KR102288387B1 - 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 photosensitive resin composition comprising a solvent, a photosensitive resin film prepared using the same, and an electronic device including the photosensitive resin film is provided.
[Formula 1]

(In Formula 1, 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.

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 a naphthoquinonediazide compound (that is, a photosensitive diazoquinone compound) and a polybenzoxazole (PBO) precursor to an unexposed part, thereby converting the photosensitive diazoquinone compound to an indenecarboxylic acid compound. By transforming it to , it takes advantage of the fact that the dissolution rate in the alkaline aqueous solution is increased. 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 separate additive to the heat-resistant resin precursor has been proposed as a method of increasing the residual film during development (controlling developability) and increasing the sensitivity. However, the lifting improvement after development is not satisfactory only with the conventionally used additives, and there is a limit in satisfying the recent needs for continuous high sensitivity for throughput improvement due to the characteristics of the photosensitive material.

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

One embodiment is to provide a photosensitive resin composition capable of improving sensitivity by improving developability by using a dissolution regulator having a specific structure.

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) 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,

L ¹ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

R ¹ is a substituted or unsubstituted C3 to C20 aliphatic ring group or a substituted or unsubstituted C6 to C20 aromatic ring group, wherein the aliphatic ring group does not include an unsaturated bond;

R ² to R ⁴ are each independently a hydroxyl group or a C1 to C10 trifluoroalkyl ^{group, wherein at least one of R 2} to R ⁴ is a hydroxyl group, and at least one of R ² to R ⁴ is a C1 to C10 trifluoroalkyl group am.

R ¹ may be a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C6 to C20 aryl group.

R ¹ is an unsubstituted C3 to C20 cycloalkyl group, a C1 to C10 alkyl group substituted C3 to C20 cycloalkyl group, a hydroxy group substituted C3 to C20 cycloalkyl group, an unsubstituted C6 to C20 aryl group, a C1 to C10 alkyl group It may be a substituted C6 to C20 aryl group or a C6 to C20 aryl group substituted with a hydroxy group.

R ² and R ⁴ may each independently be a C1 to C10 trifluoroalkyl group, and R ³ may be a hydroxyl group.

The compound represented by Formula 1 may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin.

The compound represented by Formula 1 may be represented by any one of Formulas 2 to 6 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

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

The photosensitive resin composition comprises 1 part by weight to 50 parts by weight of the photosensitive diazoquinone compound based on 100 parts by weight of the alkali-soluble resin, and 1 part by weight to 30 parts by weight of the compound represented by Formula 1, 100 parts by weight to 300 parts by weight of the solvent may be included.

The photosensitive resin composition may further include an additive such as a diecide, an alkanolamine, a leveling agent, a silane 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 photosensitive resin composition according to the exemplary embodiment may have excellent sensitivity by improving developability by using a dissolution control agent having a specific structure.

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 hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or 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, azo bonds, and the like.

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 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,

L ¹ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

R ¹ is a substituted or unsubstituted C3 to C20 aliphatic ring group or a substituted or unsubstituted C6 to C20 aromatic ring group, wherein the aliphatic ring group does not include an unsaturated bond.

R ² to R ⁴ are each independently a hydroxyl group or a C1 to C10 trifluoroalkyl ^{group, wherein at least one of R 2} to R ⁴ is a hydroxyl group, and at least one of R ² to R ⁴ is a C1 to C10 trifluoroalkyl group am.

When the photosensitive resin composition according to an embodiment is used as a protective film or insulating layer in a semiconductor or display device, the composition is coated and then developed and cured after UV exposure to be applied. Sensitivity is very important for throughput improvement due to the characteristics of the process material, and the photosensitive resin composition according to an embodiment uses the compound represented by Formula 1 as a dissolution control agent, so that the sensitivity can be significantly improved compared to the conventional standard.

Hereinafter, each component will be described in detail.

(C) a compound represented by formula (1)

The photosensitive resin composition according to the exemplary embodiment includes the compound represented by Formula 1 as a dissolution control agent, thereby greatly improving sensitivity and heat resistance. Specifically, when developing the photosensitive resin composition comprising the compound represented by Formula 1 as a dissolution control agent with an aqueous alkali solution, the dissolution rate and sensitivity of the exposed part are greatly increased, thereby improving developability, which ultimately leads to high-resolution patterning and Enables high heat resistance.

For example, in Formula 1, R ¹ may be a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C6 to C20 aryl group.

For example, R ¹ is an unsubstituted C3 to C20 cycloalkyl group, a C1 to C10 alkyl group substituted C3 to C20 cycloalkyl group, a hydroxy group substituted C3 to C20 cycloalkyl group, an unsubstituted C6 to C20 aryl group, C1 to C10 It may be a C6 to C20 aryl group substituted with an alkyl group or a C6 to C20 aryl group substituted with a hydroxy group.

For example, R ¹ may be a C3 to C20 cycloalkyl group substituted with a hydroxyl group or a C6 to C20 aryl group substituted with a hydroxyl group. When R ¹ has a hydroxyl group as a substituent, a sensitivity improvement effect may be superior to that of a case in which there is no substituent or has other substituents such as a methyl group.

For example, L ¹ may be a substituted or unsubstituted C1 to C20 alkylene group. When L ¹ is an alkylene group, a sensitivity improvement effect may be superior to that of a single bond.

For example, in Formula 1, R ² and R ⁴ may each independently represent a C1 to C10 trifluoroalkyl group, and R ³ may be a hydroxyl group.

For example, the compound represented by Formula 1 may be included in an amount of 1 part by weight to 30 parts by weight based on 100 parts by weight of an alkali-soluble resin to be described later. When the compound represented by Formula 1 is included within the above content range, it may have an effect of improving sensitivity.

For example, the compound represented by Formula 1 may be represented by any one of Formulas 2 to 6, but is not necessarily limited thereto.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

(A) alkali-soluble resin

The alkali-soluble resin used in the photosensitive resin composition includes a polybenzoxazole precursor, a polyimide precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, a (meth)acrylate resin, or a combination thereof. In , a polybenzoxazole precursor, a polyimide precursor, or a combination thereof may be used as the alkali-soluble resin, but the type of the alkali-soluble resin is not necessarily limited thereto.

The polybenzoxazole precursor includes a repeating unit represented by the following Chemical Formula 7 or includes a repeating unit of the following Chemical Formulas 7 and 8, and has a thermally polymerizable functional group at at least one end portion.

[Formula 7]

[Formula 8]

In Formulas 7 and 8, X ₁ is an aromatic organic group or a tetravalent aliphatic organic group, Y ₁ and Y ₂ are each independently an aromatic organic group or a divalent aliphatic organic _{group, X 2} is an aromatic organic group, 2 It is a divalent aliphatic organic group, a divalent alicyclic organic group, or an organic group having a structure represented by the following formula (9).

[Formula 9]

In Formula 9,

R ₂₃ to R ₂₆ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 alkoxy group or a hydroxy group,

R ₂₇ and R ₂₈ are each independently a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,

k is an integer from 1 to 50;

The form of the polybenzoxazole precursor is not particularly limited, and all of the random, block, or alternating copolymers are possible.

In addition, when the polybenzoxazole precursor includes both the repeating unit of Chemical Formula 7 and the repeating unit of Chemical Formula 8, the repeating unit of Chemical Formula 8 is included in an amount of more than 50 mol%, for example, 60 mol% or more and less than 100 mol% it's good

For example, X ₁ is 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-triflumethylphenyl)hexafluoropropane , 2,2'-bis(4-amino-3-hydroxy-5-trifluoromethylphenyl)hexafluoropropane, 2,2'-bis(4-amino-3-hydroxy-6-trifluoro Methylphenyl)hexafluoropropane, 2,2'-bis(4-amino-3-hydroxy-2-trifluoromethylphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxy -5-pentafluoroethylphenyl)hexafluoropropane, 2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2'-(3-amino-4-hydroxy-5-penta Fluoroethylphenyl)hexafluoropropane, 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-trifluoromethylphenyl)-2'-(3-hydroxy-4-amino-5-trifluoromethylphenyl)hexafluoropropane, 2-(3-amino-4-hydro Roxy-6-trifluoromethylphenyl)-2'-(3-hydroxy-4-amino-5-trifluoromethylphenyl)hexafluoropropane, 2,6-bis[[[5-[1-( Derived from amino-4-hydroxyphenyl)-2,2,2-trifluoro-1-(triflomethyl)ethyl]-2-hydroxyphenyl]amino]methyl]-4-methylphenol and combinations thereof It may be a residue that becomes, but is not limited thereto.

In addition, X ₁ may be a residue represented by a compound represented by Formula 10 or Formula 11 below.

[Formula 10]

[Formula 11]

(In Chemical Formulas 10 and 11,

A ₁ may be selected from the group consisting of O, CO, CR ₈ R ₉ , SO _{2 , S and a single bond,}

R ₈ and R ₉ may be each independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group, preferably, R ₈ and R ₉ are a fluoroalkyl group,

R ₅ to R ₇ may be each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a hydroxyl group, a carboxylic acid group, and a thiol group,

n ₁ may be an integer of 1 to 2,

n ₂ and n ₃ may each independently be an integer of 1 to 3.)

In addition, X ₂ may be derived from aromatic diamines, silicone diamines and cycloaliphatic diamines.

Specific examples of the aromatic diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6- Naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether , 1,4-bis(4-aminophenoxy)benzene, and the like, but is not limited thereto. In addition, these aromatic diamine monomers can be used individually or in mixture.

Specific examples of the silicone diamine include bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)tetramethylsiloxane, bis(p-aminophenyl)tetramethyldisiloxane, bis(γaminopropyl)tetramethyl Disiloxane, 1,4-bis(γaminopropyldimethylsilyl)benzene, bis(4-aminobutyl)tetramethyldisiloxane, bis(γaminopropyl)tetraphenyldisiloxane, 1,3-bis(aminopropyl)tetra and methyldisiloxane, but is not limited thereto.

Specific examples of the alicyclic diamine include, but are not limited to, cyclohexyldiamine, methylenebiscyclohexylamine, and the like.

In addition, the aromatic diamine, silicone diamine, and alicyclic diamine may be used alone or in combination, and an aromatic diamine, silicone diamine or alicyclic diamine may be appropriately mixed and used.

In addition, Y ₁ and Y ₂ may be representative of dicarboxylic acid or a residue of a dicarboxylic acid derivative.

Specific examples of the dicarboxylic acid may include Y(COOH) ₂ (where Y is the same as _{Y 1} and Y _{2 ).}

Specific examples of the dicarboxylic acid derivative include _{an active compound that is a carbonyl halide derivative or an active ester derivative obtained by reacting Y(COOH) 2} with 1-hydroxy-1,2,3-benzotriazole. there is. Examples thereof include 4,4'-oxydibenzoyl chloride, diphenyloxydicarboxylic acid chloride, bis(phenylcarboxylic acid chloride) sulfone, bis(phenylcarboxylic acid chloride) ether, bis(phenylcarboxylic acid) Chloride) a compound selected from the group consisting of phenone, phthalic carboxylic acid dichloride, terephthalic acid dichloride, isophthalic carboxylic acid dichloride, carboxylic acid dichloride, diphenyloxydicarboxylate benzotriazole, and combinations thereof, etc. can be heard

In addition, Y ₁ and Y ₂ may be represented by any one of the following Chemical Formulas 12 to 14.

[Formula 12]

[Formula 13]

[Formula 14]

In Formulas 12 to 14,

R ₁₀ to R ₁₃ are each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₆ , n ₈ and n ₉ may each independently be an integer of 1 to 4, n ₇ may be an integer of 1 to 3,

A ₂ may be O, CR ₁₄ R ₁₅ , CO, CONH, S or SO ₂ , wherein R ₁₄ and R ₁₅ are each independently hydrogen, a substituted or unsubstituted alkyl group, or a fluoroalkyl group.

In addition, the polybenzoxazole precursor has a thermally polymerizable functional group derived from a reactive end-blocking monomer on either or both of the branched chain ends.

The reactive end-blocking monomer is preferably a monoamine having a double bond, a monoanhydride having a double bond, or a combination thereof.

The monoamines having the double bond may include toluidine, dimethylaniline, ethylaniline, aminophenol, aminobenzyl alcohol, aminoindan, aminoacetophenone, or a combination thereof, but is not limited thereto.

The monoanhydrides having the double bond are 5-norbornene-2,3-dicarboxyanhydride of the following formula 15, 3,6-epoxy-1,2,3,6-tetrahydride of the following formula 16 Loftalic anhydride, isobutenylsuccinic anhydride of the following formula 17, maleic anhydride, aconitic anhydride, 4,5,6-tetrahydrophthalic anhydride (3 ,4,5,6-tetrahydrophthalic anhydride), cis-1,2,3,6,-tetrahydrophthalic anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride), itaconic anhydride ( itaconic anhydride: IA), citraconicanhydride (CA), 2,3-dimethylmaleicanhydride (DMMA), or a combination thereof　and the like may be used, but is not limited thereto.

[Formula 15]

[Formula 16]

[Formula 17]

In addition, the following Chemical Formulas 18 to 22 are representative examples of a thermally polymerizable functional group located at the terminal of the polybenzoxazole precursor, and the thermally polymerizable functional group may be crosslinked in a heating process.　

[Formula 18]

(In Formula 18, R ₁₆ is H, CH ₂ COOH, or CH ₂ CHCHCH ₃ .)

[Formula 19]

(In Formula 19, R ₁₇ and R ₁₈ are each independently H or CH ₃ .)

[Formula 20]

[Formula 21]

(In Formula 21, R ₁₉ is H or CH ₃ , and R ₂₀ is CH ₂ or an oxygen atom.)

[Formula 22]

(In Formula 22, R ₂₁ and R ₂₂ are each independently H, CH ₃ or OCOCH ₃ .)

The polybenzoxazole precursor may have a weight average molecular weight (M _w ) of 3,000 g/mol to 300,000 g/mol. When the weight average molecular weight is within the above range, sufficient physical properties can be obtained, and handling is easy due to excellent solubility in organic solvents.

The polyimide precursor may include repeating units represented by Chemical Formulas 23 and 24 below. By including the repeating unit represented by the following Chemical Formula 23, the resin can be cured quickly during high-temperature curing, and thermal properties can be improved during high-temperature curing by including the repeating unit represented by the following Chemical Formula 24.　

[Formula 23]

[Formula 24]

In Chemical Formulas 23 to 24, X ₃ is an aromatic organic group or a divalent alicyclic organic group, Y ₃ and Y ₄ are each independently an aromatic organic group or a tetravalent alicyclic organic group, and X ₄ is an aromatic oil. a group, a divalent alicyclic organic group, or a functional group represented by Chemical Formula 9, and R ₁₀₀ to R ₁₀₃ are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.

In the photosensitive resin composition, when the sum of the repeating unit represented by Chemical Formula 23 and the repeating unit represented by Chemical Formula 24 is 100 mol%, the repeating unit represented by Chemical Formula 23 is 5 mol% to 50 mol%, The repeating unit represented by Chemical Formula 24 may be included in an amount of 50 mol% to 95 mol%.

The polyimide precursor may have a weight average molecular weight (M _w ) of 3,000 g/mol to 300,000 g/mol.

(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 Formulas 71 and 73 to 75, but are not limited thereto.

[Formula 71]

In Formula 71,

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 72a or a functional group represented by the following Chemical Formula 72b, wherein Q may not be a hydrogen atom at the same time,

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

[Formula 72a]

[Formula 72b]

[Formula 73]

In Formula 73,

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 71,

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

[Formula 74]

In Formula 74,

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 71,

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 75]

In Formula 75,

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 71.

The photosensitive diazoquinone compound is preferably included in an amount of 1 part by weight to 50 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 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 compound represented by Formula 1, the alkali-soluble resin, the photosensitive diazoquinone compound, and other additives to be described later.

The solvent is an organic solvent, specifically N-methyl-2-pyrrolidone, gamma-butyrolactone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol di Ethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate (methyl lactate), ethyl lactate (ethyl lactate), butyl lactate (butyl lactate), methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate (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 300 parts by weight, for example, 100 parts by weight to 250 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.

(E) other additives

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

The photosensitive resin composition is a diecide (eg, malonic acid, etc.), an alkanolamine (eg, 3-amino-1,2- propanediol, etc.), a leveling agent, a silane 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 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-glycy and doxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and these may be used alone or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 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 ®} , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^® and the like of Dai Nippon Inki Chemical Co., Ltd.; ^{Prorad FC-135 ®} , copper FC-170C ^® , copper FC-430 ^® , copper FC-431 ^®, etc. of Sumitomo Re-M Co., Ltd.; ^{Saffron S-112 ®} , Copper S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^{® from} Asahi Grass Co., Ltd., etc.; May be selected from commercially available under the name, such as Toray Silicone ^® (Note)社SH-28PA, the copper ^® -190, copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

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, Those commercially available under the names BYK-325 and BYK-378 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 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.

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)

(Alkali-soluble resin: polybenzoxazole precursor synthesis)

Preparation Example 1

2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3, while passing nitrogen through a 4-neck flask equipped with a stirrer, temperature control device, nitrogen gas injection device and cooler 67 g of 3-hexafluoropropane and 370 g of N-methyl-2-pyrrolidone (NMP) were added and dissolved.

When the solid is completely dissolved, 26 g of pyridine as a catalyst is added, and a solution obtained by dissolving 49 g of 4,4'-oxydibenzoyl chloride in 370 g of NMP while maintaining the temperature at 0° C. to 5° C. is slowly placed in a 4-necked flask for 30 minutes. drop it After the dropping is completed, the reaction is performed at 0° C. to 5° C. for 1 hour, and the temperature is raised to room temperature to react for 3 hours.

7.5 g of 5-norborene-2,3-dicarboxyanhydride was added thereto, stirred at 80° C. for 24 hours, and then the reaction was terminated. The reaction mixture is put into a solution of water/methanol = 10/1 (volume ratio) to form a precipitate, the precipitate is filtered and washed sufficiently with water, and then dried under vacuum at 80° C. for at least 24 hours to obtain a polybenzoxazole precursor .

(Preparation of photosensitive resin composition)

Example 1

30 g of the polybenzoxazole precursor of Preparation Example 1 was added to and dissolved in a solvent of 52 g of γ (gamma)-butyrolactone (GBL), and then the compound represented by the following Chemical Formula 2 (1,1,1,3,3) ,3-Hexafluoro-2-phenylpropan-2-ol, A Chemtek Product List) 1.5 g, a photosensitive diazoquinone compound having the structure of the following formula A (MIPHOTO TPA517; Miwon Corporation) 4.5 g, a silane coupling agent (KBM-573) ; Shin-Etsu) and 0.009 g of a silicone surfactant (BYK-378; BYK Chem) were added and dissolved, followed by filtration through a 0.45 μm fluororesin filter to obtain a photosensitive resin composition.

[Formula 2]

[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.)

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 3 g of the compound represented by Formula 2 was used instead of 1.5 g, and 55 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g.

Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 4.5 g of the compound represented by Formula 2 was used instead of 1.5 g, and 57 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g. .

Example 4

Except for using the compound represented by the following formula (3) (4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]phenol, Aldrich) instead of the compound represented by the formula (2), In the same manner as in Example 1, a photosensitive resin composition was prepared.

[Formula 3]

Example 5

A photosensitive resin composition was prepared in the same manner as in Example 4, except that 3 g of the compound represented by Formula 3 was used instead of 1.5 g, and 55 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g.

Example 6

A photosensitive resin composition was prepared in the same manner as in Example 4, except that 4.5 g of the compound represented by Formula 3 was used instead of 1.5 g, and 57 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g. .

Example 7

In the same manner as in Example 1, except that the compound represented by the following formula (4) (Cyclohexanemethanol, 4-hydroxy-α,α-bis(trifluoromethyl)-, SMS) was used instead of the compound represented by the formula (2), the photosensitive resin The composition is prepared.

[Formula 4]

Example 8

A photosensitive resin composition was prepared in the same manner as in Example 7, except that 3 g of the compound represented by Formula 4 was used instead of 1.5 g, and 55 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g.

Example 9

A photosensitive resin composition was prepared in the same manner as in Example 7, except that 4.5 g of the compound represented by Formula 4 was used instead of 1.5 g, and 57 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g. .

Example 10

Except for using the compound represented by the following formula (5) (2-benzyl-1,1,1,3,3,3-hexafluoro-2-propanol, Chemieliva Pharmaceutical Product List) instead of the compound represented by the formula (2), A photosensitive resin composition was prepared in the same manner as in Example 1.

[Formula 5]

Example 11

A photosensitive resin composition was prepared in the same manner as in Example 10, except that 3 g of the compound represented by Formula 5 was used instead of 1.5 g, and 55 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g.

Example 12

A photosensitive resin composition was prepared in the same manner as in Example 10, except that 4.5 g of the compound represented by Formula 5 was used instead of 1.5 g, and 57 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g. .

Example 13

In the same manner as in Example 1, except that the compound represented by the following formula (6) (Benzenemethanol, 2-methyl-α, α-bis (trifluoromethyl)-, Shanghai Chemhere Product List) was used instead of the compound represented by the formula (2) to prepare a photosensitive resin composition.

[Formula 6]

Example 14

A photosensitive resin composition was prepared in the same manner as in Example 13, except that 3 g of the compound represented by Formula 6 was used instead of 1.5 g, and 55 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g.

Example 15

A photosensitive resin composition was prepared in the same manner as in Example 13, except that 4.5 g of the compound represented by Formula 6 was used instead of 1.5 g, and 57 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g. .

Comparative Example 1

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula 2 was not used, and 51 g of γ (gamma)-butyrolactone (GBL) was used instead of 52 g.

Comparative Example 2

A compound represented by the following formula C-1 instead of the compound represented by the formula 2 (2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3- A photosensitive resin composition was prepared in the same manner as in Example 1, except that hexafluoro-2-propanol, Aldrich) was used.

[Formula C-1]

Comparative Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by the following formula C-2 (Cas No. 1965-09-9, 1717, CheMall) was used instead of the compound represented by the formula 2 do.

[Formula C-2]

Evaluation 1: Sensitivity evaluation

After coating the photosensitive resin compositions according to Examples 1 to 15 and Comparative Examples 1 to 3 on an 8-inch wafer, heated on a hot plate at 120° C. for 4 minutes to form a 10 μm thick coating film. Using a mask engraved with patterns of various sizes on the coating film, exposure was performed with an i-line stepper (NSR i11D, Nikon) with varying exposure doses, and then 50/50 seconds (2 puddles) in 2.38% TMAH aqueous solution at room temperature. After liver development, the exposed parts are dissolved and removed, and then washed with pure water for 30 seconds to form a pattern. Curing is performed at 280° C. for 60 minutes under a nitrogen atmosphere.

Thickness is measured using ST-5000 (K-MAC), and CD is measured by S-9260 (Hitachi). Sensitivity was evaluated by measuring 7㎛ hole pattern exposure dose and CD, and the results are shown in Table 1 below.

Evaluation 2: Mechanical Properties

The photosensitive resin compositions according to Examples 1 to 15 and Comparative Examples 1 to 3 were spin-coated on a glass plate, and subjected to sequential heat treatment at 180° C. for 60 minutes and 300° C. for 60 minutes in a furnace oven under a nitrogen stream to obtain a thickness. After forming a film of 10 μm, a cut is made on the edge and peeled off using water. After drying the peeled film at 100° C. for about 30 minutes to remove water, the film is cut to a size of 100 X 10 mm based on ASTM-D882. Elongation at break was measured using UTM analysis, and the results are shown in Table 1 below.

7 μm hole E _op (mJ/cm ² ) Elongation (%) Example 1 580 70 Example 2 550 60 Example 3 530 60 Example 4 570 70 Example 5 540 65 Example 6 520 60 Example 7 510 65 Example 8 490 60 Example 9 470 70 Example 10 500 60 Example 11 460 65 Example 12 440 60 Example 13 550 65 Example 14 530 65 Example 15 510 70 Comparative Example 1 650 60 Comparative Example 2 610 50 Comparative Example 3 620 60

From Table 1, it can be seen that the photosensitive resin composition according to an embodiment can greatly improve the sensitivity by using a compound having a specific structure as a dissolution control agent.

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 (11)

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

In Formula 1,
L ¹ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,
R ¹ is a substituted or unsubstituted C3 to C20 aliphatic ring group or a substituted or unsubstituted C6 to C20 aromatic ring group, wherein the aliphatic ring group does not include an unsaturated bond;
R ² to R ⁴ are each independently a hydroxyl group or a C1 to C10 trifluoroalkyl ^{group, wherein at least one of R 2} to R ⁴ is a hydroxyl group, and at least one of R ² to R ⁴ is a C1 to C10 trifluoroalkyl group am.
According to claim 1,
wherein R ¹ is a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C6 to C20 aryl group.
According to claim 1,
R ¹ is an unsubstituted C3 to C20 cycloalkyl group, a C1 to C10 alkyl group substituted C3 to C20 cycloalkyl group, a hydroxy group substituted C3 to C20 cycloalkyl group, an unsubstituted C6 to C20 aryl group, a C1 to C10 alkyl group A photosensitive resin composition comprising a substituted C6 to C20 aryl group or a C6 to C20 aryl group substituted with a hydroxy group.
According to claim 1,
wherein R ² and R ⁴ are each independently a C1 to C10 trifluoroalkyl group, and R ³ is a hydroxyl group.
According to claim 1,
The compound represented by Formula 1 is included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin.
According to claim 1,
The compound represented by Formula 1 is a photosensitive resin composition represented by any one of Formulas 2 to 6 below.
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

According to claim 1,
The alkali-soluble resin is a polybenzoxazole precursor, a polyimide precursor, or a combination thereof.
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,
1 part by weight to 30 parts by weight of the compound represented by Formula 1,
A photosensitive resin composition comprising 100 parts by weight to 300 parts by weight of the solvent.
According to claim 1,
The photosensitive resin composition further comprises an additive of a diecide, an alkanolamine, a leveling agent, a silane coupling agent, a surfactant, an epoxy compound, a radical polymerization initiator, a thermal latent acid generator, or a combination thereof.
A photosensitive resin film prepared by using the photosensitive resin composition of any one of claims 1 to 9.
An electronic device comprising the photosensitive resin film of claim 10 .