KR102570572B1 - Photosensitive resin composition, photosensitive resin layer and display device using the same - Google Patents

Abstract

(A) an alkali-soluble resin containing a structural unit represented by Formula 1 below; (B) a photosensitive diazoquinone compound; and (C) a photosensitive resin composition containing a solvent, a photosensitive resin film prepared using the same, and a display device including the photosensitive resin film.
[Formula 1]

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

Description

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

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

A method of sealing a semiconductor device with an epoxy resin composition for the purpose of protecting the semiconductor device from an external environment such as moisture or mechanical shock has been commercially performed. Conventionally, when sealing a semiconductor device, semiconductor chips were manufactured by dicing a wafer, and then packaging was performed in units of semiconductor chips. Next, a process of dicing into semiconductor chips was developed. In general, the former method is referred to as chip scale packaging (CSP), and the latter process is referred to as wafer level packaging (WLP) and panel level packaging (PLP).

Wafer-level packaging has advantages over chip-scale packaging processes such as high process yield and reduced semiconductor mounting space due to its thin package thickness. However, in the case of wafer-level packaging or panel-level packaging, warpage due to the difference in thermal expansion rate between the wafer or panel and the encapsulant is large because the film forming area is larger than that of chip-scale packaging that encapsulates individual chips. There is a problem. If warpage occurs, it affects the yield and wafer handling of subsequent processes. In addition, liquid-type epoxy resins or silicone resins are mainly used as sealing materials for wafer-level packaging or panel-level packaging. After sealing, there is a problem that the reliability of the semiconductor package is weak.

Therefore, there is a demand for the development of an insulating film for a redistriburion layer (RDL) capable of implementing low warpage and excellent reliability even when wafer-level packaging or panel-level packaging is applied.

In order to meet the above needs, development of a photosensitive resin composition capable of forming an insulating film for a redistribution layer continues. In general, a photosensitive polyimide resin composition in which photosensitivity is imparted to a polyimide resin itself has been mainly used. It is because the pattern formation process can be simplified by using the photosensitive polyimide resin composition. However, in the case of an insulating film (cured film) for a redistribution layer prepared using a conventional photosensitive polyimide resin composition, there is a problem in that corrosion resistance and chemical resistance are deteriorated. Conventional photosensitive polyimide resin has a problem in that it cannot achieve high heat resistance and high reliability because it cannot be cured at a low temperature.

One embodiment is to provide a photosensitive resin composition capable of improving sensitivity through improvement of 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) an alkali-soluble resin containing a structural unit represented by the following formula (1); (B) a photosensitive diazoquinone compound; And (C) it provides a photosensitive resin composition containing a solvent.

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently an organic group including a substituted or unsubstituted C3 to C20 aliphatic ring group, a substituted or unsubstituted C6 to C20 aromatic ring group, or a combination thereof, provided that R ² is *-S -* and at least one selected from the group consisting of structural unit-containing linking groups represented by the following formula L,

[Formula L]

In the above formula L,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group, *-SiR ⁵ R ⁶ -* (where R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C10 alkyl group), or a combination thereof.

The alkali-soluble resin containing the structural unit represented by Formula 1 may be a polymer between an anhydride monomer and a diamine monomer.

The total weight of the anhydride monomer and the total weight of the diamine monomer may be the same based on the total weight of the monomers constituting the alkali-soluble resin containing the structural unit represented by Formula 1.

The diamine monomer includes a phenol-type diamine monomer and a sulfide-type diamine monomer, and the phenol-type diamine monomer and the sulfide-type diamine monomer are based on the total amount of monomers constituting the alkali-soluble resin containing the structural unit represented by Formula 1. :1 to 2:2 by weight.

The phenol-type diamine monomer may be represented by Chemical Formula 2-1 below, and the sulfide-type diamine monomer may be represented by Chemical Formula 2-2 below.

[Formula 2-1]

[Formula 2-2]

In Formula 2-2,

R ³ and R ⁴ are each independently a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group;

n1 and n2 are each independently an integer of 0 to 4.

The diamine monomer may further include a diamine monomer represented by Chemical Formula 2-3.

[Formula 2-3]

In Chemical Formula 2-3,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group, *-SiR ⁵ R ⁶ -* (where R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C10 alkyl group) or a combination thereof;

L ³ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group;

n3 is an integer from 1 to 20;

The anhydride monomer may include monomers represented by Chemical Formulas 3-1 and 3-2 below.

[Formula 3-1]

[Formula 3-2]

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

The photosensitive resin composition may further include an additive such as a diacid, an alkanolamine, a leveling agent, a silane coupling agent, a surfactant, an epoxy compound, a radical polymerization initiator, a latent acid generator, or a combination thereof.

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

Another embodiment provides a display device including the photosensitive resin film.

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

The photosensitive resin composition according to an embodiment includes an alkali-soluble resin having a specific structure, thereby improving adhesion to a metal layer, in particular, a copper metal layer, thereby realizing an insulating film for a redistribution layer having excellent heat resistance and reliability.

1 is a schematic diagram of a die shear tester for evaluating the adhesive strength of a photosensitive resin composition.

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 herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group, and , "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 means an arylene group, and "alkoxyylene group" means 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 its salt, sulfonic acid group or its salt, phosphoric acid or its salt, 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 substituent of a combination thereof.

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

In addition, unless otherwise specified in the present specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible.

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

Unless otherwise specified in the present specification, unsaturated bonds include not only multiple bonds between carbon atoms but also those containing other molecules such as carbonyl bonds and azo bonds.

Unless otherwise defined in the chemical formula within this specification, if 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 in this specification, "*" means a moiety connected to the same or different atom or chemical formula.

The photosensitive resin composition according to one embodiment includes (A) an alkali-soluble resin containing a structural unit represented by Formula 1 below; (B) a photosensitive diazoquinone compound; and (C) a solvent.

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently an organic group including a substituted or unsubstituted C3 to C20 aliphatic ring group, a substituted or unsubstituted C6 to C20 aromatic ring group, or a combination thereof, provided that R ² is *-S -* and at least one selected from the group consisting of structural unit-containing linking groups represented by the following formula L,

[Formula L]

In the above formula L,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group.

When the photosensitive resin composition according to one embodiment is used as a protective film or an insulating layer in a semiconductor or display device, the composition is coated, UV exposed, developed, and cured before application. As the WLP and PLP markets increase, the use of photosensitive resin compositions for redistribution layers is increasing. In the past, it was common to use an adhesion promoter as a separate additive to improve adhesion with a metal layer. However, according to one embodiment, the adhesion to the metal layer, particularly the copper metal layer, can be greatly improved without using a separate adhesion promoter, so that the low-temperature curing type high reliability required for the redistribution layer resin can be easily achieved. . In addition, the photosensitive resin composition according to one embodiment includes an alkali-soluble resin having a structure suitable for a positive type rather than a negative type.

Each component is specifically described below.

(A) alkali soluble resin

Alkali-soluble resins used in the photosensitive resin composition include polybenzoxazole precursors, polyimide precursors, novolak resins, bisphenol A resins, bisphenol F resins, (meth)acrylate resins, or combinations thereof. In the polybenzoxazole precursor, polyimide precursor, or a combination thereof may be used as an alkali-soluble resin, but in one embodiment, an alkali-soluble resin containing a structural unit represented by Formula 1 is used.

Since the alkali-soluble resin containing the structural unit represented by Formula 1 has a group represented by R ² , adhesion to a metal layer, particularly a copper metal layer, can be very easily improved, and in addition to this, it has a structure derived from phenolic diamine. It is also easy to greatly improve developability by applying to a positive-type composition. In addition, by having a structural unit-containing linking group represented by the above formula (L), the glass transition temperature of the alkali-soluble resin may be adjusted to reduce the stress of the finally prepared insulating film (cured film).

Furthermore, since the alkali-soluble resin containing the structural unit represented by Formula 1 has a closed ring structure, compared to a conventional alkali-soluble resin having an open ring structure, such as a polyamic acid structure or a polyhydroxyamide structure, when cured at a low temperature, characteristics are very good. And, as can be seen from the polybenzoxazole structure, not all alkali-soluble resins having a closed ring structure are suitable for low-temperature curing, so the photosensitive resin composition according to one embodiment is alkali-soluble containing structural units represented by Formula 1 By including the resin, an insulating film (cured film) having excellent adhesion to the metal layer, suitable for low-temperature curing, and excellent film properties can be provided.

For example, the structural unit-containing alkali-soluble resin represented by Formula 1 may be a polymer between an anhydride monomer and a diamine monomer. At this time, the total weight of the anhydride monomer and the total weight of the diamine monomer based on the total amount of monomers constituting the alkali-soluble resin containing the structural unit represented by Formula 1 may be the same. In this case, the film properties of the finally manufactured insulating film (cured film) can be further improved.

For example, the diamine monomer includes a phenol-type diamine monomer and a sulfide-type diamine monomer, wherein the phenol-type diamine monomer and the sulfide-type diamine monomer are based on the total amount of monomers constituting the alkali-soluble resin containing the structural unit represented by Formula 1. Diamine monomers may be included in a weight ratio of 2:1 to 2:2. In this case, it is possible to satisfy the low-temperature curing characteristics while maximizing the bonding force between the finally manufactured insulating film (cured film) and the metal layer. For example, when the sulfide-type diamine monomer is included in a greater weight than the phenol-type diamine monomer, the bonding force between the insulating film and the metal layer is further improved, but the pattern characteristics cannot be satisfied, and the phenol-type diamine monomer is twice as much as the sulfide-type diamine monomer. When included in an excessive weight, the bonding force between the insulating film and the metal layer is greatly reduced, which may be undesirable.

For example, the phenol-type diamine monomer may be represented by the following Chemical Formula 2-1, and the sulfide-type diamine monomer may be represented by the following Chemical Formula 2-2, but the sulfide-type diamine monomer is not necessarily limited to the following structure.

[Formula 2-1]

[Formula 2-2]

In Formula 2-2,

R ³ and R ⁴ are each independently a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group;

n1 and n2 are each independently an integer of 0 to 4.

Meanwhile, the diamine monomer may further include a diamine monomer represented by Chemical Formula 2-3, but the diamine monomer is not necessarily limited to the following structure.

[Formula 2-3]

In Formula 2-3,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group, *-SiR ⁵ R ⁶ -* (where R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C10 alkyl group) or a combination thereof;

L ³ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group;

n3 is an integer from 1 to 20;

For example, the anhydride monomer may include monomers represented by Chemical Formula 3-1 and Chemical Formula 3-2, but is not necessarily limited thereto, and for example, represented by Chemical Formula 3-3 or Chemical Formula 3-4 may be

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

The weight average molecular weight (M _w ) of the alkali-soluble resin may be preferably 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.

(B) photosensitive diazoquinone compound

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

Representative examples of the photosensitive diazoquinone compound include compounds represented by the following Chemical Formula 71 and Chemical Formulas 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 formula 72a, or a functional group represented by the following formula 72b, 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 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 Chemical 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 from 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 OQs, and the other aromatic ring may contain 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 above.

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

(C) Solvent

The photosensitive resin composition may include a solvent capable of easily dissolving components such as the alkali-soluble resin, the photosensitive diazoquinone compound, and other additives to be described later.

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

The solvent may be appropriately selected and used according to 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 100 parts by weight to 500 parts by weight, for example, 100 parts by weight to 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the content of the solvent is within the above range, a film having a sufficient thickness may be coated, and solubility and coating properties may be excellent.

(D) other additives

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

The photosensitive resin composition is diacid (eg, malonic acid, etc.), 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 latent heat acid generator, a development regulator, a curing agent, or additives of combinations thereof. The amount of these additives used 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, or an epoxy group in order to improve adhesion to a substrate.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycyl 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 part by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane-based coupling agent is included within the above range, adhesion, storability, and the like may be excellent.

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

As the fluorine-based surfactant, BM Chemie's BM-1000 ^® , BM-1100 ^® , etc.; Mecha Pack F 142D ^® , F 172 ^® , F 173 ® , F 183 ^{® ,} F 554 ^® , etc. of Dainippon Ink Kagaku Kogyo Co., Ltd.; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^® , etc. of Sumitomo SMT Co., Ltd.; Saffron S-112 ^® , S-113 ^® , S-131 ® , S-141 ^® , S-145 ^® and the like of Asahi ^Grass Co., Ltd.; Toray Silicone Co., Ltd.'s SH-28PA ^® , Copper-190 ^® , Copper-193 ^® , SZ-6032 ^® , SF-8428 ^® , etc. can be used.

The silicone surfactants include BYK Chem's BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, Those commercially available 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 may be secured, stains may 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 novolak epoxy resin, a tetramethyl biphenyl epoxy resin, a bisphenol A type epoxy resin, an alicyclic epoxy resin, or a combination thereof may be used. can

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

The epoxy compound may be used in an amount of 0.01 part 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, storage stability, adhesion and other properties may be improved.

In addition, the photosensitive resin composition may further include a thermal latent acid generator. Examples of the heat latent acid generator include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid; perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid, trifluorobutanesulfonic acid and the like; alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid and the like; or a combination thereof, but is not limited thereto.

The latent heat acid generator is a catalyst for dehydration and cyclization of polyamide containing a phenolic hydroxyl group of a polybenzoxazole precursor, and can smoothly proceed with cyclization 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 (insulating film) prepared by exposing, developing, and curing the photosensitive resin composition described above.

The photosensitive resin film (insulating film) manufacturing method is as follows.

(1) coating 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, or the like, on a substrate such as a glass substrate or an ITO substrate subjected to a predetermined pretreatment, A coating film is formed by removing the solvent by heating at a temperature of °C to 150 °C for 1 minute to 10 minutes.

(2) exposure step

After passing through a mask for pattern formation necessary for the photosensitive resin film obtained above, 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, X-rays, electron beams, etc. may be used.

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

(3) Development stage

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

(4) post-processing step

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

Another embodiment provides a display device including the photosensitive resin film (insulating film).

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

(Example)

(Synthesis of alkali-soluble resin)

Preparation Examples 1 to 6 and Comparative Preparation Example 1

The anhydride monomer was dissolved in N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injection device, and a condenser. When the solid was completely dissolved, diamine monomer was added and stirred at room temperature for 2 hours. Thereafter, the temperature was raised to 90 °C, and pyridine and Ac ₂ O were added and stirred for 3 hours. Thereafter, the temperature in the reactor was cooled to room temperature, water was added to the reaction mixture to form a precipitate, the precipitate was filtered, sufficiently washed with water, and dried at a reduced pressure of 50 ° C. for 24 hours or more to prepare an alkali-soluble resin. Types and weight ratios of monomers used in the synthesis of alkali-soluble resins are shown in Table 1 below.

Anhydride monomer (weight ratio) Diamine monomer (weight ratio) Preparation Example 1
(80)
(20)
(40)
(40)
(20) Preparation Example 2 Same as Preparation Example 1
(30)
(40)
(30) Preparation Example 3 Same as Preparation Example 1 (20)
(40)
(40) Production Example 4 Same as Preparation Example 1 (40)
(40)
(20) Preparation Example 5 Same as Preparation Example 1 (30)
(40)
(30) Preparation Example 6 Same as Preparation Example 1 (20)
(40)
(40) Comparative Preparation Example 1 Same as Preparation Example 1 (60)
(40) -

(Preparation of photosensitive resin composition)

Examples 1 to 6 and Comparative Example 1

4.5 g of 4-NQD (photosensitive diazoquinone compound), 3.0 g of TPPA (development control agent), KBM-573 (silane couple Ring agent) 0.6 g, BYK-378 (leveling agent) 0.01 g, Triglycidyl Isocyanurate (curing agent) 3.0 g, and GBL (solvent) 53 g were added and dissolved, and then filtered through a 0.45 μm polypropylene resin filter to obtain a photosensitive composition.

(Evaluation 1: Adhesion evaluation)

The photosensitive resin composition according to Examples 1 to 16 and Comparative Example 1 was coated on a Cu wafer to a thickness of 10 μm, and heated on a hot plate at 120° C. for 4 minutes to form a photosensitive resin film. The photosensitive resin film was cured at 220° C. for 120 minutes under nitrogen conditions.

Adhesion was measured using a die shear tester (DAGE series 4000PXY, manufactured by DAGE) by performing EMC molding on the cured film, and the results are shown in Table 2 below.

Die shear test (kgf) Example 1 25 Example 2 28 Example 3 29 Example 4 26 Example 5 27 Example 6 28 Comparative Example 1 13

(Evaluation 2: mechanical properties of membrane)

The photosensitive resin composition according to Examples 1 to 6 and Comparative Example 1 was spin-coated on an Al wafer, patterned to a pattern size of 10 X 120 mm, and then heat-treated in a furnace oven at 220° C. for 120 minutes under a nitrogen stream. to form a film having a thickness of 10 μm, and then peeled off by dipping in 9% hydrochloric acid aqueous solution. After drying the peeled film at 100 ° C. for about 30 minutes to remove water, the elongation at break was measured using UTM analysis based on ASTM-D882, and the results are shown in Table 3 below.

7 ㎛ hole E _op (mJ/cm ² ) Elongation (%) Example 1 540 70 Example 2 530 80 Example 3 520 80 Example 4 570 65 Example 5 540 65 Example 6 530 70 Comparative Example 1 650 60

Through Tables 1 and 2, the photosensitive resin composition according to one embodiment includes the structural unit-containing alkali-soluble resin represented by Chemical Formula 1, thereby improving adhesion to the metal layer, and also exhibiting very high film properties. excellence can be ascertained.

The present invention is not limited to the above embodiments, but can be manufactured in a variety of different forms, and those skilled in the art to which the present invention pertains may 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, the embodiments described above should be understood as illustrative in all respects and not limiting.

Claims (11)

(A) an alkali-soluble resin containing a structural unit represented by Formula 1 below;
(B) a photosensitive diazoquinone compound; and
(C) Solvent
A photosensitive resin composition comprising:
[Formula 1]

In Formula 1,
R ¹ and R ² are each independently an organic group including a substituted or unsubstituted C3 to C20 aliphatic ring group, a substituted or unsubstituted C6 to C20 aromatic ring group, or a combination thereof, provided that R ² is *-S -* and at least one selected from the group consisting of structural unit-containing linking groups represented by the following formula L,
[Formula L]

In the above formula L,
L ¹ is a substituted or unsubstituted C1 to C20 alkylene group, *-SiR ⁵ R ⁶ -* (where R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C10 alkyl group), or a combination thereof.
According to claim 1,
The alkali-soluble resin containing the structural unit represented by Formula 1 is a polymer between an anhydride monomer and a diamine monomer photosensitive resin composition.
According to claim 2,
Based on the total amount of monomers constituting the structural unit-containing alkali-soluble resin represented by Formula 1, the total weight of the anhydride monomer and the total weight of the diamine monomer are equal to each other photosensitive resin composition.
According to claim 2,
The diamine monomer includes a phenol-type diamine monomer and a sulfide-type diamine monomer,
Based on the total amount of monomers constituting the structural unit-containing alkali-soluble resin represented by Formula 1, the phenol-type diamine monomer and the sulfide-type diamine monomer are included in a weight ratio of 2: 1 to 2: 2 photosensitive resin composition.
According to claim 4,
The photosensitive resin composition wherein the phenol-type diamine monomer is represented by the following Chemical Formula 2-1, and the sulfide-type diamine monomer is represented by the following Chemical Formula 2-2:
[Formula 2-1]

[Formula 2-2]

In Formula 2-2,
R ³ and R ⁴ are each independently a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group;
n1 and n2 are each independently an integer of 0 to 4.
According to claim 4,
The photosensitive resin composition wherein the diamine monomer further comprises a diamine monomer represented by Chemical Formula 2-3:
[Formula 2-3]

In Chemical Formula 2-3,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group, *-SiR ⁵ R ⁶ -* (where R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C10 alkyl group) or a combination thereof;
L ³ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group;
n3 is an integer from 1 to 20;
According to claim 2,
The anhydride monomer is a photosensitive resin composition comprising monomers represented by the following Chemical Formulas 3-1 and 3-2.
[Formula 3-1]

[Formula 3-2]

According to claim 1,
The photosensitive resin composition,
About 100 parts by weight of the alkali-soluble resin
1 to 50 parts by weight of the photosensitive diazoquinone compound,
A photosensitive resin composition comprising 100 parts by weight to 500 parts by weight of the solvent.
According to claim 1,
The photosensitive resin composition further comprises an additive of a diacid, an alkanolamine, a leveling agent, a silane coupling agent, a surfactant, an epoxy compound, a radical polymerization initiator, a latent acid generator, or a combination thereof.
A photosensitive resin film prepared using the photosensitive resin composition according to any one of claims 1 to 9.
A display device comprising the photosensitive resin film of claim 10 .