KR20220011057A - Photosensitive resin composition, photosensitive resin layer and electronic device using the same - Google Patents

Abstract

Provided are a photosensitive resin composition comprising a polyamic acid resin containing a structural unit represented by following chemical formula 1, a photosensitive resin film prepared using the same, and an electronic device comprising the photosensitive resin film. In chemical formula 1, each substituent is the same as defined in the specification. The photosensitive resin composition according to one embodiment has high elongation even after low-temperature curing (220℃ or less) by comprising the polyamic acid resin containing a specific structural unit, and thus has excellent reliability in a package.

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.

BACKGROUND ART Conventionally, polyimide resins having excellent heat resistance, electrical properties, and mechanical properties have been used for insulating materials for electronic parts and for passivation films, surface protective films, interlayer insulating films, and the like of semiconductor devices. Among these polyimide resins, when the photosensitive polyimide precursor is provided in the form of a composition, heat due to curing after application, exposure and development of the composition is imidized to easily form a heat-resistant relief pattern film. Such a photosensitive polyimide precursor composition has the characteristic of enabling a significant process shortening compared with the conventional non-photosensitive type polyimide material.

On the other hand, a semiconductor device (hereinafter, also referred to as an "element") is mounted on a printed circuit board by various methods according to the purpose. In a conventional device, it was generally manufactured by a wire bonding method in which a thin wire was connected from the external terminal (pad) of the device to the lead frame. However, these days, as the speed of the device progresses and the operating frequency reaches GHz, the difference in the wiring length of each terminal during mounting has reached a level that affects the operation of the device. For this reason, it is necessary to precisely control the length of the mounting wiring in the mounting of high-end devices.

However, it has been difficult to satisfy recent demands by the conventional wire bonding method.

Therefore, flip chip mounting has been proposed in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is turned over (flips) and mounted directly on a printed circuit board. In this flip-chip mounting, the wiring distance can be precisely controlled. For this reason, flip-chip mounting is adopted for devices for high-end applications that handle high-speed signals, or for mobile phones because of their small size, and the demand is rapidly expanding. When a polyimide material is used for flip chip mounting, a metal wiring layer forming process is performed after the pattern of the polyimide layer is formed. The metal wiring layer is usually formed as follows. First, after plasma etching the surface of the polyimide layer to roughen the surface, a metal layer serving as a seed layer for plating is formed by sputtering to a thickness of 1 µm or less. Then, a metal wiring layer is formed by electroplating using this metal layer as an electrode. In this case, Ti is generally used as the metal serving as the seed layer, and Cu is used as the metal of the redistribution layer formed by electroplating.

One embodiment is to provide a photosensitive resin composition which is excellent in the film remaining rate and the stress characteristics at the same time, and has excellent elongation even after low-temperature curing (220° C. or less).

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 provides a photosensitive resin composition comprising a polyamic acid resin containing a structural unit represented by the following formula (1).

[Formula 1]

In Formula 1,

X ¹ is represented by the following formula 1-1,

[Formula 1-1]

In Formula 1-1,

L ¹ is an ether group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof;

Y ¹ is a divalent residue derived from a diamine compound,

R ¹ and R ² are each independently represented by the following formula 1-2,

[Formula 1-2]

In Formula 1-2,

L ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or these is a combination of

R ³ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

The Chemical Formula 1-1 may be represented by the following Chemical Formula 1-1-1.

[Formula 1-1-1]

In Formula 1-1-1,

L ³ to L ⁵ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group.

Formula 1-1-1 may be represented by Formula 1-1-1A, Formula 1-1-1B, or Formula 1-1-1C.

[Formula 1-1-1A]

[Formula 1-1-1B]

[Formula 1-1-1C]

In the formula 1-1-1A,

R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

Y ¹ may be represented by the following Chemical Formula 2-1.

[Formula 2-1]

In Formula 2-1,

L ⁶ to L ⁸ are each independently an ether group or a substituted or unsubstituted C6 to C20 arylene group.

The polyamic acid resin may have a weight average molecular weight of 15,000 g/mol to 30,000 g/mol.

The photosensitive resin composition may further include a radical polymerization initiator and a solvent.

The photosensitive resin composition may include 1 to 50 parts by weight of the radical polymerization initiator based on 100 parts by weight of the polyamic acid resin, and 100 to 800 parts by weight of the solvent.

The photosensitive resin composition may further include an additive of a diacid, an alkanolamine, a leveling agent, a fluorine-based surfactant, a photosensitive diazoquinone compound, 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.

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

The photosensitive resin composition according to an embodiment has high elongation even after low-temperature curing (220° C. or less) by including the polyamic acid resin containing a specific structural unit, and thus has excellent reliability in the package.

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, "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 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 amino group, an imino group, an azi Togi, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, mercapto 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 structural unit-containing polyamic acid resin represented by Formula 1 below.

[Formula 1]

In Formula 1,

X ¹ is represented by the following formula 1-1,

[Formula 1-1]

In Formula 1-1,

L ¹ is an ether group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof;

Y ¹ is a divalent residue derived from a diamine compound,

R ¹ and R ² are each independently represented by the following formula 1-2,

[Formula 1-2]

In Formula 1-2,

L ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or these is a combination of

R ³ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

Hereinafter, each component will be described in detail.

(A) polyamic acid resin

Since the polyamic acid resin includes the structural unit represented by Formula 1, it is possible to provide a photosensitive resin composition capable of improving the elongation of the coated surface after curing at room temperature and low temperature.

In Formula 1, X ¹ is a residue derived from a long dianhydride structure, and is represented by Formula 1-1. Specifically, in Formula 1-1, L ¹ is a combination of an ether linking group (*-O-*) and an arylene group (substituted or unsubstituted C6 to C20 aryl group), or an ether linking group (*-O-*) and an alkylene group (substituted or unsubstituted C1 to C20 alkyl group), or an ether linkage group (*-O-*), an arylene group (substituted or unsubstituted C6 to C20 aryl group) and an alkylene group (substituted or unsubstituted) C1 to C20 alkyl groups), and when L ¹ has the structure as described above, as the length increases, a very flexible chain unit is formed, and a cured film with high elongation after low temperature curing can be provided. have. Furthermore, in Formula 1, ^{the functional groups represented by R 1} and R ² include a (meth)acrylate group at the terminal, so that crosslinking performance is improved, thereby further multiplying the above-described effect.

For example, Chemical Formula 1-1 may be represented by the following Chemical Formula 1-1-1.

[Formula 1-1-1]

In Formula 1-1-1,

L ³ to L ⁵ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, provided that L ³ to L ⁵ are not a single bond at the same time.

Since Formula 1-1-1 has a specific structure and has a long length, the flexibility of the polyamic acid resin can be greatly improved, which ultimately leads to the coating surface (cured film) when the photosensitive resin composition is coated and cured. By greatly improving the elongation of the package, reliability in the package can be improved. And whether the reliability in the package is improved can be confirmed through the elongation after curing at a low temperature. The photosensitive resin composition according to an embodiment provides a cured film with high elongation after curing at a low temperature.

For example, Formula 1-1-1 may be represented by Formula 1-1-1A, Formula 1-1-1B, or Formula 1-1-1C, but is not limited thereto.

[Formula 1-1-1A]

[Formula 1-1-1B]

[Formula 1-1-1C]

In the formula 1-1-1A,

R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

For example, in Formula 1, X ¹ is 4,4′′anhydride), 5,5′-((1,1′-Biphenyl)-4,4′-diylbis(oxy))bis-1,3-isobenzofurandione or It may be a residue derived from 1,4-Bis(3,4-dicarboxyphenoxy)benzene dianhydride.

For example, Formula 1-1-1A may be represented by Formula 1-1-1A-1, Formula 1-1-1B may be represented by Formula 1-1-1B-1, and Formula 1-1-1B-1 1-1-1C may be represented by the following formula 1-1-1C-1.

[Formula 1-1-1A-1]

[Formula 1-1-1B-1]

[Formula 1-1-1C-1]

For example, when L ¹ is an ether group in Formula 1-1, Formula 1-1 may be represented by Formula 1-1-2.

[Formula 1-1-2]

For example, Y ¹ is a residue derived from a diamine compound having a specific structure, and may be specifically represented by the following Chemical Formula 2-1.

[Formula 2-1]

In Formula 2-1,

L ⁶ to L ⁸ are each independently an ether group or a substituted or unsubstituted C6 to C20 arylene group.

As Y ¹ is represented by Chemical Formula 2-1, the cured film of the photosensitive resin composition according to the exemplary embodiment may have a high elongation even after low-temperature curing without deterioration of the residual film rate characteristic.

For example, in Formula 2-1, L ⁶ and L ⁸ are each independently an ether group, and L ⁷ may be a substituted or unsubstituted C6 to C20 arylene group.

For example, in Formula 1, Y ¹ may be a residue derived from 1,3-Bis(4-aminophenoxy)benzene.

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

[Formula 2-1-1]

In Formula 1, when Y ¹ is a residue of the structure derived from a diamine compound, it may have a high elongation after curing at a low temperature, thereby improving reliability in the package.

The polyamic acid resin may have a weight average molecular weight (Mw) of 15,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the polyamic acid resin is within the above range, the elongation after curing at a low temperature is excellent, so that the reliability in the package is excellent and the pattern characteristics such as no residue generation can also be excellent.

(B) radical polymerization initiator

The photosensitive resin composition according to an embodiment may include a radical polymerization initiator. As the radical polymerization initiator, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound may be used.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt -Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino propane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc. are mentioned.

Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diiso A propyl thioxanthone etc. are mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine; 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho1-yl)-4,6 -Bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloro and romethyl)-6-piperonyl-s-triazine and 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

Examples of the oxime-based compound include O-acyloxime-based compound, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime) -1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. can be used Specific examples of the O-acyloxime compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane -1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2- Dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime -O-acetate　 etc. can be used.

As the radical polymerization initiator, a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a biimidazole-based compound, or a fluorene-based compound may be used in addition to the above compound.

The radical polymerization initiator may be included in an amount of 1 to 10 parts by weight, for example, 1 to 7 parts by weight, based on 100 parts by weight of the polyamic acid resin. When the photopolymerization initiator is included within the above range, photopolymerization occurs sufficiently, so that the sensitivity is excellent and the transmittance is improved.

(C) solvent

The photosensitive resin composition may further include a solvent capable of easily dissolving each component, such as the polyamic acid resin and the radical polymerization initiator.

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

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

The solvent is preferably used in an amount of 100 parts by weight to 800 parts by weight, for example, 100 parts by weight to 500 parts by weight, based on 100 parts by weight of the polyamic acid 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.

(D) other additives

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

The photosensitive resin composition is a diacid such as malonic acid and an alkanolamine such as 3-amino-1,2-propanediol in order to prevent stains or spots during coating, leveling characteristics, or generation of residues due to undeveloped properties. , a leveling agent, a silane-based coupling agent, a surfactant, an epoxy compound, a radical polymerization initiator, a thermal latent acid generator, or a combination thereof. The amount of these additives used can be easily adjusted according to desired physical properties.

For example, the silane-based coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, and an epoxy group in order to improve adhesion to the substrate.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γisocyanatepropyltriethoxysilane, γglycidoxypropyl and trimethoxysilane and β-epoxycyclohexyl)ethyl trimethoxysilane, and these may be used alone or in combination of two or more.

The silane-based 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.

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

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 coat method, a roll coat method, a screen printing method, and an applicator method on a substrate such as a glass substrate or an ITO substrate subjected to a predetermined pretreatment, 70 A coating film is formed by heating at ℃ to 150 ℃ for 1 minute to 10 minutes to remove the solvent.

(2) exposure step

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

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

(3) development step

As a developing method, after the exposure step, by dissolving and removing the unexposed part using an organic developer, only the exposed part 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 for 2 hours in a furnace at 220° C. under _{N 2 conditions.}

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.

(Manufacture of polyamic acid resin)

Synthesis Example 1

226.5 g of 4,4''anhydride) (BPADA) was placed in a separable flask with a capacity of 2 liters, and 114.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 70.9 g of pyridine while stirring at room temperature. After completion of the exothermic reaction by the reaction, it was allowed to cool to room temperature and was allowed to stand still for an additional 16 hours. Next, under ice cooling, a solution obtained by dissolving 179.5 g of dicyclohexylcarbodiimide (DCC) in 150 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension of 118.13 g of 1,3-Bis(4-aminophenoxy)benzene in 440 ml of γ-butyrolactone was added over 30 minutes while stirring. Further, after stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added, followed by stirring for 1 hour. After that, 400 ml of γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 liters of ethyl alcohol to produce a polymer precipitate. The resulting polymer was collected by filtration and dissolved in 1.5 liters of γ-butyrolactone to obtain a polymer solution. Polymer (polyamic acid resin) was obtained by dripping the obtained polymer solution into 14 liters of water, making a polymer precipitate, and vacuum-drying after filtering and collecting the obtained deposit. The weight average molecular weight (M _w ) was measured to be 20,000 g/mol.

Synthesis Example 2

Synthesis Example 1 and Synthesis Example 1 except that 5,5'-((1,1'-Biphenyl)-4,4'-diylbis(oxy))bis-1,3-isobenzofurandione was used instead of 4,4′′anhydride) In the same manner, a polyamic acid resin having a weight average molecular weight of 23,500 g/mol was obtained.

Synthesis Example 3

A polyamic acid resin having a weight average molecular weight of 15,000 g/mol was obtained in the same manner as in Synthesis Example 1, except that 1,4-Bis(3,4-dicarboxyphenoxy)benzene dianhydride was used instead of 4,4′′anhydride). .

Synthesis Example 4

A polyamic acid resin having a weight average molecular weight of 21,000 g/mol was obtained in the same manner as in Synthesis Example 1, except that 4,4'anhydride was used instead of 4,4''anhydride).

Synthesis Example 5

Polyamic acid having a weight average molecular weight of 25,500 g/mol in the same manner as in Synthesis Example 1, except that the compound represented by the following formula N-1 (Merck) was used instead of 1,3-Bis(4-aminophenoxy)benzene resin was obtained.

[Formula N-1]

Synthesis Example 6

Except that 4,4'anhydride was used instead of 4,4'anhydride), proceed in the same manner as in Synthesis Example 1, except that the content of 1,3-Bis(4-aminophenoxy)benzene was lowered, and the weight average molecular weight was 13,500 g/ mol of polyamic acid resin was obtained.

Synthesis Example 7

Except that 4,4'anhydride was used instead of 4,4'anhydride), proceed in the same manner as in Synthesis Example 1, except that the content of 1,3-Bis(4-aminophenoxy)benzene was increased, and stirred at room temperature for 4 hours. A polyamic acid resin having a weight average molecular weight of 32,000 g/mol was obtained.

Comparative Synthesis Example 1

4,4′′anhydride), except that Benzene-1,2,4,5-tetracarboxylic dianhydride was used, and in the same manner as in Synthesis Example 1, a polyamic acid resin having a weight average molecular weight of 12,000 g/mol was obtained.

Comparative Synthesis Example 2

In the same manner as in Synthesis Example 1, except that 1,4-Phenylene Bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) was used instead of 4,4′-(4,4′anhydride) , a polyamic acid resin having a weight average molecular weight of 20,000 g/mol was obtained.

(Preparation of photosensitive resin composition)

Example 1

100 g of the polyamic acid resin of Synthesis Example 1 was added to and dissolved in a solvent of 300 g of γ-gamma)-butyrolactone (GBL), then 20 g of a polymerization initiator OXE-01 (BASF) was added and dissolved, and a homogeneous solution was obtained under a yellow light. stirred until Thereafter, it was filtered through a 0.2 µm fluororesin filter to obtain a photosensitive resin composition.

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the polyamic acid resin of Synthesis Example 2 was used instead of the polyamic acid resin of Synthesis Example 1.

Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the polyamic acid resin of Synthesis Example 3 was used instead of the polyamic acid resin of Synthesis Example 1.

Example 4

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the polyamic acid resin of Synthesis Example 4 was used instead of the polyamic acid resin of Synthesis Example 1.

Example 5

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the polyamic acid resin of Synthesis Example 5 was used instead of the polyamic acid resin of Synthesis Example 1.

Example 6

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the polyamic acid resin of Synthesis Example 6 was used instead of the polyamic acid resin of Synthesis Example 1.

Example 7

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the polyamic acid resin of Synthesis Example 7 was used instead of the polyamic acid resin of Synthesis Example 1.

Comparative Example 1

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the polyamic acid resin of Comparative Synthesis Example 1 was used instead of the polyamic acid resin of Synthesis Example 1.

Comparative Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the polyamic acid resin of Comparative Synthesis Example 2 was used instead of the polyamic acid resin of Synthesis Example 1.

evaluation

After coating the photosensitive resin compositions according to Examples 1 to 7 and Comparative Examples 1 and 2 on a wafer on which Cu is deposited, heating (curing) for 2 minutes at 220°C low temperature), a cured film having a thickness of 10 μm After the cured film is immersed in 10% hydrochloric acid (or 1% hydrofluoric acid) diluted in water for about 120 minutes, a coating film is obtained.

(Evaluation 1: Remaining film rate)

The difference in thickness before/after curing was calculated in %.

(Evaluation 2: room temperature/low temperature elongation)

The elongation of the coating film was measured with a UTM facility, and only the maximum value was obtained after measuring 10 samples.

- Temperature condition: 25℃-55℃

- Grip thickness: 50mm

- Cross head speed: 5mm/min

(Evaluation 3: Stress Characteristics)

A cured film was prepared by coating the photosensitive resin compositions according to Examples 1 to 7, Comparative Examples 1 and 2 to a thickness of 10 μm on an 8-inch wafer. Bare wafer stress and the stress difference of the 8-inch wafer coated with the composition were measured using FLX-2320S (TOHO tech.).

The results of the evaluation are shown in Table 1 below.

Remaining film rate (%) Elongation (%) after curing at room temperature Elongation after low temperature curing (%) Stress (MPa) Example 1 91.5 80 64 32 Example 2 91.0 84 66 20 Example 3 91.5 82 62 34 Example 4 91.0 80 60 35 Example 5 91.0 60 45 37 Example 6 91.0 60 40 31 Example 7 89.0 60 50 38 Comparative Example 1 91.0 35 15 60 Comparative Example 2 91.0 70 25 55

Through Table 1, the photosensitive resin composition according to an embodiment of the present invention includes a polyamic acid resin containing a specific structure, and thus higher elongation characteristics after low temperature curing than the photosensitive resin composition not including the polyamic acid resin. It can be seen that low stress characteristics can be achieved.

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 (10)

A photosensitive resin composition comprising a polyamic acid resin containing a structural unit represented by the following formula (1):
[Formula 1]

In Formula 1,
X ¹ is represented by the following formula 1-1,
[Formula 1-1]

In Formula 1-1,
L ¹ is an ether group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof;
Y ¹ is a divalent residue derived from a diamine compound,
R ¹ and R ² are each independently represented by the following formula 1-2,
[Formula 1-2]

In Formula 1-2,
L ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or these is a combination of
R ³ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.
According to claim 1,
The L ¹ is a photosensitive resin composition represented by the following Chemical Formula 1-1-1:
[Formula 1-1-1]

In Formula 1-1-1,
L ³ to L ⁵ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, provided that L ³ to L ⁵ are not a single bond at the same time.
3. The method of claim 2,
Formula 1-1-1 is a photosensitive resin composition represented by Formula 1-1-1A, Formula 1-1-1B, or Formula 1-1-1C:
[Formula 1-1-1A]

[Formula 1-1-1B]

[Formula 1-1-1C]

In the formula 1-1-1A,
R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
According to claim 1,
The Y ¹ is a photosensitive resin composition represented by the following Chemical Formula 2-1:
[Formula 2-1]

In Formula 2-1,
L ⁶ to L ⁸ are each independently an ether group or a substituted or unsubstituted C6 to C20 arylene group.
According to claim 1,
The polyamic acid resin is a photosensitive resin composition having a weight average molecular weight of 15000 g / mol to 30000 g / mol.
According to claim 1,
The photosensitive resin composition further comprises a radical polymerization initiator and a solvent.
7. The method of claim 6,
The photosensitive resin composition,
With respect to 100 parts by weight of the polyamic acid resin
1 part by weight to 50 parts by weight of the radical polymerization initiator,
A photosensitive resin composition comprising 100 parts by weight to 800 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 fluorine-based surfactant, a photosensitive diazoquinone compound, or a combination thereof.
A photosensitive resin film prepared by using the photosensitive resin composition of any one of claims 1 to 8.
An electronic device comprising the photosensitive resin film of claim 9 .