KR102288385B1 - Photosensitive resin composition, photosensitive resin layer and electronic device using the same - Google Patents

Abstract

[화학식 2]

(상기 화학식 1 및 화학식 2에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a dissolution control agent comprising a first phenol resin represented by the following formula (1) and a second phenol resin represented by the following formula (2); and (D) a solvent, wherein the first phenolic resin and the second phenolic resin are included in a weight ratio of 10:90 to 30:70, a photosensitive resin film prepared using the photosensitive resin composition, and the photosensitive resin film An electronic device is provided.
[Formula 1]

[Formula 2]

(In Formulas 1 and 2, each substituent is as defined in the specification.)

Description

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

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

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

However, due to the recent increase in environmental problems, countermeasures against organic solvents have been demanded, and similarly to photoresists, a heat-resistant photosensitive resin material that can be developed with an alkaline aqueous solution has been proposed.

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

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

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

When the cured film is applied to a semiconductor device as a surface protective film and an interlayer insulating film, it is required to have high reliability. Although there are various indices for evaluating the reliability, in particular, sensitivity and residue characteristics are important. Moreover, the shape of a hardening relief pattern must be favorable, it must have sufficient alkali solubility, there are few residual films at the time of image development, and it must be excellent in adhesiveness with a board|substrate.

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

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

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

One embodiment is (A) alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a dissolution control agent comprising a first phenol resin represented by the following formula (1) and a second phenol resin represented by the following formula (2); and (D) a solvent, wherein the first phenol resin and the second phenol resin are included in a weight ratio of 10:90 to 30:70.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ¹ to R ³ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C5 alkyl group,

p, q and r are each independently an integer of 0 to 3,

a, b and c are each independently a positive integer.

The second phenolic resin may be a block copolymer, an alternating copolymer, or a random copolymer.

The dissolution control agent may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin.

The alkali-soluble resin may be a polyhydroxyamide resin.

The photosensitive resin composition contains 1 to 100 parts by weight of the photosensitive diazoquinone compound based on 100 parts by weight of the alkali-soluble resin, 0.1 to 20 parts by weight of the dissolution control agent, and 100 parts by weight of the solvent It may contain from 500 parts by weight to 500 parts by weight.

The photosensitive resin composition includes a dissolution regulator, a sensitivity sensitizer, a crosslinking agent, a diacid, an alkanolamine, a leveling agent, a coupling agent, a surfactant, an epoxy compound, and a radical polymerization having a structure different from that of the first phenol resin and the second phenol resin. It may further include an additive of an 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.

In the photosensitive resin composition according to an embodiment, by mixing and using a dissolution control agent including two different phenolic resins in a specific ratio, the residual film rate, sensitivity, and residual properties can be improved at the same time.

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

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

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

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

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

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

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

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

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

The photosensitive resin composition according to an embodiment includes (A) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a dissolution control agent comprising a first phenol resin and a second phenol resin; and (D) a solvent, wherein the first phenol resin is a copolymer represented by the following Chemical Formula 1, the second phenol resin is a copolymer represented by the following Chemical Formula 2, and the first phenol resin and the second phenol The resin is included in a weight ratio of 10:90 to 30:70.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ¹ to R ³ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C5 alkyl group,

p, q and r are each independently an integer of 0 to 3,

a, b and c are each independently a positive integer.

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. Reliability, in particular, the residual film rate, sensitivity and residual characteristics are very important due to the nature of the process material. The photosensitive resin composition according to an embodiment uses a dissolution control agent including the first phenol resin and the second phenol resin to provide an excellent residual film rate. It is possible to improve sensitivity and residue properties while maintaining it.

Hereinafter, each component will be described in detail.

(C) dissolution regulator

The dissolution control agent includes two different phenolic resins. The phenol resin may include the first phenol resin represented by Chemical Formula 1 and the second phenol resin represented by Chemical Formula 2, thereby improving sensitivity and residue characteristics while maintaining an excellent residual film ratio.

In Formulas 1 and 2, a, b, and c mean the number of moles, and may be an integer of 1 to 1,000, such as an integer of 1 to 500. That is, the second phenolic resin may be a copolymer in which the structural unit represented by the following Chemical Formula 2a and the structural unit represented by the following Chemical Formula 2b are included in a molar ratio of b:c.

[Formula 2a]

[Formula 2b]

In Formulas 2a and 2b,

R ² and R ³ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C5 alkyl group,

q and r are each independently an integer of 0 to 3.

For example, Chemical Formula 1 may be represented by Chemical Formula 1-1, and Chemical Formula 2 may be represented by Chemical Formula 2-1.

[Formula 1-1]

[Formula 2-1]

In Formulas 1-1 and 2-1,

R ¹ to R ³ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C5 alkyl group,

p, q and r are each independently an integer of 0 to 3,

a, b and c are each independently a positive integer.

The first phenolic resin and the second phenolic resin are included in a weight ratio of 10:90 to 30:70. When the first phenolic resin and the second phenolic resin are included in the above weight ratio range, it is easy to control the dissolution rate for TMAH, which will be described later, while maintaining an excellent residual film rate, and at the same time, it is possible to improve sensitivity and residue characteristics. If the content of the first phenolic resin compared to the second phenolic resin is too small (eg, the first phenolic resin: the second phenolic resin = 5:95), the dissolution rate for TMAH becomes too fast, so that it is impossible to control the remaining film rate Similarly, if the content of the first phenol resin compared to the second phenol resin is too large (eg, the first phenol resin: the second phenol resin = 35: 65), the dissolution rate for TMAH becomes too slow, so that the sensitivity control is difficult It becomes difficult and the residue inside the pattern cannot be improved.

For example, the dissolution control agent may be included in an amount of 0.1 parts by weight to 20 parts by weight, for example, 1 part by weight to 15 parts by weight, for example 3 parts by weight to 12 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the dissolution control agent is within the above range, it is possible to secure the photosensitive resin composition having excellent sensitivity, resolution, and residue removability, and furthermore, a photosensitive resin composition capable of forming a highly sensitive pattern after curing, and at the same time improve the heat resistance of the insulating film.

(A) alkali-soluble resin

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

The polyhydroxyamide resin may include a structural unit represented by Formula 4 below, and the polyimide precursor may include a structural unit represented by Formula 5 below.

[Formula 4]

In Formula 4,

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

Y ¹ and Y ² are each independently a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group,

m1 is an integer from 2 to 1000, m2 is an integer from 0 to 500, and m1/(m1+m2) > 0.5.

[Formula 5]

In Formula 5,

X ³ 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 ³ 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 4, X ¹ is an aromatic organic group and may be a residue derived from an aromatic diamine.

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

Examples of X ¹ and X ² may include, but are not limited to, a functional group represented by Formula 6 or Formula 7 below.

[Formula 6]

[Formula 7]

In Formulas 6 and 7,

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

Specific examples of the dicarboxylic acid derivative include 4,4'-oxydibenzoylchloride, diphenyloxydicarbonyldichloride, bis(phenylcarbonylchloride)sulfone, bis(phenylcarbonylchloride)ether, bis(phenylcarbonylchloride) ) phenone, phthaloyl dichloride, terephthaloyl dichloride, isophthaloyl dichloride, dicarbonyl dichloride, diphenyloxydicarboxylate dibenzotriazole, or a combination thereof, but is not limited thereto.

Examples of Y ¹ and Y ² may include functional groups represented by the following Chemical Formulas 8 to 10, but are not limited thereto.

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 8 to 10,

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

Specifically, X ³ 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 5, Y ³ is an aromatic organic group, a tetravalent to hexavalent aliphatic organic group, or a tetravalent to hexavalent alicyclic organic group. Specifically, Y ³ is an aromatic organic group or a tetravalent to hexavalent alicyclic organic group.

Y ³ 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 be a polyhydroxyamide resin.

The alkali-soluble resin may have a weight average molecular weight (Mw) of 3,000 g/mol to 300,000 g/mol, and specifically may have a weight average molecular weight (Mw) of 5,000 g/mol to 30,000 g/mol. When it has a weight average molecular weight (Mw) in the above range, it is possible to obtain a sufficient remaining film rate in the 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 Formulas 11 and 13 to 15, but are not limited thereto.

[Formula 11]

In the above formula (11),

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 12a or a functional group represented by the following Chemical Formula 12b, 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 12a]

[Formula 12b]

[Formula 13]

In the above formula (13),

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 11,

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

[Formula 14]

In the formula (14),

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 11,

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 15]

In the formula (15),

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 11 above.

The photosensitive diazoquinone compound is preferably included in an amount of 1 to 100 parts by weight, for example 5 to 50 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 a dissolution regulator including the first phenol resin and the second phenol resin.

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 500 parts by weight, for example, 100 parts by weight to 400 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the content of the solvent is within the above range, a film having a sufficient thickness may be coated, and solubility and coatability may be excellent.

(E) other additives

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

The photosensitive resin composition is a dissolution control agent, a sensitivity sensitizer, a crosslinking agent, diacids such as malonic acid, 3-amino-1, an alkanolamine such as 2-propanediol, a leveling agent, a 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 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 coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxy and propyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and these may be used alone or in combination of two or more.

The 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 ®} , 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 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.

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

(3) development step

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

(4) post-processing step

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

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

(Example)

(Synthesis of alkali-soluble resin)

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

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

1.1 g of 5-norborene-2,3-dicarboxyanhydride was added thereto, and after stirring at 70° C. for 24 hours, the reaction was terminated. The reaction mixture was poured into a solution of water/methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and thoroughly washed with water, and then dried under vacuum at 80° C. for at least 24 hours to obtain a polyhydroxyamide resin. .

(Polymerization of dissolution control agent)

Polymerization Example 1: First phenolic resin

In a flask with a capacity of 1.0 liter, 1.00 mol of m-cresol, 1.50 mol of p-cresol, 1.25 mol of salicylic acid, 0.002 mol of p-toluene sulfonic acid monohydrate, and 100 g of propylene glycol monomethyl ether were mixed and stirred at 70° C. to dissolve the solid and mixed. A solution (reaction solution) was obtained. The obtained reaction liquid was heated to 120 degreeC with the oil bath. The reaction solution was stirred at 120°C continuously for 5 hours, and after reacting, the temperature of the liquid was lowered to 60°C. After completion of the reaction, the acid was removed using a mixture of water and methanol.

Polymerization Example 2: Second phenolic resin

In a flask with a capacity of 1.0 liter, 1.00 mol of m-cresol, 1.50 mol of p-cresol, 0.50 mol of salicylic acid, 0.75 mol of formaldehyde, 0.002 mol of p-toluene sulfonic acid monohydrate, and 100 g of propylene glycol monomethyl ether were mixed and stirred at 70°C. The solid was dissolved to obtain a mixed solution (reaction solution). The obtained reaction liquid was heated to 120 degreeC with the oil bath. The reaction solution was stirred at 120°C continuously for 5 hours, and after reacting, the temperature of the liquid was lowered to 60°C. After completion of the reaction, the acid was removed using a mixture of water and methanol.

(Preparation of photosensitive resin composition)

Examples 1 to 4 and Comparative Examples 1 to 4

After dissolving 100 g of the polyhydroxyamide resin in a solvent of 300 g of γ (gamma)-butyrolactone (GBL), 30 g of a photosensitive diazoquinone compound (MIPHOTO TPD425, Miwon Commercial Co., Ltd.) and the first The phenol resin and the second phenol resin were added and dissolved in the weight ratio shown in Table 1 below, followed by stirring under a yellow light until a homogeneous solution was obtained. Thereafter, it was filtered through a 0.20 µm fluororesin filter to obtain a photosensitive resin composition.

weight ratio first phenolic resin Second phenolic resin Example 1 10 90 Example 2 15 85 Example 3 20 80 Example 4 30 70 Comparative Example 1 0 100 Comparative Example 2 5 95 Comparative Example 3 35 65 Comparative Example 4 100 0

evaluation

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

(Evaluation 1: Remaining film rate)

The thickness difference before/after image development was computed in %, and it was set as the residual film rate.

(Evaluation 2: Sensitivity)

The exposure amount representing the 7 µm pattern dimension after development was calculated as the sensitivity.

(Evaluation 3: scum)

- O: No composition remains inside the hole pattern after development

- X: The composition inside the hole pattern remains after development

Remaining film rate (%) Sensitivity (mJ/cm ² ) Scum Example 1 91.3 540 X Example 2 90.9 525 X Example 3 89.5 510 X Example 4 89.0 500 X Comparative Example 1 94.0 750 O Comparative Example 2 92.8 680 O Comparative Example 3 85.9 460 O Comparative Example 4 79.0 440 O

Through Table 1, the photosensitive resin composition according to an embodiment of the present invention contains the structural unit-containing first phenol resin represented by Formula 1 and the structural unit-containing second phenol resin represented by Formula 2 in a specific ratio. It can be confirmed that, by using a dissolution controlling agent that

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 (8)

(A) alkali-soluble resin;
(B) a photosensitive diazoquinone compound;
(C) a dissolution control agent comprising a first phenol resin represented by the following formula (1) and a second phenol resin represented by the following formula (2); and
(D) solvent
including,
The photosensitive resin composition comprising the first phenol resin and the second phenol resin in a weight ratio of 10:90 to 30:70:
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
R ¹ to R ³ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C5 alkyl group,
p, q and r are each independently an integer of 0 to 3,
a, b and c are each independently a positive integer.
According to claim 1,
The photosensitive resin composition of the second phenolic resin is a block copolymer, an alternating copolymer or a random copolymer.
According to claim 1,
The photosensitive resin composition comprising the dissolution control agent in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin.
According to claim 1,
The photosensitive resin composition wherein the alkali-soluble resin is a polyhydroxyamide resin.
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 100 parts by weight of the photosensitive diazoquinone compound,
0.1 parts by weight to 20 parts by weight of the dissolution control agent,
A photosensitive resin composition comprising 100 parts by weight to 500 parts by weight of the solvent.
According to claim 1,
The photosensitive resin composition includes a dissolution regulator, a sensitivity sensitizer, a crosslinking agent, a diacid, an alkanolamine, a leveling agent, a coupling agent, a surfactant, an epoxy compound, and a radical polymerization agent having a structure different from that of the first phenol resin and the second phenol resin. The photosensitive resin composition further comprising an additive of an 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 6.
An electronic device comprising the photosensitive resin film of claim 7.