KR102193440B1 - Photosensitive resin composition, photosensitive resin layer using the same and electronic device - Google Patents

Abstract

(A) an alkali-soluble resin comprising a first polybenzoxazole precursor and a second polybenzoxazole precursor having different weight average molecular weights; (B) photosensitive diazoquinone compound; And (C) a solvent, wherein the weight average molecular weight of the first polybenzoxazole precursor is less than the weight average molecular weight of the second polybenzoxazole precursor, and the first polybenzoxazole precursor is the second poly A photosensitive resin composition comprising 10 parts by weight to 70 parts by weight relative to 100 parts by weight of a benzoxazole precursor, a photosensitive resin film manufactured using the same, and an electronic device including the photosensitive resin film are provided.

Description

Photosensitive resin composition, photosensitive resin film and electronic device using the same {PHOTOSENSITIVE RESIN LAYER USING THE SAME AND ELECTRONIC DEVICE}

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

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

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

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

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

The photosensitive resin composition can form a positive relief pattern by exposure and development by an alkaline aqueous solution. In addition, heat cured film properties are obtained.

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

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

Accordingly, a method of adding a phenol compound to a heat-resistant resin precursor has been proposed as a method of increasing the residual film during development (adjusting development properties) and increasing sensitivity. However, with conventionally used phenolic compounds, improvement of lifting after development is not satisfactory, and there is a limit in meeting the high standards for heat resistance and sensitivity in recent years.

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

One embodiment is to provide a photosensitive resin composition having high heat resistance and high sensitivity without using a separate phenolic compound.

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

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

In one embodiment, (A) an alkali-soluble resin including a first polybenzoxazole precursor and a second polybenzoxazole precursor having different weight average molecular weights; (B) photosensitive diazoquinone compound; And (C) a solvent, wherein the weight average molecular weight of the first polybenzoxazole precursor is less than the weight average molecular weight of the second polybenzoxazole precursor, and the first polybenzoxazole precursor is the second poly It provides a photosensitive resin composition comprising 10 parts by weight to 70 parts by weight based on 100 parts by weight of the benzoxazole precursor.

The weight average molecular weight of the first polybenzoxazole precursor and the weight average molecular weight of the second polybenzoxazole precursor may differ by 5000 g/mol or more.

The weight average molecular weight of the first polybenzoxazole precursor may be 4000 g/mol or less, and the weight average molecular weight of the second polybenzoxazole precursor may be 9000 g/mol or more.

The first polybenzoxazole precursor may be included in an amount of 10 to 40 parts by weight based on 100 parts by weight of the second polybenzoxazole precursor.

The photosensitive resin composition includes 10 parts by weight to 70 parts by weight of the first polybenzoxazole precursor, and 10 parts by weight to the photosensitive diazoquinone compound, based on 100 parts by weight of the second polybenzoxazole precursor. It includes 100 parts by weight, and may include 150 parts by weight to 300 parts by weight of the solvent.

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

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

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

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

The photosensitive resin composition according to an embodiment does not use a phenolic compound as a separate additive, but by modifying the composition of a polybenzoxazole precursor in an alkali-soluble resin, and has better heat resistance than when using a phenolic compound as a separate additive. And sensitivity.

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

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

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

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

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

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

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

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

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

The photosensitive resin composition according to an embodiment includes: (A) an alkali-soluble resin including a first polybenzoxazole precursor and a second polybenzoxazole precursor having different weight average molecular weights; (B) photosensitive diazoquinone compound; And (C) a solvent.

And, the weight average molecular weight of the first polybenzoxazole precursor is less than the weight average molecular weight of the second polybenzoxazole precursor, the first polybenzoxazole precursor 100 parts by weight of the second polybenzoxazole precursor It is included in 10 parts by weight to 70 parts by weight.

When the photosensitive resin composition according to an embodiment is used as a protective film or an insulating layer in a semiconductor or display device, the composition is coated and then developed and cured after UV exposure. Sensitivity and heat resistance are very important for improving throughput due to the characteristics of the process material.The photosensitive resin composition according to an embodiment is two types of polybenzoxazoles having different weight average molecular weights without the use of conventional phenol compounds, etc. By using a precursor, sensitivity and heat resistance can be improved.

Hereinafter, each component will be described in detail.

(A) alkali-soluble resin

The alkali-soluble resin used in the photosensitive resin composition includes a polybenzoxazole precursor, a polyimide precursor, a novolac resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, or a combination thereof, and in one embodiment, a weight average Two types of polybenzoxazole precursors having different molecular weights are used.

The polybenzoxazole precursor may include a structural unit represented by Formula 1 below.

[Formula 1]

In Formula 1,

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

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

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

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

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

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

Examples of X ⁰ and X ¹ include functional groups represented by the following Formulas 2 and 3, but are not limited thereto.

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,

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

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

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

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

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

Examples of Y ⁰ and Y ¹ include functional groups represented by the following Chemical Formulas 4 to 6, but are not limited thereto.

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 4 to 6,

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 Examples are C1 to C30 fluoroalkyl groups.

The two kinds of polybenzoxazole precursors constituting the alkali-soluble resin are composed of a first polybenzoxazole precursor having a small weight average molecular weight and a second polybenzooxazole precursor having a large weight average molecular weight. In addition, the first polybenzoxazole precursor is included in an amount of 10 to 70 parts by weight based on 100 parts by weight of the second polybenzoxazole precursor.

When the two types of polybenzoxazoles have the above configuration, they may have excellent sensitivity and heat resistance without using separate additives such as phenol compounds.

Specifically, the weight average molecular weight of the first polybenzoxazole precursor and the weight average molecular weight of the second polybenzoxazole precursor may differ by 5000 g/mol or more. That is, the weight average molecular weight of the first polybenzoxazole precursor may be less than 5000 g/mol or more than the weight average molecular weight of the second polybenzoxazole precursor. When a difference between the weight average molecular weight of the first polybenzoxazole precursor and the weight average molecular weight of the second polybenzoxazole precursor is 5000 g/mol or more, it may have a greater effect on improving sensitivity and heat resistance. For example, when the difference between the weight average molecular weight of the first polybenzoxazole precursor and the weight average molecular weight of the second polybenzoxazole precursor is less than 5000 g/mol, the effect of improving sensitivity and heat resistance is insignificant, such as phenol compounds. It is difficult to see that it is more advantageous in terms of sensitivity and heat resistance than the photosensitive resin composition using the additive of.

More specifically, the weight average molecular weight of the first polybenzoxazole precursor may be 4000 g/mol or less, and the weight average molecular weight of the second polybenzoxazole precursor may be 9000 g/mol or more. When the upper limit of the molecular weight of the first polybenzoxazole precursor exceeds 4000 g/mol, the difference in molecular weight with the second polybenzoxazole precursor having a higher molecular weight decreases, making it difficult to have an effect of improving sensitivity, and the second polybenzox When the lower limit of the weight average molecular weight of the oxazole precursor is less than 9000 g/mol, the difference in molecular weight with the first polybenzoxazole precursor having a smaller molecular weight is also reduced, making it difficult to have an effect of improving heat resistance.

For example, the weight average molecular weight of the first polybenzoxazole precursor may be 2000 g/mol to 4000 g/mol, and the weight average molecular weight of the second polybenzoxazole precursor may be 9000 g/mol to 15000 g/mol have.

For example, the first polybenzoxazole precursor may be included in an amount of 10 to 40 parts by weight based on 100 parts by weight of the second polybenzoxazole precursor. In this case, the first polybenzoxazole precursor is more excellent in sensitivity and heat resistance improvement effect than when it is included in 10 parts by weight to 70 parts by weight relative to 100 parts by weight of the second polybenzoxazole precursor.

(B) photosensitive diazoquinone compound

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

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

[Formula 21]

In Chemical Formula 21,

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

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

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

[Formula 22a]

[Formula 22b]

[Formula 23]

In Chemical Formula 23,

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

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

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

[Formula 24]

In Chemical Formula 24,

A ³ may be CO or CR ⁵⁰⁰ R ⁵⁰¹ , 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, and Q is the same as defined in Formula 21,

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

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

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

[Formula 25]

In Chemical Formula 25,

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

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

Q is the same as defined in Chemical Formula 21.

The photosensitive diazoquinone compound is preferably contained in an amount of 10 to 100 parts by weight, for example, 10 to 30 parts by weight, based on 100 parts by weight of the second polybenzoxazole precursor. When the content of the photosensitive diazoquinone compound is within the above range, the pattern is well formed without residue by exposure, there is no loss of film thickness during development, and a good pattern can be obtained.

(C) 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 other additives described below.

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

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

The solvent is preferably used in an amount of 150 to 300 parts by weight, for example, 170 to 280 parts by weight based on 100 parts by weight of the second polybenzoxazole precursor. When the content of the solvent is within the above range, a film having a sufficient thickness can be coated, and solubility and coating properties are excellent.

(D) other additives

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

The photosensitive resin composition includes malonic acid, 3-amino-1,2-propanediol, a leveling agent, a silane coupling agent, an interface in order to prevent stains or spots during coating, leveling properties, or the generation of residues due to undeveloped It may contain an activator, a radical polymerization initiator, or an additive of a combination thereof. The amount of these additives can be easily adjusted according to the 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, or 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, and γ-glycy Doxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, 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 are excellent.

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

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Mechapack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^{® of} Dai Nippon Ink & Chemicals Co., Ltd.; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; 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 ®.

As the silicone surfactant, BYK Chem's BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, What is marketed under names such as BYK-325 and BYK-378 can be used.

The surfactant may be used in an amount of 0.001 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 IZO substrate or a glass substrate is excellent.

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

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

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

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

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

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

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

The photosensitive resin film manufacturing method is as follows.

(1) Application and film formation step

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

(2) exposure step

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

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

(3) development stage

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

(4) Post-processing step

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

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 the first polybenzoxazole precursor)

Manufacturing Example 1

2,2-bis(3-amino-4-hardoxyphenyl)-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. Add 67 g of 3-hexafluoropropane and 370 g of N-methyl-2-pyrrolidone (NMP) to dissolve.

When the solid is completely dissolved, 17 g of pyridine was added as a catalyst and 31 g of 4,4'-oxydibenzoyl chloride was added to 480 g of NMP while maintaining the temperature at 0°C to 5°C. The solution was slowly added to a 4-neck flask equipped with 30 minutes. Let it drip. After the dropping is complete, the reaction is carried out at 0°C to 5°C for 1 hour, and the temperature is raised to room temperature, followed by reaction for 3 hours.

Here, 27.2 g of 5-norborene-2,3-dicarboxyanhydride was added and stirred at 80° C. for 24 hours, and the reaction was terminated. The reaction mixture was added to a solution of water/methanol = 10/1 (volume ratio) to generate a precipitate, the precipitate was filtered and sufficiently washed with water, and then dried under vacuum at 80° C. for 24 hours or more to form the first of Preparation Example 1. A polybenzoxazole precursor (weight average molecular weight: 3800 g/mol) is obtained.

Manufacturing Example 2

2,2-bis(3-amino-4-hardoxyphenyl)-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. Add 67 g of 3-hexafluoropropane and 370 g of N-methyl-2-pyrrolidone (NMP) to dissolve.

When the solid is completely dissolved, 18 g of pyridine was added as a catalyst and 34 g of 4,4'-oxydibenzoyl chloride was added to 480 g of NMP while maintaining the temperature at 0°C to 5°C. Let it drip. After the dropping is complete, the reaction is carried out at 0°C to 5°C for 1 hour, and the temperature is raised to room temperature, followed by reaction for 3 hours.

Here, 24.1 g of 5-norborene-2,3-dicarboxionhydride was added and stirred at 80° C. for 24 hours, and the reaction was terminated. The reaction mixture was added to a solution of water/methanol = 10/1 (volume ratio) to generate a precipitate, the precipitate was filtered and sufficiently washed with water, and dried under vacuum at 80° C. for 24 hours or more to form the first of Preparation Example 2. A polybenzoxazole precursor (weight average molecular weight: 3500 g/mol) is obtained.

Manufacturing Example 3

2,2-bis(3-amino-4-hardoxyphenyl)-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. Add 67 g of 3-hexafluoropropane and 370 g of N-methyl-2-pyrrolidone (NMP) to dissolve.

When the solid is completely dissolved, 19 g of pyridine was added as a catalyst and 36 g of 4,4'-oxydibenzoyl chloride was added to 480 g of NMP while maintaining the temperature at 0°C to 5°C. Let it drip. After the dropping is complete, the reaction is carried out at 0°C to 5°C for 1 hour, and the temperature is raised to room temperature, followed by reaction for 3 hours.

Here, 22.5 g of 5-norborene-2,3-dicarboxionhydride was added and stirred at 80° C. for 24 hours, and the reaction was terminated. The reaction mixture was added to a solution of water/methanol = 10/1 (volume ratio) to generate a precipitate, the precipitate was filtered and sufficiently washed with water, and dried under vacuum at 80° C. for 24 hours or more to form the first of Preparation Example 3. A polybenzoxazole precursor (weight average molecular weight: 3800 g/mol) is obtained.

Comparative Production Example 1

2,2-bis(3-amino-4-hardoxyphenyl)-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. Add 67 g of 3-hexafluoropropane and 370 g of N-methyl-2-pyrrolidone (NMP) to dissolve.

When the solid is completely dissolved, 19 g of pyridine was added as a catalyst and 36 g of 4,4'-oxydibenzoyl chloride was added to 480 g of NMP while maintaining the temperature at 0°C to 5°C. Let it drip. After the dropping is complete, the reaction is carried out at 0°C to 5°C for 1 hour, and the temperature is raised to room temperature, followed by reaction for 3 hours.

Here, 22.5 g of 5-norborene-2,3-dicarboxionhydride was added and stirred at 80° C. for 24 hours, and the reaction was terminated. The reaction mixture was added to a solution of water/methanol = 10/1 (volume ratio) to generate a precipitate, the precipitate was filtered and sufficiently washed with water, and then dried under vacuum at 80° C. for 24 hours or more to prepare the preparation of Comparative Preparation Example 1. 1 A polybenzoxazole precursor (weight average molecular weight: 7000 g/mol) is obtained.

(Synthesis of the second polybenzoxazole precursor)

Manufacturing Example 4

2,2-bis(3-amino-4-hardoxyphenyl)-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. Add 67 g of 3-hexafluoropropane and 370 g of N-methyl-2-pyrrolidone (NMP) to dissolve.

When the solid is completely dissolved, 26 g of pyridine was added as a catalyst, and 49 g of 4,4'-oxydibenzoyl chloride was dissolved in 370 g of NMP while maintaining the temperature at 0℃ to 5℃. Let it drip. After the dropping is complete, the reaction is carried out at 0°C to 5°C for 1 hour, and the temperature is raised to room temperature, followed by reaction for 3 hours.

7.5 g of 5-norborene-2,3-dicarboxionhydride was added thereto and stirred at 80° C. for 24 hours, and the reaction was terminated. The reaction mixture was added to a solution of water/methanol = 10/1 (volume ratio) to generate a precipitate, the precipitate was filtered and sufficiently washed with water, and dried under vacuum at 80° C. for 24 hours or more to form the second of Preparation Example 4. A polybenzoxazole precursor (weight average molecular weight: 11000 g/mol) is obtained.

(Production of photosensitive resin composition)

Example 1

3 g of the first polybenzoxazole precursor of Preparation Example 1 and 30 g of the second polybenzoxazole of Preparation Example 4 were dissolved in a solvent of γ (gamma)-butyrolactone (GBL) 55 g, and then the following formula A Photosensitive diazoquinone compound (MIPHOTO TPA517; Miwon Sangsa) 4.5 g, silane coupling agent (KBM-573; Shin-Etsu) 0.6 g, and silicon-based surfactant (BYK-378; BYK Chem) 0.009 g were added and dissolved. It is filtered through a µm fluororesin filter to obtain a photosensitive resin composition.

[Formula A]

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

And the other is a hydrogen atom.)

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 6 g of the first polybenzoxazole precursor of Preparation Example 1 was used instead of 3 g, and 59 g of (gamma)-butyrolactone (GBL) was used instead of 55 g. To manufacture.

Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 9 g of the first polybenzoxazole precursor of Preparation Example 1 was used instead of 3 g, and 63 g of (gamma)-butyrolactone (GBL) was used instead of 55 g. To manufacture.

Example 4

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 12 g of the first polybenzoxazole precursor of Preparation Example 1 was used instead of 3 g, and 67 g of (gamma)-butyrolactone (GBL) was used instead of 55 g. To manufacture.

Example 5

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 15 g of the first polybenzoxazole precursor of Preparation Example 1 was used instead of 3 g, and 71 g of (gamma)-butyrolactone (GBL) was used instead of 55 g. To manufacture.

Example 6

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 18 g of the first polybenzoxazole precursor of Preparation Example 1 was used instead of 3 g, and 75 g of (gamma)-butyrolactone (GBL) was used instead of 55 g. To manufacture.

Example 7

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 21 g of the first polybenzoxazole precursor of Preparation Example 1 was used instead of 3 g, and 79 g of (gamma)-butyrolactone (GBL) was used instead of 55 g. To manufacture.

Example 8

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the first polybenzoxazole precursor of Preparation Example 2 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 9

A photosensitive resin composition was prepared in the same manner as in Example 2, except that the first polybenzoxazole precursor of Preparation Example 2 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 10

A photosensitive resin composition was prepared in the same manner as in Example 3, except that the first polybenzoxazole precursor of Preparation Example 2 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 11

A photosensitive resin composition was prepared in the same manner as in Example 4, except that the first polybenzoxazole precursor of Preparation Example 2 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 12

A photosensitive resin composition was prepared in the same manner as in Example 5, except that the first polybenzoxazole precursor of Preparation Example 2 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 13

A photosensitive resin composition was prepared in the same manner as in Example 6, except that the first polybenzoxazole precursor of Preparation Example 2 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 14

A photosensitive resin composition was prepared in the same manner as in Example 7, except that the first polybenzoxazole precursor of Preparation Example 2 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 15

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the first polybenzoxazole precursor of Preparation Example 3 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 16

A photosensitive resin composition was prepared in the same manner as in Example 2, except that the first polybenzoxazole precursor of Preparation Example 3 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 17

A photosensitive resin composition was prepared in the same manner as in Example 3, except that the first polybenzoxazole precursor of Preparation Example 3 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 18

A photosensitive resin composition was prepared in the same manner as in Example 4, except that the first polybenzoxazole precursor of Preparation Example 3 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 19

A photosensitive resin composition was prepared in the same manner as in Example 5, except that the first polybenzoxazole precursor of Preparation Example 3 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 20

A photosensitive resin composition was prepared in the same manner as in Example 6, except that the first polybenzoxazole precursor of Preparation Example 3 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Example 21

A photosensitive resin composition was prepared in the same manner as in Example 7, except that the first polybenzoxazole precursor of Preparation Example 3 was used instead of the first polybenzoxazole precursor of Preparation Example 1.

Comparative Example 1

The same as in Example 1, except that the first polybenzoxazole precursor of Comparative Preparation 1 was used instead of the first polybenzoxazole precursor of Preparation Example 1, and the second polybenzoxazole precursor was not used. To prepare a photosensitive resin composition.

Comparative Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the first polybenzoxazole precursor was not used and 51 g of (gamma)-butyrolactone (GBL) was used instead of 55 g.

Comparative Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 9 g of t-butylphenol was used instead of 3 g of the first polybenzoxazole precursor of Preparation Example 1.

evaluation

The photosensitive resin compositions according to Examples 1 to 21 and Comparative Examples 1 to 3 were coated on an 8-inch wafer, and then heated on a hot plate at 120° C. for 4 minutes to form a coating film having a thickness of 10 μm. Using a mask with patterns of various sizes on the coating film, exposure with an i-line stepper (NSR i11D, Nikon) with a change in exposure amount, 50/50 seconds (2 puddles) in 2.38% TMAH aqueous solution at room temperature After dissolving and removing the exposed part by developing it, the pattern is formed by washing with pure water for 30 seconds. Curing is carried out at 280° C. for 60 minutes in a nitrogen atmosphere.

The thickness is measured using ST-5000 (K-MAC), and the CD is measured with S-9260 (Hitachi). Sensitivity is evaluated by measuring 7㎛ hole pattern exposure dose and CD, and heat resistance is evaluated by scratching the cured film with double-sided razor blades, making a pallet and raising the temperature to 10℃ per minute by TA instrument discovery facility, and reducing the wt% loss up to 600℃. Measure and evaluate. The sample loading weight is 5 mg to 10 mg, and the initial weight is 100 wt%, and the amount of weight reduction according to temperature is measured. And check the temperature at which the 5 wt% reduction occurs. The sensitivity and heat resistance evaluation results measured by the above method are shown in Table 1 below.

7 ㎛ hole E _op (mJ/cm ² ) 5 wt% loss temp. (℃) Example 1 500 382 Example 2 480 380 Example 3 470 378 Example 4 440 380 Example 5 480 380 Example 6 460 379 Example 7 470 379 Example 8 490 385 Example 9 480 385 Example 10 470 380 Example 11 450 382 Example 12 460 381 Example 13 460 380 Example 14 480 382 Example 15 490 380 Example 16 470 382 Example 17 460 385 Example 18 440 385 Example 19 500 381 Example 20 490 380 Example 21 480 380 Comparative Example 1 610 350 Comparative Example 2 650 380 Comparative Example 3 450 330

Through Table 1, the photosensitive resin composition according to an embodiment greatly improves heat resistance and sensitivity without using a separate phenolic compound as an additive by changing the composition of the polybenzoxazole precursor constituting the alkali-soluble resin. You can see that you can.

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

Claims (8)

(A) an alkali-soluble resin comprising a first polybenzoxazole precursor and a second polybenzoxazole precursor having different weight average molecular weights;
(B) photosensitive diazoquinone compound; And
(C) solvent
Including,
The weight average molecular weight of the first polybenzoxazole precursor is 4000 g/mol or less, and the weight average molecular weight of the second polybenzoxazole precursor is 9000 g/mol or more,
The first polybenzoxazole precursor is a photosensitive resin composition comprising 10 parts by weight to 70 parts by weight based on 100 parts by weight of the second polybenzoxazole precursor.
delete delete The method of claim 1,
The first polybenzoxazole precursor is a photosensitive resin composition containing 10 parts by weight to 40 parts by weight based on 100 parts by weight of the second polybenzoxazole precursor.
The method of claim 1,
The photosensitive resin composition,
Based on 100 parts by weight of the second polybenzoxazole precursor
Including 10 parts by weight to 70 parts by weight of the first polybenzoxazole precursor,
Including 10 parts by weight to 100 parts by weight of the photosensitive diazoquinone compound,
A photosensitive resin composition comprising 150 parts by weight to 300 parts by weight of the solvent.
The method of claim 1,
The photosensitive resin composition further includes an additive of malonic acid, 3-amino-1,2-propanediol, a leveling agent, a silane coupling agent, a surfactant, a radical polymerization initiator, or a combination thereof.
A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1 and 4 to 6.
An electronic device comprising the photosensitive resin film of claim 7.