KR102287214B1 - Photosensitive resin composition, photosensitive resin layer and electronic device using the same - Google Patents

Abstract

[화학식 2-2]

[화학식 2-3]

[화학식 2-4]

[화학식 2-5]

(상기 화학식 1 및 화학식 2-2 내지 화학식 2-5에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) an alkali-soluble resin comprising a structural unit represented by the following Chemical Formula 1, and including any one or more structural units selected from the group consisting of structural units represented by the following Chemical Formulas 2-2 to 2-5; (B) a photosensitive diazoquinone compound; and (C) a photosensitive resin composition comprising a solvent, a photosensitive resin film prepared using the same, and an electronic device including the photosensitive resin film.
[Formula 1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

(In Formula 1 and Formula 2-2 to Formula 2-5, each substituent is as defined in the specification.)

Description

Photosensitive resin composition, photosensitive resin film and electronic device using the same

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

Conventionally, polyimide resins, polybenzoxazole resins, etc., which have excellent heat resistance, electrical properties, mechanical properties, and the like, have been widely used for surface protective films and interlayer insulating films used for display device panel materials and 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, a heat-resistant photosensitive resin material that can be developed with an alkaline aqueous solution has been proposed.

Among them, a method of using an alkaline aqueous solution-soluble hydroxypolyamide resin (polybenzoxazole precursor) that becomes a heat-resistant resin after heat curing is mixed with a photoacid generator such as a naphthoquinonediazide compound as a photosensitive resin composition is proposed. has been

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

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

When the cured film is applied to a semiconductor device as a surface protective film and an interlayer insulating film, it is required to have high reliability. Although there are various indicators for evaluating the reliability, in particular, it is important that the tensile elongation (elongation) of the cured film is high in order to withstand repeated expansion and contraction of the film according to the temperature. Moreover, the shape of a hardening relief pattern must be favorable, it must have sufficient alkali solubility, there are few residual films at the time of image development, and it must be excellent in adhesiveness with a board|substrate.

One embodiment is to provide a photosensitive resin composition having excellent film remaining rate, sensitivity, elongation, and residue properties at the same time.

Another embodiment is to provide a photosensitive resin film prepared 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 comprising at least one structural unit selected from the group consisting of a structural unit represented by the following Chemical Formula 1 and a structural unit represented by the following Chemical Formulas 2-1 to 2-5; (B) a photosensitive diazoquinone compound; And (C) provides a photosensitive resin composition comprising a solvent.

[Formula 1]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Formula 1 and Formula 2-1 to Formula 2-5,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ² and R ³ 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 C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl ester group, a substituted or unsubstituted C6 to C20 aryl ester group, or a substituted or unsubstituted C6 to C20 aryl group,

Z ¹ is a residue of an acid dianhydride,

X ¹ and X ² are each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

Y ¹ and Y ² 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 It is a C30 alicyclic organic group.

The alkali-soluble resin may include a structural unit represented by Formula 1, and may include any one or more structural units selected from the group consisting of structural units represented by Formulas 2-1 and 2-2.

The alkali-soluble resin may include a structural unit represented by Formula 1, and may include any one or more structural units selected from the group consisting of structural units represented by Formulas 2-3 to 2-5.

The alkali-soluble resin includes a structural unit represented by Formula 1, and includes any one or more structural units selected from the group consisting of structural units represented by Formulas 2-1 and 2-2, and Formula 2- 3 to may include any one or more structural units selected from the group consisting of structural units represented by Chemical Formulas 2-5.

The Z ¹ is butanetetracarboxylic dianhydride

(butanetetracarboxylic dianhydride), pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicyclopentanetetracarboxylic Bicyclohexanetetracarboxylic dianhydride, cyclopropanetetracarboxylic dianhydride, methylcyclohexanetetracarboxylic dianhydride

(methylcyclohexanetetracarboxylic dianhydride), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride), pyromellitic dianhydride , 3,4,9,10-perylenetetracarboxylic dianhydride (3,4,9,10-perylenetetracaboxylicdianhydride), 4,4-sulfonyldiphthalic dianhydride (4,4-sulfonyldiphthalic dianhydride), 3,3',4,4'-biphenyl tetracarboxylic dianhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride), 1,2,5,6-naphthalenetetracarboxylic dianhydride (1,2,5,6-naphthalenetetracaboxylic dianhydride), 2,3,6,7-naphthalenetetracarboxylic dianhydride (2,3,6,7-naphthalenetetracaboxylic dianhydride), 1,4,5,8- Naphthalenetetracarboxylic dianhydride (1,4,5,8-naphthalene tetracaboxylic dianhydride), 2,3,5,6-pyridinetetracarboxylic dianhydride (2,3,5,6-pyridinetetracaboxylic dianhydride) , m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride (m-terphenyl-3,3',4,4'-tetracaboxylic dianhydride), p-terphenyl-3,3 ',4,4'-tetracarboxylic dianhydride (p-terphenyl-3,3',4,4'-tetracaboxylic dianhydride), 4,4-oxydiphthalic die

Anhydride (4,4-oxydiphthalic dianhydride), 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenoxy) phenylpropane dianhydride (1 ,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenoxy)phenylpropanedianhydride), 1,1,1,3,3,3-hexafluoro-2,2-bis ( 3,4-dicarboxyphenoxy)phenylpropanedianhydride (1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenoxy)phenylpropane dianhydride), 2,2-bis [4-(2,3-dicarboxyphenoxy)phenyl]propanedianhydride (2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propanedianhydride), 2,2-bis[4-(3 ,4-dicarboxyphenoxy)phenyl]propane dianhydride (2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride), 1,1,1,3,3,3,-hexa Fluoro-2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride (1,1,1,3,3,3-hexafluoro-2,2-bis[4- (2,3-dicarboxyphenoxy)phenyl]propane dianhydride) and 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane Derived from any one or more acid dianhydrides selected from the group consisting of dianhydride (1,1,1,3,3,3-hexafluoro-2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride) It may be a tetravalent functional group.

The alkali-soluble resin may have a weight average molecular weight of 1,000 g/mol to 300,000 g/mol.

The photosensitive resin composition may include 1 part by weight to 50 parts by weight of the photosensitive diazoquinone compound, and 100 parts by weight to 500 parts by weight of the solvent based on 100 parts by weight of the alkali-soluble resin.

The photosensitive resin composition may further include an additive of a diecide, an alkanolamine, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.

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

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

The specific details of other aspects of the invention are included in the detailed description below.

The photosensitive resin composition according to an exemplary embodiment may include an alkali-soluble resin containing a specific structural unit, thereby improving the residual film ratio, sensitivity, elongation, and residual properties at the same time.

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

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, and "cycloalkenyl group" means a C3 to C20 cycloalkenyl group, , "heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C7 to C20 arylalkyl group, "alkylene group" means a C1 to C20 alkylene group, "arylene group" means a C6 to C20 arylene group, "alkylarylene group" means a C7 to C20 alkylarylene group, and "heteroarylene group" means a C3 to C20 hetero It refers to an arylene group, and "alkoxyylene group" refers to a C1 to C20 alkoxyylene group.

Unless otherwise specified herein, "substitution" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), a hydroxyl 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 a salt thereof, sulfonic acid group or a salt thereof, phosphoric acid or a 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 means substituted with a substituent.

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

In addition, unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible.

Unless otherwise defined herein, "combination" means mixing or copolymerization. Also, "copolymerization" means block copolymerization, alternating copolymerization or random copolymerization, and "copolymer" means block copolymer, alternating copolymer or random copolymer.

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

Unless otherwise defined in the chemical formulas 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 to the position.

Unless otherwise defined herein, "*" means a moiety connected to the same or different atoms or chemical formulas.

The photosensitive resin composition according to an embodiment is (A) an alkali comprising at least one structural unit selected from the group consisting of a structural unit represented by the following Chemical Formula 1 and a structural unit represented by the following Chemical Formulas 2-1 to 2-5 soluble resin; (B) a photosensitive diazoquinone compound; and (C) a solvent.

[Formula 1]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Formula 1 and Formula 2-1 to Formula 2-5,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ² and R ³ 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 C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl ester group, a substituted or unsubstituted C6 to C20 aryl ester group, or a substituted or unsubstituted C6 to C20 aryl group,

Z ¹ is a residue of an acid dianhydride,

X ¹ and X ² are each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

Y ¹ and Y ² 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 It is a C30 alicyclic organic group.

When the photosensitive resin composition according to an embodiment is used as a protective film or an insulating layer in a semiconductor or display device, the composition is coated and then developed and cured after UV exposure to be applied. Reliability, in particular, elongation and adhesion are very important due to the characteristics of the process material. By using an alkali-soluble resin having a specific structural unit for the photosensitive resin composition according to an embodiment, the sensitivity, elongation, and residue properties are improved while maintaining an excellent residual film rate. All can be improved. Specifically, the structural unit represented by Formula 1 included in the alkali-soluble resin can be introduced through a click-ene reaction, and since the structural unit functions as a flexible chain unit, it is possible to greatly improve the stretching force.

Hereinafter, each component will be described in detail.

(A) alkali-soluble resin

The alkali-soluble resin may be a polyhydroxyamide resin, a polyimide precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, a (meth)acrylate resin, or a combination thereof.

For example, the alkali-soluble resin may be a (meth)acrylate resin. In this case, the alkali-soluble resin may include a structural unit represented by Formula 1, and may include any one or more structural units selected from the group consisting of structural units represented by Formulas 2-1 and 2-2.

For example, the alkali-soluble resin may be a polyhydroxyamide resin. In this case, the alkali-soluble resin may include any one or more structural units selected from the group consisting of structural units represented by Chemical Formula 1 and structural units represented by Chemical Formulas 2-3 to 2-5.

For example, the alkali-soluble resin may be a combination of a (meth)acrylate resin and a polyhydroxyamide resin. In this case, the alkali-soluble resin includes a structural unit represented by Formula 1, and includes any one or more structural units selected from the group consisting of structural units represented by Formulas 2-1 and 2-2, and wherein It may include any one or more structural units selected from the group consisting of structural units represented by 2-3 to Formula 2-5.

For example, when the alkali-soluble resin is 'polyhydroxyamide resin' or 'a combination of (meth)acrylate resin and polyhydroxyamide resin', the alkali-soluble resin is represented by Chemical Formulas 2-4 and 2-5 The displayed structural unit must be included.

In Formulas 2-4 and 2-5, X ¹ is an aromatic organic group and may be a residue derived from an aromatic diamine.

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 Ropropane, 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 Ropropane, 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 -(3-hydroxy-4-amino-5-trifluoromethylphenyl) at least one selected from hexafluoropropane may be used However, the present invention is not limited thereto.

Examples of X ¹ and X ² may include, but are not limited to, a functional group represented by Formula 4 or Formula 5 below.

[Formula 4]

[Formula 5]

In Formulas 4 and 5,

A ¹ may be a single bond, O, CO, CR ⁴⁷ R ⁴⁸ , SO ₂ or S, wherein 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 from 0 to 2, and n11 and n12 are each independently an integer from 0 to 3.

In Formulas 2-4 and 2-5, Y ¹ and Y ² are each independently an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent alicyclic organic group, a residue of dicarboxylic acid or It may be a residue of a dicarboxylic acid derivative. Specifically, Y ¹ and Y ² 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'-oxydibenzoylchloride, diphenyloxydicarbonyldichloride, bis(phenylcarbonylchloride)sulfone, bis(phenylcarbonylchloride)ether, bis(phenylcarbonylchloride) ) phenone, phthaloyl dichloride, terephthaloyl dichloride, isophthaloyl dichloride, dicarbonyl dichloride, diphenyloxydicarboxylate dibenzotriazole, or a combination thereof, but is not limited thereto.

Examples of Y ¹ and Y ² may include functional groups represented by the following Chemical Formulas 6 to 8, but are not limited thereto.

[Formula 6]

[Formula 7]

[Formula 8]

In 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 , wherein R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, specifically is a C1 to C30 fluoroalkyl group.

For example, in Formula 2-3, Z ¹ is butanetetracarboxylic dianhydride

(butanetetracarboxylic dianhydride), pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicyclopentanetetracarboxylic Bicyclohexanetetracarboxylic dianhydride, cyclopropanetetracarboxylic dianhydride, methylcyclohexanetetracarboxylic dianhydride

(methylcyclohexanetetracarboxylic dianhydride), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride), pyromellitic dianhydride , 3,4,9,10-perylenetetracarboxylic dianhydride (3,4,9,10-perylenetetracaboxylicdianhydride), 4,4-sulfonyldiphthalic dianhydride (4,4-sulfonyldiphthalic dianhydride), 3,3',4,4'-biphenyl tetracarboxylic dianhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride), 1,2,5,6-naphthalenetetracarboxylic dianhydride (1,2,5,6-naphthalenetetracaboxylic dianhydride), 2,3,6,7-naphthalenetetracarboxylic dianhydride (2,3,6,7-naphthalenetetracaboxylic dianhydride), 1,4,5,8- Naphthalenetetracarboxylic dianhydride (1,4,5,8-naphthalene tetracaboxylic dianhydride), 2,3,5,6-pyridinetetracarboxylic dianhydride (2,3,5,6-pyridinetetracaboxylic dianhydride) , m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride (m-terphenyl-3,3',4,4'-tetracaboxylic dianhydride), p-terphenyl-3,3 ',4,4'-tetracarboxylic dianhydride (p-terphenyl-3,3',4,4'-tetracaboxylic dianhydride), 4,4-oxydiphthalic die

Anhydride (4,4-oxydiphthalic dianhydride), 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenoxy) phenylpropane dianhydride (1 ,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenoxy)phenylpropanedianhydride), 1,1,1,3,3,3-hexafluoro-2,2-bis ( 3,4-dicarboxyphenoxy)phenylpropanedianhydride (1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenoxy)phenylpropane dianhydride), 2,2-bis [4-(2,3-dicarboxyphenoxy)phenyl]propanedianhydride (2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propanedianhydride), 2,2-bis[4-(3 ,4-dicarboxyphenoxy)phenyl]propane dianhydride (2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride), 1,1,1,3,3,3,-hexa Fluoro-2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride (1,1,1,3,3,3-hexafluoro-2,2-bis[4- (2,3-dicarboxyphenoxy)phenyl]propane dianhydride) and 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane Derived from any one or more acid dianhydrides selected from the group consisting of dianhydride (1,1,1,3,3,3-hexafluoro-2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride) It may be a tetravalent functional group, but is not necessarily limited thereto.

The alkali-soluble resin may have a weight average molecular weight (Mw) of 1,000 g/mol to 300,000 g/mol, and specifically may have a weight average molecular weight (Mw) of 5,000 g/mol to 50,000 g/mol. When it has a weight average molecular weight (Mw) in the above range, it is possible to obtain a sufficient remaining film rate in the unexposed part during development with an aqueous alkali solution, and to efficiently perform patterning.

(B) photosensitive diazoquinone compound

As the photosensitive diazoquinone compound, a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure may be preferably used.

Representative examples of the photosensitive diazoquinone compound include compounds represented by the following Chemical Formula 9 and Chemical Formulas 11 to 13, but are not limited thereto.

[Formula 9]

In Formula 9,

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 Chemical Formula 10a or a functional group represented by the following Chemical Formula 10b, wherein Q cannot be a hydrogen atom at the same time,

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

[Formula 10a]

[Formula 10b]

[Formula 11]

In the above formula (11),

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

D ⁴ to D ⁶ may each independently be OQ, wherein Q is the same as defined in Formula 9,

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

[Formula 12]

In the above formula (12),

A ³ may be CO or CR ⁵⁰⁰ R ⁵⁰¹ , wherein 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, wherein Q is the same as defined in Formula 9,

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 may be OQ, one aromatic ring may include 1 to 3 OQs, and the other aromatic ring may include 1 to 4 OQs.

[Formula 13]

In the above formula (13),

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, an integer of 2 to 4,

Q is the same as defined in Formula 9 above.

The photosensitive diazoquinone compound is preferably included in an amount of 1 to 50 parts by weight, for example 5 to 40 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, a pattern can be formed without a residue by exposure, there is no film thickness loss during development, and a good pattern can be obtained.

(C) solvent

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

The solvent uses 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 (methyl pyruvate), ethyl pyruvate (ethyl pyruvate), methyl-3-methyl Toxy propionate or a combination thereof may be used, but is not limited thereto.

The solvent may be appropriately selected and used according to the process of forming the 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 400 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 may be coated, and solubility and coatability may be excellent.

(D) other additives

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

The photosensitive resin composition is a dieside such as malonic acid and an alkanolamine such as 3-amino-1,2-propanediol in order to prevent stains or spots during coating, leveling properties, or generation of residues due to undeveloped properties. , a leveling agent, a silane-based coupling agent, a surfactant, an epoxy compound, a radical polymerization initiator, a thermal latent acid generator, or a combination thereof. The amount of these additives can be easily adjusted according to 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, and an epoxy group in order to improve adhesion to the substrate.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycan Cydoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. are mentioned, and these can be used individually or in mixture of 2 or more types.

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 may be excellent.

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

Examples of the fluorine-based surfactant include BM-1000 ^® , BM-1100 ^® and the like by BM Chemie; ^{Mechapack F 142D ®} , Mechapack F 172 ^® , Mechapack F 173 ^® , Mechapack F 183 ^® , Mechapack F 554 ^® and the like of Dainippon Ink Chemical Co., Ltd.; ^{Prorad FC-135 ®} , Prorad FC-170C ^® , Prorad FC-430 ^® , Prorad FC-431 ^®, etc. from Sumitomos Reem Co., Ltd.; Asahi Grass Co., Ltd. Saffron S-112 ^® , Saffron S-113 ^® , Saffron S-131 ^® , Saffron S-141 ^® , Saffron S-145 ^®, etc.; Toray Silicone Co., Ltd.'s SH-28PA ^® , SH-190 ^® , SH-193 ^® , SZ-6032 ^® , SF-8428 ^®, etc. may be used.

The silicone-based surfactants include BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, What is marketed under the name of BYK-325 etc. 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 wettability to an ITO substrate or a glass substrate may be excellent.

In addition, the photosensitive resin composition may further include an epoxy compound as an additive to improve adhesion. As the epoxy compound, an epoxy novolac acrylic carboxylate resin, an ortho cresol novolak 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. 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, adhesion and other properties.

In addition, the photosensitive resin composition may further include a thermal latent acid generator. Examples of the thermal 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, butanesulfonic acid and the like; Or a combination thereof may be mentioned, but is not limited thereto.

The thermal latent acid generator is a catalyst for the dehydration reaction of the polyamide containing a phenolic hydroxyl group of the polybenzoxazole precursor and the cyclization reaction, so that the cyclization reaction can proceed smoothly even if 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.

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

The electronic device may be a semiconductor device.

The method for manufacturing the photosensitive resin film is as follows.

(1) Application and coating film formation step

After applying the photosensitive resin composition to a desired thickness using a method such as a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, etc. on a substrate such as a glass substrate or an ITO substrate subjected to a predetermined pretreatment, 70 A 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 pattern required for the obtained photosensitive resin film, actinic 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. may be used, and in some cases, an X-ray, an electron beam, etc. may be used.

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

(3) development step

As a developing method, after the exposure step, by dissolving and removing the exposed portion using a developer, only the unexposed portion remains to obtain a pattern.

(4) post-processing step

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

Hereinafter, preferred embodiments of the present invention will be 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 Example 1: Alkali-soluble resin 1 synthesis

In a 1L 3-neck flask equipped with a cooling tube and a stirrer, 9 g of 2,2'-azobis(2,4-dimethylvaleronitrile), 120 g of styrene monomer, 30 g of methyl methacrylic acid, and 350 g of propylene glycol monomethyl ether acetate were charged. 509 g of an acrylate-based resin having a molecular weight of 15,000 g/mol, having the structural unit of Formula E-1, diluted with propylene glycol monomethyl ether acetate by 30 wt% in propylene glycol monomethyl ether acetate, by adding nitrogen and stirring for 3 hours at 80 ° C. could

[Formula E-1]

Synthesis Example 2: Alkali-soluble resin 2 synthesis

Acryl having a molecular weight of 13,500 g/mol having a structural unit with the following Chemical Formula E-2 in the same manner as in Synthesis Example 1 except that 112.5 g of styrene monomer and 7.5 g of 1,2-ethylenedithiol were used instead of 120 g of styrene monomer A rate-based resin was obtained.

[Formula E-2]

Synthesis Example 3: Alkali-soluble resin 3 synthesis

2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3, 12.4 g of 3-hexafluoropropane and 125 g of N-methyl-2-pyrrolidone (NMP) were added and dissolved.

When the solid is completely dissolved, 4.2 g of pyridine as a catalyst is added, and a solution obtained by dissolving 9.4 g of 4,4'-oxydibenzoyl chloride in 100 g of NMP while maintaining the temperature at 0°C to 5°C is placed in a 4-necked flask equipped with 30 It was dripped slowly over a minute. After the dropping was completed, the reaction was carried out at 0° C. to 5° C. for 1 hour, and the temperature was raised to room temperature to react for 1 hour.

1.1 g of 5-norborene-2,3-dicarboxyanhydride was added thereto, and after stirring at 70° C. for 24 hours, the reaction was terminated. 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 thoroughly washed with water, and then dried under vacuum at a temperature of 80° C. for at least 24 hours to obtain a polyhydroxyamide resin ( molecular weight: 12,000 g/mol) was obtained.

Synthesis Example 4: Alkali-soluble resin 4 synthesis

In Synthesis Example 3, after adding 1.1 g of 5-norborene-2,3-dicarboxyanhydride and stirring at 70° C. for 24 hours, 2,2′-azobis(2,4-dimethylvalero) A polyhydroxyamide resin (molecular weight: 11,400 g/mol) was obtained in the same manner as in Synthesis Example 3, except that an additional reaction was performed using 9 g of nitrile) and 7.5 g of 1,2-ethylenedithiol.

(Preparation of photosensitive resin composition)

Example 1

100 g of the alkali-soluble resin of Synthesis Example 2 was added to and dissolved in a solvent of 300 g of γ (gamma)-butyrolactone (GBL), followed by 20 g of a photosensitive diazoquinone compound (MIPHOTO TPD425, Miwon Commercial Co., Ltd.) After dissolution, the mixture was stirred under a yellow light until it became a homogeneous solution. Thereafter, it was filtered through a 0.20 µm fluororesin filter to obtain a photosensitive resin composition.

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the alkali-soluble resin of Synthesis Example 4 was used instead of the alkali-soluble resin of Synthesis Example 2.

Comparative Example 1

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the alkali-soluble resin of Synthesis Example 1 was used instead of the alkali-soluble resin of Synthesis Example 2.

Comparative Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the alkali-soluble resin of Synthesis Example 3 was used instead of the alkali-soluble resin of Synthesis Example 2.

evaluation

After coating the photosensitive resin compositions according to Examples 1 and 2, Comparative Examples 1 and 2 on a wafer on which aluminum is deposited, heating (curing) for 4 minutes on a hot plate at 120° C., curing to a thickness of 10 μm A film was formed, and the residual film ratio, sensitivity, and elongation were evaluated for the cured film, and the results are shown in Table 1 below.

(Evaluation 1: Remaining film rate)

Calculate the difference in thickness before/after development in %

(Evaluation 2: Sensitivity)

The exposure dose indicating the pattern dimension of 7 μm after development is calculated as the sensitivity

(Evaluation 3: Elongation)

After immersing the cured film coated on the wafer in 10% hydrochloric acid (or 1% hydrofluoric acid) diluted in water for about 20 minutes, a cured film was obtained. The elongation of the obtained cured film was measured with a UTM facility, and only the maximum value was obtained after measuring 10 samples.

- Grip thickness: 50mm

- Cross head speed: 5mm/min

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Remaining film rate (%) Sensitivity (mJ/cm ² ) Elongation (%) Example 1 91.0 480 50 Example 2 91.0 450 70 Comparative Example 1 88.5 520 20 Comparative Example 2 87.5 500 35

Referring to Table 1, the photosensitive resin composition according to an embodiment of the present invention includes an alkali-soluble resin containing a specific structure, thereby maintaining an excellent residual film ratio than the photosensitive resin composition not including the alkali-soluble resin while simultaneously maintaining sensitivity and elongation. It can be seen that all of them can be improved.

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

Claims (10)

(A) an alkali-soluble resin comprising a structural unit represented by the following Chemical Formula 1, and including any one or more structural units selected from the group consisting of structural units represented by the following Chemical Formulas 2-2 to 2-5;
(B) a photosensitive diazoquinone compound; and
(C) solvent
A photosensitive resin composition comprising:
[Formula 1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Formula 1 and Formula 2-2 to Formula 2-5,
L ¹ is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,
R ³ is 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 C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl ester group, a substituted or unsubstituted C6 to C20 aryl ester group or a substituted or unsubstituted C6 to C20 aryl group;
Z ¹ is a residue of an acid dianhydride,
X ¹ and X ² are each independently a substituted or unsubstituted C6 to C30 aromatic organic group,
Y ¹ and Y ² 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 It is a C30 alicyclic organic group.
According to claim 1,
The alkali-soluble resin comprises a structural unit represented by the formula (1),
A photosensitive resin composition comprising any one or more structural units selected from the group consisting of structural units represented by Formula 2-2.
According to claim 1,
The alkali-soluble resin comprises a structural unit represented by the formula (1),
A photosensitive resin composition comprising at least one structural unit selected from the group consisting of structural units represented by Chemical Formulas 2-3 to 2-5.
According to claim 1,
The alkali-soluble resin comprises a structural unit represented by the formula (1),
It contains any one or more structural units selected from the group consisting of structural units represented by the following Chemical Formulas 2-1 and 2-2,
[Formula 2-1]

In Formula 2-1,
R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ² is 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 C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkylester group, a substituted or unsubstituted C6 to C20 aryl ester group or a substituted or unsubstituted C6 to C20 aryl group;
A photosensitive resin composition comprising at least one structural unit selected from the group consisting of structural units represented by Chemical Formulas 2-3 to 2-5.
According to claim 1,
The Z ¹ is butanetetracarboxylic dianhydride
(butanetetracarboxylic dianhydride), pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicyclopentanetetracarboxylic Bicyclohexanetetracarboxylic dianhydride, cyclopropanetetracarboxylic dianhydride, methylcyclohexanetetracarboxylic dianhydride
(methylcyclohexanetetracarboxylic dianhydride), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride), pyromellitic dianhydride , 3,4,9,10-perylenetetracarboxylic dianhydride (3,4,9,10-perylenetetracaboxylicdianhydride), 4,4-sulfonyldiphthalic dianhydride (4,4-sulfonyldiphthalic dianhydride), 3,3',4,4'-biphenyl tetracarboxylic dianhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride), 1,2,5,6-naphthalenetetracarboxylic dianhydride (1,2,5,6-naphthalenetetracaboxylic dianhydride), 2,3,6,7-naphthalenetetracarboxylic dianhydride (2,3,6,7-naphthalenetetracaboxylic dianhydride), 1,4,5,8- Naphthalenetetracarboxylic dianhydride (1,4,5,8-naphthalene tetracaboxylic dianhydride), 2,3,5,6-pyridinetetracarboxylic dianhydride (2,3,5,6-pyridinetetracaboxylic dianhydride) , m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride (m-terphenyl-3,3',4,4'-tetracaboxylic dianhydride), p-terphenyl-3,3 ',4,4'-tetracarboxylic dianhydride (p-terphenyl-3,3',4,4'-tetracaboxylic dianhydride), 4,4-oxydiphthalic die
Anhydride (4,4-oxydiphthalic dianhydride), 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenoxy) phenylpropane dianhydride (1 ,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenoxy)phenylpropanedianhydride), 1,1,1,3,3,3-hexafluoro-2,2-bis ( 3,4-dicarboxyphenoxy)phenylpropanedianhydride (1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenoxy)phenylpropane dianhydride), 2,2-bis [4-(2,3-dicarboxyphenoxy)phenyl]propanedianhydride (2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propanedianhydride), 2,2-bis[4-(3 ,4-dicarboxyphenoxy)phenyl]propane dianhydride (2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride), 1,1,1,3,3,3,-hexa Fluoro-2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride (1,1,1,3,3,3-hexafluoro-2,2-bis[4- (2,3-dicarboxyphenoxy)phenyl]propane dianhydride) and 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane Derived from any one or more acid dianhydrides selected from the group consisting of dianhydride (1,1,1,3,3,3-hexafluoro-2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride) A photosensitive resin composition having a tetravalent functional group.
According to claim 1,
The alkali-soluble resin is a photosensitive resin composition having a weight average molecular weight of 1,000 g / mol to 300,000 g / mol.
According to claim 1,
The photosensitive resin composition,
With respect to 100 parts by weight of the alkali-soluble resin
1 part by weight to 50 parts by weight of the photosensitive diazoquinone compound,
A photosensitive resin composition comprising 100 parts by weight to 500 parts by weight of the solvent.
According to claim 1,
The photosensitive resin composition further comprises an additive of a diacid, an alkanolamine, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.
A photosensitive resin film prepared by using the photosensitive resin composition of any one of claims 1 to 8.
An electronic device comprising the photosensitive resin film of claim 9 .