C20 aryl group,

However, ^{at least one of R 7} to R ¹¹ and at least one of R ¹² to R ¹⁶ is a hydroxy group,

L ¹ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkyrene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

For example, the dissolution control agent may be represented by any one of the following Formulas 9-1 to 9-7.

[Chemical Formula 9-1]

(In Formula 9-1, R ⁶⁰¹ is a hydrogen atom or CH ₃ , and R ⁶⁰² to R ⁶⁰⁶ are each independently a hydrogen atom, OH or CH ₃ )

[Chemical Formula 9-2]

(In Formula 9-2, R ⁶⁰⁷ to R ⁶¹² are the same or each independently a hydrogen atom, OH or CH ₃ .)

[Chemical Formula 9-3]

(In Formula 9-3, R ⁶¹³ to R ⁶¹⁸ are each independently a hydrogen atom, OH or CH ₃ , and R ⁶¹⁹ and R ⁶²⁰ are each independently a hydrogen atom or CH ₃ ).

[Chemical Formula 9-4]

[Chemical Formula 9-5]

(In Formula 9-5, R ⁶²¹ to R ⁶²⁶ are each independently a hydrogen atom or OH.)

[Chemical Formula 9-6]

[Chemical Formula 9-7]

The amount of the dissolution control agent is preferably 1 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the dissolution control agent is included within the above range, it is possible to increase the dissolution rate and sensitivity of the exposed portion when developing with an alkaline aqueous solution, and also play a role of enabling high-resolution patterning without developing scum during development.

(F) other additives

The photosensitive resin composition according to an embodiment may further include other additives.

The photosensitive resin composition includes malonic acid, 3-amino-1,2-propanediol, leveling agent, silane-based coupling agent, Surfactants, radical polymerization initiators, or additives of a combination thereof may be included. The amount of these additives used can be easily adjusted according to the desired physical properties.

For example, the silane-based coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to the substrate.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, and γ-gly Cidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.

The silane-based coupling agent may be included in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane-based coupling agent is included within the above range, adhesion and storage properties are excellent.

For example, the surfactant is added to prevent uneven film thickness or improve developability, and may include a fluorine-based surfactant and/or a silicone-based surfactant.

In the fluorine-based surfactant, BM Chemie社of ^{BM-1000 ®®, BM-1100} ®® and the like; ^{Mechapack F 142D ® ®} , F 172 ^{® ®} , F 173 ^{® ®} , F 183 ^{® ®} , F 554 ^{® ®,} etc. of Dai Nippon Inki Chemical Co., Ltd.; Sumitomo M. (Note)社pro rod FC-135 ^®®, copper FC-170C ^®®, copper FC-430 ^®®, copper FC-431 ^®® and the like; Asahi Glass Co., Ltd.'s Saffron S- ^112®® , copper S- ^113®® , copper S- ^131®® , copper S- ^141®® , copper S- ^145®®, etc.; It may be selected from commercially available under the name, such as Toray Silicone (Note)社SH-28PA ^®®, copper -190 ^®®, copper ^{-193 ®®, SZ-6032 ®®,} SF-8428 ®®.

As the silicone surfactant, BYK Chem's BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, A commercially available product such as BYK-325 can be used.

The surfactant may be used in an amount of 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is ensured, stains do not occur, and wetting properties for IZO substrates or glass substrates are excellent.

In addition, the photosensitive resin composition may further include an epoxy compound as an additive to improve adhesion and the like. As the epoxy compound, an epoxy novolac acrylic carboxylate resin, an ortho cresol novolac epoxy resin, a phenol novolac epoxy resin, a tetramethyl biphenyl epoxy resin, a bisphenol A type epoxy resin, an alicyclic epoxy resin, or a combination thereof may be used. I can.

When the epoxy compound is further included, a radical polymerization initiator such as a peroxide initiator or an azobis-based initiator may be further included.

The epoxy compound may be used in an amount of 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included within the above range, it is possible to improve storage properties and economical adhesion and other properties.

In addition, the photosensitive resin composition may further include a thermal latent acid generator. Examples of the thermally latent acid generator include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid; Perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid and trifluorobutanesulfonic acid; Alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid; Or a combination thereof may be mentioned, but the present invention is not limited thereto.

The thermally latent acid generator is a catalyst for dehydration and cyclization of a polyamide containing a phenolic hydroxyl group of a polybenzoxazole precursor, and may smoothly proceed with a cyclization reaction even when the curing temperature is lowered.

In addition, a certain amount of other additives such as antioxidants and stabilizers may be added to the photosensitive resin composition within a range that does not impair physical properties.

Another embodiment provides a photosensitive resin film prepared by exposing, developing, and curing the above-described photosensitive resin composition.

The photosensitive resin film manufacturing method is as follows.

(1) Application and film formation step

After applying the photosensitive resin composition to a desired thickness on a substrate such as a glass substrate or an ITO substrate subjected to a predetermined pretreatment using a method such as a spin or slit coating method, a roll coating method, a screen printing method, or an applicator method, 70 The coating film is formed by heating at ℃ ℃ to 150 ℃ ℃ for 1 minute to 10 minutes to remove the solvent.

(2) exposure step

After interposing a mask to form a necessary pattern on the obtained photosensitive resin film, active rays of 200 nm to 500 nm are irradiated. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used, and in some cases, an X-ray, an electron beam, and the like can be used.

The exposure amount varies depending on the type, blending amount, and dry film thickness of each component of the composition, but is 500 mJ/cm ² (using a 365 nm sensor) or less when a high-pressure mercury lamp is used.

(3) development stage

As a developing method, after the exposure step, the exposed portion is dissolved and removed using a developer, so that only the unexposed portion remains to obtain a pattern.

(4) Post-processing step

There is a post-heating process for obtaining an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, and storage stability for the image pattern obtained by development in the above process. For example, it may be heated in a convection oven at 250° C. for 1 hour after development.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited by the following examples.

(Example)

(Synthesis of alkali-soluble resin)

11.0 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide was added to N-methyl-2-while passing nitrogen through a 4-neck flask equipped with a stirrer, temperature controller, nitrogen gas injection device, and cooler. It was dissolved in 280 g of pyrrolidone (NMP). When the solid is completely dissolved, 9.9 g of pyridine is added to the solution, and 13.3 g of 4,4'-oxydibenzoyl chloride is added to N-methyl-2-pyrrolidone (NMP) while maintaining the temperature at 0°C to 5°C. The solution dissolved in 142 g was slowly added dropwise for 30 minutes. After dropping, the reaction was carried out at 0°C to 5°C for 1 hour, and the temperature was raised to room temperature and stirred for 1 hour to terminate the reaction. To this, 1.6 g of 5-norbornene-2,3-dicarboxionhydride was added and stirred at 70° C. for 24 hours to complete the reaction. The reaction mixture was added to a solution of water/methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and sufficiently washed with water. A polybenzoxazole (PBO) precursor having a weight average molecular weight of 11,100 g/mol was prepared by drying at a temperature of 80° C. and vacuum for more than 24 hours.

(Production of photosensitive resin composition)

Examples 1 to 7 and Comparative Examples 1 to 5

According to the compositions shown in Tables 1 and 2 below, the polybenzoxazole precursor was added to and dissolved in γγ (gamma)-butyrolactone (GBL), and then photosensitive diazoquinone compound, cresol-based novolac resin, crosslinking agent And a silane coupling agent (addition of a phenolic compound in some cases), and after stirring at room temperature for 1 hour, a leveling agent was further added and dissolved, and then filtered through a 0.45 μm PE syringe filter to obtain a photosensitive resin composition.

(Unit: g) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 (A) alkali-soluble resin (A-1) 25.0 25.0 25.0 25.0 25.0 25.0 25.0 (A-2) 6.5 6.5 6.5 6.5 6.5 6.5 6.5 (B) photosensitive diazoquinone compound 6.0 6.0 6.0 6.0 6.0 6.0 6.0 (C) crosslinking agent (C-1) 1.0 3.0 5.0 7.0 9.0 0.5 10.0 (C-2) - - - - - - - (C-3) - - - - - - - (C-4) - - - - - - - (C-5) - - - - - - - (D) solvent 50.0 50.0 50.0 50.0 50.0 50.0 50.0 (E) dissolution regulator 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (F) other additives (F-1) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (F-2) 0.2 0.2 0.2 0.2 0.2 0.2 0.2

(Unit: g) Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 4 Example 5 (A) alkali-soluble resin (A-1) 25.0 25.0 25.0 25.0 25.0 (A-2) 6.5 6.5 6.5 6.5 6.5 (B) photosensitive diazoquinone compound 6.0 6.0 6.0 6.0 6.0 (C) crosslinking agent (C-1) - - - - - (C-2) - - - 7.0 - (C-3) - - - - 7.0 (C-4) - 7.0 - - - (C-5) - - 7.0 - - (D) solvent 50.0 50.0 50.0 50.0 50.0 (E) dissolution regulator 5.0 5.0 5.0 5.0 5.0 (F) other additives (F-1) 0.3 0.3 0.3 0.3 0.3 (F-2) 0.2 0.2 0.2 0.2 0.2

(A) alkali-soluble resin

(A-1) polybenzoxazole precursor

(A-2) Cresol-based novolac resin (KCR-6100)

(B) photosensitive diazoquinone compound (formula A)

[Formula A]

로 치환되어 있고, 나머지 하나는 수소 원자이다.)(In Formula A, Q ¹ , Q ² and Q ³ , two are

And the other is a hydrogen atom.)

(C) crosslinking agent

(C-1) Tris(butoxycarbonylamino) triazine (Cytec company)

(C-2) Tris(metoxycarbonylamino) triazine (Cytec company)

(C-3) Compound represented by the following formula C-3 (Cytec Corporation)

[Chemical Formula C-3]

(C-4) p-xylene glycol (Cytec company)

(C-5) Hexamethoxymethylmelamine (Cytec company)

(D) solvent

γ (gamma)-butyrolactone (GBL)

(E) dissolution regulator (chemical formula B)

[Formula B]

(F) other additives

(F-1) Silane coupling agent (KBM-573 (2%))

(F-2) Leveling agent (BYK-378)

evaluation

<Mechanical properties>

The photosensitive resin composition according to Examples 1 to 7 and Comparative Examples 1 to 5 was spin-coated on a glass plate, followed by heat treatment at 180° C. for 60 minutes and 300° C. for 60 minutes in a furnace oven under nitrogen flow to obtain a thickness After forming a 10 µm film, a cut is made on the edge and then peeled off with water. The peeled film is dried at 100° C. for about 30 minutes to remove water, and then the film is cut to a size of 100 X 10 mm based on ASTM-D882. The elongation at break was measured using UTM analysis, and the results are shown in Table 3 below.

<Heat resistance>

The photosensitive resin composition according to Examples 1 to 7 and Comparative Examples 1 to 5 was spin-coated on a glass plate, followed by heat treatment at 180° C. for 60 minutes and 300° C. for 60 minutes in a furnace oven under nitrogen flow to obtain a thickness After forming a 10 μm film, it was measured using a thermogravimetric analysis (TGA-Q500). When the temperature was raised from room temperature to 600°C in a nitrogen atmosphere at 10°C/min, the temperature of the portion having a mass loss of 5% compared to the initial mass was confirmed, and the results are shown in Table 3 below.

T _5% (℃) Strength (kgf/mm ² ) Young's modulus (kgf/mm ² ) Elongation(%) Residual stress (Mpa) Example 1 465 8.0 270.0 65.0 27 Example 2 468 9.0 258.0 63.0 28 Example 3 470 10.0 300.0 61.0 30 Example 4 470 11.2 315.0 58.0 30 Example 5 475 11.3 320.0 50.0 30 Example 6 450 7.0 255.0 68.0 25 Example 7 475 11.3 320.0 50.0 30 Comparative Example 1 420 7.0 250.0 70.0 23 Comparative Example 2 470 11.0 310.0 55.0 38 Comparative Example 3 485 12.0 330.0 45.0 40 Comparative Example 4 435 7.5 270 50 25 Comparative Example 5 430 8 260 50 24

From Table 3, it was confirmed that the photosensitive resin composition according to an embodiment contains a compound of a specific structure as a crosslinking agent, thereby improving flexibility (at the same time maintaining the same level of heat resistance) than the photosensitive resin composition not including the crosslinking agent of the structure I can.

The present invention is not limited to the above embodiments, but may be manufactured in a variety of different forms, and those of ordinary skill in the art to which the present invention pertains, other specific forms without changing the technical spirit or essential features of the present invention. It will be appreciated that it can be implemented as Therefore, it should be understood that the embodiments described above are illustrative and non-limiting in all respects.

Claims (10)

(A) alkali-soluble resin;
(B) photosensitive diazoquinone compound;
(C) a crosslinking agent represented by the following formula (1); And
(D) solvent
Photosensitive resin composition comprising:
[Formula 1]

In Formula 1,
R ¹ to R ³ are each independently a substituted or unsubstituted C3 to C10 alkoxy group,
R ⁴ to R ⁶ are each independently a hydrogen atom or *-C(=O)R ⁷ (R ⁷ is a C3 to C10 alkoxy group).
delete The method of claim 1,
The R ⁴ to R ⁶ are each independently a hydrogen atom photosensitive resin composition.
The method of claim 1,
The compound represented by Formula 1 is a photosensitive resin composition comprising 3 parts by weight to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin.
The method of claim 1,
The alkali-soluble resin is a photosensitive resin composition comprising a polybenzoxazole precursor, a polyimide precursor, a novolac resin, or a combination thereof.
The method of claim 1,
The photosensitive resin composition further comprises a dissolution control agent.
The method of claim 1,
The photosensitive resin composition,
Based on 100 parts by weight of the alkali-soluble resin
5 parts by weight to 50 parts by weight of the photosensitive diazoquinone compound,
Including 1 part by weight to 20 parts by weight of the crosslinking agent,
A photosensitive resin composition comprising 100 parts by weight to 500 parts by weight of the solvent.
The method of claim 1,
The photosensitive resin composition further comprises an additive of malonic acid, 3-amino-1,2-propanediol, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.
A photosensitive resin film produced using the photosensitive resin composition of any one of claims 1 and 3 to 8.
An electronic device comprising the photosensitive resin film of claim 9.