KR102319968B1 - Positive photosensitive resin composition, photosensitive resin layer and electronic device using the same - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a compound represented by the following formula (1); and (D) a positive photosensitive resin composition including a solvent, a photosensitive resin film prepared using the same, and an electronic device including the photosensitive resin film.
[Formula 1]

(In Formula 1, each substituent is as defined in the specification.)

Description

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

The present disclosure relates to a positive 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.

Especially, the method of using as the photosensitive resin composition which mixed the hydroxypolyamide resin soluble in alkaline aqueous solution used as heat-resistant resin after heat-hardening with photo-acid generators, such as a naphthoquinone diazide compound, is proposed.

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.

However, in a manufacturing process of a semiconductor or the like, microfabrication is in progress, and the interval between the pattern and the pattern is getting shorter. For this reason, when the film reduction during development is increased, in the unexposed portion adjacent to the open exposed portion, even if the dissolution rate of the unexposed portion is small, contact with the developer occurs not only from the top of the film but also from the side during development. Therefore, the pattern shape becomes too thin, and in the manufacturing process of a semiconductor device WHEREIN: It will reduce the reliability of a semiconductor package.

Then, it is necessary to develop almost without dissolving an unexposed part (this phenomenon is said to be high in image development residual film rate). However, when the development remaining film ratio is made high, a high exposure amount is required for development of the exposed portion (this is referred to as low sensitivity).

Accordingly, a method of adding a phenolic compound to a heat-resistant resin precursor has been proposed as a method of increasing the residual film (controlling developability) and increasing the sensitivity during development. However, conventionally used phenolic compounds have limitations in improving the sensitivity and the film remaining rate, and furthermore, there is a problem in that scum is generated when the sensitivity or the remaining film rate is improved.

Therefore, research to develop a positive photosensitive resin composition capable of solving the above problems is continuing.

One embodiment is to provide a positive photosensitive resin composition capable of improving the remaining film rate and sensitivity without generating scum.

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

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

One embodiment is (A) alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a compound represented by the following formula (1); And (D) provides a photosensitive resin composition comprising a solvent.

[Formula 1]

In Formula 1,

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 substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group,

n is an integer of 0 or 1.

Formula 1 may be represented by Formula 1-1 or Formula 1-2 below.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

R ⁴ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group;

R ⁵ is an unsubstituted C1 to C20 alkyl group,

R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group,

n is an integer of 0 or 1.

Formula 1-1 may be represented by any one of Formulas 1-1-1 to 1-1-3.

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

In Formulas 1-1-1 to 1-1-3,

R ⁷ is a substituted or unsubstituted C1 to C20 alkoxy group,

R ⁸ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group;

R ⁹ is *-CR ^a R ^b R ^c (R ^a , R ^b and R ^c are each independently a substituted or unsubstituted C1 to C10 alkyl group, wherein at least one of ^{R a} , R ^b and R ^{c is the other two} different from).

Formula 1-2 may be represented by Formula 1-2-1 or Formula 1-2-2.

[Formula 1-2-1]

[Formula 1-2-2]

In Formula 1-2-1 and Formula 1-2-2,

R ⁵ is an unsubstituted C1 to C20 alkyl group,

R ¹⁰ is a substituted or unsubstituted C1 to C20 alkyl group.

The compound represented by Formula 1 may be represented by any one of Formulas 1A to 1F below.

[Formula 1A]

[Formula 1B]

[Formula 1C]

[Formula 1D]

[Formula 1E]

[Formula 1F]

The compound represented by Formula 1 may be included in an amount of 0.5 to 40 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 novolak resin, or a combination thereof.

The positive photosensitive resin composition may further include a crosslinking agent.

The photosensitive resin composition comprises 5 parts by weight to 50 parts by weight of the photosensitive diazoquinone compound based on 100 parts by weight of the alkali-soluble resin, and 0.5 parts by weight to 40 parts by weight of the compound represented by Formula 1, 100 parts by weight to 500 parts by weight of the solvent may be included.

The photosensitive resin composition may further include an additive of a diacid, an alkanolamine, 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.

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 positive photosensitive resin composition according to an embodiment includes a compound having a specific structure, thereby improving the sensitivity and the remaining film rate without scum, so that it can be usefully used in manufacturing a circuit protection film used in electronic devices such as semiconductor devices. have.

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 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 includes (A) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a compound represented by the following formula (1); and (D) a solvent.

[Formula 1]

In Formula 1,

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 substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group,

n is an integer of 0 or 1.

The positive photosensitive resin composition according to an exemplary embodiment uses the compound represented by Formula 1 having both a polar group and a non-polar group as a dissolution control agent, thereby improving the remaining film rate and sensitivity without destroying the pattern. Furthermore, in the non-exposed part, it minimizes film reduction in the exposed part and dissolves well in the alkaline developer without leaving scum, and the effect is excellent in quantity and quality compared to the properties seen by the conventional dissolution control agent.

Hereinafter, each component will be described in detail.

(C) a compound represented by formula (1)

The compound represented by Formula 1 may be represented by Formula 1-1 or Formula 1-2.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

R ⁴ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group;

R ⁵ is an unsubstituted C1 to C20 alkyl group,

R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group,

n is an integer of 0 or 1.

Formula 1-1 may be represented by any one of Formulas 1-1-1 to 1-1-3.

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

In Formulas 1-1-1 to 1-1-3,

R ⁷ is a substituted or unsubstituted C1 to C20 alkoxy group,

R ⁸ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group;

R ⁹ is *-CR ^a R ^b R ^c (R ^a , R ^b and R ^c are each independently a substituted or unsubstituted C1 to C10 alkyl group, wherein at least one of ^{R a} , R ^b and R ^{c is the other two} different from).

Formula 1-2 may be represented by Formula 1-2-1 or Formula 1-2-2.

[Formula 1-2-1]

[Formula 1-2-2]

In Formula 1-2-1 and Formula 1-2-2,

R ⁵ is an unsubstituted C1 to C20 alkyl group,

R ¹⁰ is substituted or an unsubstituted C1 to C20 alkyl group.

For example, the compound represented by Formula 1 may be represented by any one of Formulas 1A to 1F below, but is not necessarily limited thereto.

[Formula 1A]

[Formula 1B]

[Formula 1C]

[Formula 1D]

[Formula 1E]

[Formula 1F]

The amount of the compound represented by Formula 1 used is preferably 0.5 parts by weight to 40 parts by weight, for example, 1 part by weight to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the content of the compound represented by Formula 1 is included within the above range, it is possible to increase the dissolution rate and sensitivity of the exposed part during development with an aqueous alkali solution, and also to allow high-resolution patterning without developing scum during development. can play a role

(A) alkali-soluble resin

The alkali-soluble resin is a resin containing a hydroxyl group, such as a polybenzoxazole precursor, a polyimide precursor, a (cresol-based) novolak resin, a bisphenol A resin, a bisphenol F resin, a (meth)acrylate resin, or a combination thereof. can be used

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 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 alicyclic organic group,

R ^x and R ^y 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 100,000, but m1 + m2 is an integer of 2 or more.

[Formula 3]

In 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 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 ⁰ and X ¹ 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 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'-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 ⁰ and Y ¹ 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.

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 as a mixture of one or more thereof.

Examples of the aromatic diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 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, a compound in which an alkyl group or a halogen atom is substituted in an aromatic ring thereof, or a combination thereof, but is not limited thereto.

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

Examples of the silicone diamine include bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)tetramethylsiloxane, bis(p-aminophenyl)tetramethyldisiloxane, bis(γaminopropyl)tetramethyldisiloxane, 1,4-bis(γaminopropyldimethylsilyl)benzene, bis(4-aminobutyl)tetramethyldisiloxane, bis(γaminopropyl)tetraphenyldisiloxane, 1,3-bis(aminopropyl)tetramethyldisiloxane Or a combination thereof may be mentioned, but 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.

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 as a mixture of one or more thereof.

Examples of the aromatic acid dianhydride include pyromellitic dianhydride; Benzophenone tetracarboxylic dianhydride, such as benzophenone-3,3',4,4'-tetracarboxylic dianhydride ; oxydiphthalic dianhydrides such as 4,4'-oxydiphthalic dianhydride; biphthalic dianhydride such as 3,3',4,4'-biphthalic dianhydride; (hexafluoroisopropyledene)diphthalic dianhydride, such as 4,4'-(hexafluoroisopropyledene)diphthalic dianhydride ; naphthalene-1,4,5,8-tetracarboxylic 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-cyclopentanetetracarboxylic dianhydride. Acid dianhydride (1,2,3,4-cyclopentanetetracarboxylic dianhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexane-1,2-dicarboxylic acid dianhydride (5- (2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexane-1,2-dicarboxylic anhydride), 4-(2,5-dioxotetrahydrofuran-3-yl)-tetralin-1,2-dicarboxylic 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, etc. may be mentioned, The present invention is not limited thereto.

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

For example, the alkali-soluble resin may include a polybenzoxazole precursor and a (cresol-based) novolak resin. When both the polybenzoxazole precursor and the (cresol-based) novolak resin are included, it may be advantageous for controlling the development rate 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, a weight average molecular weight (M _w ) of 5,000 g/mol to 30,000 g/mol. have. When it has a weight average molecular weight (M _w ) in the above range, it is possible to obtain a sufficient remaining film rate in the non-exposed 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 5 to 50 parts by weight, for example, 10 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 well formed without a residue by exposure, there is no film thickness loss 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 compound represented by Formula 1 above.

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 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 may be coated, and solubility and coatability may be excellent.

crosslinking agent

The positive photosensitive resin composition according to the exemplary embodiment may further include a crosslinking agent. The crosslinking agent may be represented by any one selected from the group consisting of the following Chemical Formulas 14-1 to 14-5.

[Formula 14-1]

[Formula 14-2]

[Formula 14-3]

[Formula 14-4]

[Formula 14-5]

In Formulas 14-1 to 14-5,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹³ to R ²² are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C1 to C10 alkoxy group,

R ²³ to R ²⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ² is a substituted or unsubstituted C1 to C10 alkylene group.

For example, R ²³ to R ²⁸ may each independently be a C1 to C10 alkyl group substituted with an epoxy group. In this case, the reaction between the crosslinking agent and the polymer may occur more smoothly, and a crosslinked structure may be easily formed.

For example, R ¹³ to R ²² may each independently be a C1 to C10 alkyl group substituted with a C1 to C5 alkoxy group. In this case, the reaction between the crosslinking agent and the polymer may occur more smoothly, and a crosslinked structure may be easily formed.

The crosslinking agent serves to prevent the taper angle from being lowered after curing of the resin composition according to the embodiment. Further, in the resin composition, when the organic film (resin film) is fired after the pattern is formed, the crosslinking agent reacts with the polymer to form a crosslinked structure. catalyzes the formation of a cross-linked structure. Accordingly, the resin composition can be cured even at a relatively low temperature of 300° C. or less, crosslinking occurs more actively, and the heat resistance and chemical resistance of the fired organic film (resin film) are increased. In addition, outgas from the film after heating and firing is reduced, thereby suppressing the occurrence of dark spots in the organic film (resin film). Also, the shrinkage of the film after curing is greatly reduced.

The crosslinking agent may be included in an amount of 10 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin.

dissolution modifier

The photosensitive resin composition according to an embodiment may further include a dissolution control agent having a structure other than the compound represented by Formula 1 above.

For example, the dissolution control agent may be represented by the following formula (15).

[Formula 15]

In the formula (15),

R ⁷¹ to R ⁸⁰ are each independently a hydrogen atom, a hydroxyl 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,

provided ^{that at least one of R 71} to R ⁷⁵ and at least one of R ⁷⁶ to R ⁸⁰ is a hydroxyl group,

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

For example, the dissolution controlling agent may be represented by any one of the following Chemical Formulas 15-1 to 15-7.

[Formula 15-1]

(In Formula 15-1, 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 )

[Formula 15-2]

(In Formula 15-2, R ⁶⁰⁷ to R ⁶¹² are the same or each independently represent a hydrogen atom, OH or CH ₃ .)

[Formula 15-3]

(In Formula 15-3, 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 ).

[Formula 15-4]

[Formula 15-5]

(In Formula 15-5, R ⁶²¹ to R ⁶²⁶ are each independently a hydrogen atom or OH.)

[Formula 15-6]

[Formula 15-7]

The amount of the dissolution control agent used is preferably 1 part by weight 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 part when developing with an aqueous alkali solution, and also play a role in high-resolution patterning without developing scum during development. .

other additives

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

The photosensitive resin composition is a diacid 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-based 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.

As the fluorine-based surfactant, BM-1000 ^® of BM Chemie, BM-1100 ^® and the like; ^{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; 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.

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

(3) development step

In the developing method, following the exposure step, the exposed portion is dissolved and removed using a developer to obtain a pattern by allowing only the unexposed portion to remain.

(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 of alkali-soluble resin)

11.0 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide was added to N-methyl-2- 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 over 30 minutes. After the dropwise addition, 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 complete the reaction. Here, 1.6 g of 5-norbornene-2,3-dicarboxyanhydride was added, and the reaction was terminated by stirring at 70° C. for 24 hours. The reaction mixture was poured into a solution of water/methanol = 10/1 (volume ratio) to produce a precipitate, the precipitate was filtered and washed sufficiently with water, and then dried at a temperature of 80° C. and vacuum for at least 24 hours to have a weight average molecular weight of 11,100 g A polybenzoxazole (PBO) precursor of /mol was prepared.

(Preparation of photosensitive resin composition)

Examples 1 to 7 and Comparative Example 1

According to the composition shown in Table 1, the polybenzoxazole precursor is added to and dissolved in γ (gamma)-butyrolactone (GBL), and then a photosensitive diazoquinone compound, a cresol-based novolak resin, the following formulas 1A to After adding the compound represented by Formula 1G, a crosslinking agent and a silane coupling agent and 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 Comparative Example 1 (A) alkali-soluble resin (A-1) 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 (A-2) 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 (B) photosensitive diazoquinone compound 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 (C) dissolution modifier (C-1) 5.0 - - - - - - - (C-2) - 5.0 - - - - - - (C-3) - - 5.0 - - - - - (C-4) - - - 5.0 - - - - (C-5) - - - - 5.0 - - - (C-6) - - - - - 5.0 - - (C-7) - - - - - - 5.0 - (C-8) - - - - - - - - (D) solvent 51.0 51.0 51.0 51.0 51.0 51.0 51.0 56.0 crosslinking agent 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 other additives (One) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (2) 0.2 0.2 0.2 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, among Q ¹ , Q ² and Q ³ , two are

, and the other one is a hydrogen atom.)

(C) dissolution regulator

(C-1) a compound represented by the following formula 1A (Sigma-Aldrich)

[Formula 1A]

(C-2) a compound represented by the following formula 1B (Sigma-Aldrich)

[Formula 1B]

(C-3) a compound represented by the following formula 1C (Sigma-Aldrich)

[Formula 1C]

(C-4) a compound represented by the following formula 1D (Sigma-Aldrich)

[Formula 1D]

(C-5) a compound represented by the following formula 1E (Sigma-Aldrich)

[Formula 1E]

(C-6) a compound represented by the following formula 1F (Sigma-Aldrich)

[Formula 1F]

(C-7) a compound represented by the following formula 1G (Sigma-Aldrich)

[Formula 1G]

(D) solvent

γ (gamma)-butyrolactone (GBL)

crosslinking agent

1,3,4,6-Tetrakis(methoxymethyl)glycoluril (TCI, T2058)

other additives

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

(2) Leveling agent (BYK-378)

evaluation

After coating the photosensitive resin compositions according to Examples 1 to 7 and Comparative Example 1 on an 8-inch wafer, it was heated on a hot plate at 120° C. for 4 minutes to form a 10 μm coating film.

Using a mask engraved with patterns of various sizes on the coating film, exposure was performed with NSR i11D, an i-line stepper from Nikon, Japan, with varying exposure doses, and then exposed at room temperature with 2.38% tetracycline. After developing for 50/50 seconds (2 puddles) in an aqueous solution of methylammonium hydroxide (TMAH), the exposed parts were dissolved and removed, and then washed with pure water for 30 seconds to form a pattern. Curing was carried out at 280° C. for 60 minutes in a nitrogen atmosphere.

For thickness measurement, the remaining film rate (%) was confirmed using ST-5000 (K-MAC), and the optimum exposure amount for accurately patterning a 7㎛ hole pattern was confirmed using Hitachi S-9260 CD-SEM, Table 2 Sensitivity (7㎛ hole E _op ), residual film rate, and scum occurrence are shown in Fig.

Assessing whether scum has occurred

O: Scum

X: No scum

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 7 μm hole E _op (mJ/cm ² ) 470 480 490 510 510 515 720 800 Remaining film rate (%) 89.0 89.5 90.0 91.0 91.0 91.0 93.5 95.0 Whether there is scum X X X X X X O O

Through Table 2, the positive photosensitive resin composition according to an embodiment contains a compound of a specific structure as a dissolution control agent, and thus, the positive photosensitive resin composition does not include a dissolution control agent of the structure. It can be seen that the film ratio is improved.

The present invention is not limited to the above embodiments, but can be manufactured in various 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 (12)

(A) 100 parts by weight of alkali-soluble resin;
(B) 5 to 50 parts by weight of the photosensitive diazoquinone compound;
(C) 0.5 to 40 parts by weight of a compound represented by any one of Formulas 1-1-1 to 1-1-3 and 1-2; and
(D) 100 parts by weight to 500 parts by weight of solvent
A positive photosensitive resin composition comprising:
[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

[Formula 1-2]

In Formulas 1-1-1 to 1-1-3,
R ⁷ is a substituted or unsubstituted C1 to C20 alkoxy group,
R ⁸ is a substituted or unsubstituted C1 to C20 alkyl group,
R ⁹ is *-CR ^a R ^b R ^c (R ^a , R ^b and R ^c are each independently a substituted or unsubstituted C1 to C10 alkyl group, wherein at least one of ^{R a} , R ^b and R ^{c is the other two} different from) and
In Formula 1-2,
R ⁵ is an unsubstituted C1 to C20 alkyl group,
R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group,
n is an integer of 0 or 1.
delete delete According to claim 1,
Formula 1-2 is a positive photosensitive resin composition represented by Formula 1-2-1 or Formula 1-2-2:
[Formula 1-2-1]

[Formula 1-2-2]

In Formula 1-2-1 and Formula 1-2-2,
R ⁵ is an unsubstituted C1 to C20 alkyl group,
R ¹⁰ is a substituted or unsubstituted C1 to C20 alkyl group.
According to claim 1,
The compound represented by any one of Formulas 1-1-1 to 1-1-3 and 1-2 is a positive photosensitive resin composition represented by any one of the following Formulas 1B to 1F.
[Formula 1B]

[Formula 1C]

[Formula 1D]

[Formula 1E]

[Formula 1F]

delete According to claim 1,
The alkali-soluble resin is a positive photosensitive resin composition comprising a polybenzoxazole precursor, a polyimide precursor, a novolak resin, or a combination thereof.
According to claim 1,
The positive photosensitive resin composition further comprises a crosslinking agent.
delete According to claim 1,
The positive photosensitive resin composition further comprises an additive of diacid, alkanolamine, leveling agent, silane-based coupling agent, surfactant, epoxy compound, radical polymerization initiator, thermal latent acid generator, or a combination thereof. A photosensitive resin composition.
A photosensitive resin film produced by using the positive photosensitive resin composition of any one of claims 1, 4, 5, 7, 8, or 10.
An electronic device comprising the photosensitive resin film of claim 11 .