KR102477633B1 - Alkali soluble resin, photosensitive resin composition including the same, photosensitive resin layer and display device - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)An alkali-soluble resin having a structural unit represented by the following Chemical Formula 1 before heating, having no condensed rings at both ends, but having a cyclic urethane functional group at at least one of both ends after heating, a photosensitive resin composition comprising the same, A photosensitive resin film prepared using the photosensitive resin composition and a display device including the photosensitive resin film are provided.
[Formula 1]

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

Description

Alkali-soluble resin, photosensitive resin composition containing the same, photosensitive resin film, and display device

The present disclosure relates to an alkali-soluble resin, a photosensitive resin composition including the same, a photosensitive resin film using the photosensitive resin composition, and a display device including the photosensitive resin film.

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 an alkali-soluble resin having no condensed ring at both ends before heating, but having a cyclic urethane functional group at at least one of both ends after heating.

Another embodiment is to provide a photosensitive resin composition containing the alkali-soluble resin.

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

Another embodiment is to provide a display device including the photosensitive resin film.

One embodiment has a structural unit represented by Formula 1 before heating, and at the same time does not have a condensed ring at both ends, but after heating, at least one of the ends has an alkali-soluble structure represented by Formula 2 below. provide resin.

[Formula 1]

In Formula 1,

R ¹ to R ³ are each independently a hydrogen atom, a hydroxyl group, *-O(C=O)R'(R' is a C1 to C10 alkyl group, a C1 to C10 alkoxy group or a C6 to C20 aryl group), *-C ( =O)OR″ (R″ is a C1 to C10 alkyl group or a C6 to C20 aryl group), a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C6 to C20 aryl group,

n is an integer of 1 or 2;

L ¹ and L ² are each independently a substituted or unsubstituted C6 to C20 aromatic organic group.

[Formula 2]

In Formula 2,

A is a C3 to C20 cycloalkane ring or a C6 to C20 aromatic ring;

R ⁴ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

L ³ and L ⁴ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

The A may be a benzene ring.

The R ⁴ is a hydrogen atom, and the L ³ and L ⁴ may each independently form a single bond.

The structural unit represented by Chemical Formula 1 may be represented by Chemical Formula 1-1 or Chemical Formula 1-2 after heating.

[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,

R ³ is a hydrogen atom, a hydroxyl group, *-O(C=O)R'(R' is a C1 to C10 alkyl group, a C1 to C10 alkoxy group, or a C6 to C20 aryl group), *-C(=O)OR'' (R″ is a C1 to C10 alkyl group or a C6 to C20 aryl group), a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted Or an unsubstituted C6 to C20 aryl group,

L ¹ is a substituted or unsubstituted C6 to C20 arylene group;

L ² is an unsubstituted C6 to C20 arylene group, a C6 to C20 arylene group substituted with a C1 to C20 alkoxy group, or a C6 to C20 arylene group substituted with a C6 to C20 aryl group.

Another embodiment is (A) the alkali-soluble resin; (B) a photosensitive diazoquinone compound; And (C) it provides a photosensitive resin composition containing a solvent.

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 800 parts by weight of the solvent based on 100 parts by weight of the alkali-soluble resin.

The photosensitive resin composition may further include the compound represented by Chemical Formula 3.

[Formula 3]

In Formula 3,

R ⁵ is a divalent to tetravalent organic group having at least 2 or more carbon atoms;

R ⁶ to R ⁸ are each independently a substituted or unsubstituted C1 to C10 alkyl group;

p is an integer from 2 to 4;

R ⁵ may be represented by Formula 4-1 or Formula 4-2 below.

[Formula 4-1]

[Formula 4-2]

In Formula 4-1 and Formula 4-2,

L ⁶ is a hetero atom;

L ⁵ and L ⁷ are each independently a substituted or unsubstituted C6 to C20 arylene group.

In Formula 3, R ⁶ to R ⁸ may be the same as each other.

The photosensitive resin composition may include 1 to 50 parts by weight of the compound represented by Chemical Formula 3 based on 100 parts by weight of the alkali-soluble resin.

The photosensitive resin composition may further include an additive of an alcohol compound, a diacid, an alkanolamine, a leveling agent, a silane coupling agent, a surfactant, an epoxy compound, a radical polymerization initiator, 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.

Alkali-soluble resin according to one embodiment does not have a condensed ring at both ends before heating, but has a structure having a cyclic urethane functional group at at least one end after heating, so that the photosensitive resin composition containing the same has a high temperature It is possible to manufacture a cured film (photosensitive resin film) having high heat resistance and mechanical properties not only during curing but also during low-temperature curing, and excellent in chemical resistance.

1 is FT-IR data before heating of an alkali-soluble resin (Preparation Example 1) according to one embodiment.
Figure 2 is FT-IR data after heating (220 ℃) of the alkali-soluble resin (Preparation Example 1) according to one embodiment.

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 alkali-soluble resin according to one embodiment has a structural unit represented by Formula 1 before heating, and at the same time does not have a condensed ring at both ends, but after heating, at least one of both ends has a structure represented by Formula 2 below have

[Formula 1]

R ¹ to R ³ are each independently a hydrogen atom, a hydroxyl group, *-O(C=O)R'(R' is a C1 to C10 alkyl group, a C1 to C10 alkoxy group or a C6 to C20 aryl group), *-C ( =O)OR″ (R″ is a C1 to C10 alkyl group or a C6 to C20 aryl group), a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C6 to C20 aryl group,

n is an integer of 1 or 2;

L ¹ and L ² are each independently a substituted or unsubstituted C6 to C20 aromatic organic group;

[Formula 2]

In Formula 2,

A is a C3 to C20 cycloalkane ring or a C6 to C20 aromatic ring;

R ⁴ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;

L ³ and L ⁴ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

The A may be a benzene ring.

The R ⁴ is a hydrogen atom, and the L ³ and L ⁴ may each independently form a single bond.

Conventionally, a "polyimide" resin that has "excellent" heat resistance, "electrical" characteristics, and "mechanical" characteristics is "used" for the "surface" protective film or "interlayer" insulating film of a semiconductor element. However, there is a demand for "thinning" and "miniaturization" of "heavyweight" bags "resin" packages where "high integration" and "large size" of semiconductor devices are in progress, and recently, "polybenzoxazole precursors" with higher resolution than "polyimide resins" are mainly used.

Furthermore, more recently, materials that can be cured even at low temperatures have been demanded, such as devices that are vulnerable to high-temperature heating processes such as MRAM (Magnet Resistive RAM) and application to RDL (Redistribution Layer).

However, conventional polyimide resins or polybenzoxazole precursors form a ring-closing structure by heating, and when the heating temperature is not high temperature but low temperature, such as 250 ° C. or less, such as 220 ° C. or less, sufficient ring-closing reaction does not proceed, There is a problem that low-temperature curing does not work properly. Accordingly, attempts have been made to lower the ring-closing temperature by introducing a flexible structure into the resin or adding additives such as acid generators, but so far, compositions or alkali-soluble resins exhibiting satisfactory physical properties compared to high-temperature curing. is not being developed.

The alkali-soluble resin according to one embodiment has the structural unit represented by Formula 1 before heating and does not have a condensed ring at both ends, but has a cyclic urethane functional group at both ends after heating, such a structure Since curing occurs sufficiently at a low temperature, for example, 250° C. or lower, for example, 220° C. or lower, it can be used in a photosensitive resin composition that is very suitable for low-temperature curing as well as high-temperature curing. In addition, the alkali-soluble resin of the above structure may be suitable for a positive-type photosensitive resin composition rather than a negative-type photosensitive resin composition.

For example, the structural unit represented by Chemical Formula 1 may be represented by Chemical Formula 1-1 or Chemical Formula 1-2 after heating.

[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,

R ³ is a hydrogen atom, a hydroxyl group, *-O(C=O)R'(R' is a C1 to C10 alkyl group, a C1 to C10 alkoxy group, or a C6 to C20 aryl group), *-C(=O)OR'' (R″ is a C1 to C10 alkyl group or a C6 to C20 aryl group), a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted Or an unsubstituted C6 to C20 aryl group,

L ¹ is a substituted or unsubstituted C6 to C20 arylene group;

L ² is an unsubstituted C6 to C20 arylene group, a C6 to C20 arylene group substituted with a C1 to C20 alkoxy group, or a C6 to C20 arylene group substituted with a C6 to C20 aryl group.

For example, in Formula 1, L ² may be an unsubstituted C6 to C20 arylene group, a C6 to C20 arylene group substituted with a C1 to C20 alkoxy group, or a C6 to C20 arylene group substituted with a C6 to C20 aryl group.

The weight average molecular weight (M _w ) of the alkali-soluble resin according to one embodiment may be 3,000 g/mol to 50,000 g/mol, for example, 3,000 g/mol to 20,000 g/mol. When the weight average molecular weight is within the above range, sufficient physical properties can be obtained even at low temperature curing, and handling is easy due to excellent solubility in organic solvents.

Another embodiment provides a photosensitive resin composition including the alkali-soluble resin.

For example, the photosensitive resin composition may include a photosensitive diazoquinone compound and a solvent, and may further include a compound represented by Chemical Formula 3 below.

[Formula 3]

In Formula 3,

R ⁵ is a divalent to tetravalent organic group having at least 2 or more carbon atoms;

R ⁶ to R ⁸ are each independently a substituted or unsubstituted C1 to C10 alkyl group;

p is an integer from 2 to 4;

The compound represented by Chemical Formula 3 may further improve low-temperature curing characteristics of the photosensitive resin composition according to an embodiment.

For example, in Chemical Formula 3, R ⁵ may be represented by Chemical Formula 4-1 or Chemical Formula 4-2.

[Formula 4-1]

[Formula 4-2]

In Formula 4-1 and Formula 4-2,

L ⁶ is a hetero atom;

L ⁵ and L ⁷ are each independently a substituted or unsubstituted C6 to C20 arylene group.

For example, in Chemical Formula 3, R ⁶ to R ⁸ may be identical to each other.

For example, in Formula 4-1, L ⁵ and L ⁷ may each independently represent a substituted or unsubstituted phenylene group, and L ⁶ may be an ether group.

In addition, the photosensitive resin composition may further include an alcohol-based compound. The alcohol-based compound can improve mechanical properties and chemical resistance even at a low curing temperature by sealing the crosslinking and alkali-soluble groups of the resin in parallel with the ring-closing reaction of the alkali-soluble resin according to one embodiment.

More specifically, the alcohol-based compound may be, for example, benzyl alcohol or p-xylylene glycol, but is not necessarily limited thereto. The benzyl alcohol may improve sensitivity and resolution of the photosensitive resin composition according to an embodiment, and the p-xylylene glycol may further improve low-temperature curing characteristics of the photosensitive resin composition according to an embodiment.

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.

The compound represented by Formula 3 is preferably included in an amount of 1 part by weight to 50 parts by weight, for example, 1 part by weight to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the content of the compound represented by Chemical Formula 3 is within the above range, mechanical properties of the film may be improved by inducing crosslinking of the resin during low-temperature curing.

The photosensitive resin composition may contain a solvent capable of easily dissolving components such as the alkali-soluble resin, the photosensitive diazoquinone compound, the compound represented by Chemical Formula 3, the alcohol-based compound, and other additives described later. there is.

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 800 parts by weight, for example, 100 parts by weight to 500 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.

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 development control agent, 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, 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 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 Example 1

2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3, 67.6 g of 3,-hexafluoropropane (6FAP) was added, and 380 g of N-methyl-2-pyrrolidone (NMP) was added and dissolved. When the solid was completely dissolved, 40.7 g of pyridine was added, and a mixture of 32.0 g of isophthaloyl chloride (IPC) and 160 g of NMP was slowly added dropwise over 60 minutes while maintaining the temperature at 0 to 5 °C. After dropping, the reaction was carried out at 5°C for 2 hours. Here, 21.7 g of ethyl chloroformate (ECF) was added at 5° C. for 30 minutes, and the reaction was terminated by stirring at room temperature for 2 hours.

The reaction solution was subjected to "precipitation/purification" in "water" to obtain a polymer (U-1; Mw 6930 g/mol) in which 40% of "terminal" and "side chain" OH was encapsulated.

Preparation Example 2

2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3, 67.3 g of 3,-hexafluoropropane (6FAP) was added, and 380 g of N-methyl-2-pyrrolidone (NMP) was added and dissolved. When the solid was completely dissolved, 34.9 g of pyridine was added, and a mixture of 33.2 g of isophthaloyl chloride (IPC) and 160 g of NMP was slowly added dropwise over 60 minutes while maintaining the temperature at 0 to 5 °C. After dropping, the reaction was carried out at 5°C for 2 hours. Here, 12.4 g of ethyl chloroformate (ECF) was added at 5° C. for 30 minutes, and the reaction was terminated by stirring at room temperature for 2 hours.

The reaction solution was subjected to "precipitation/purification" in water to obtain a polymer (U-2; Mw 9520 g/mol) in which 20% of "terminal" and "side chain" OH was encapsulated.

Preparation Example 3

2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3, 67.3 g of 3,-hexafluoropropane (6FAP) was added, and 380 g of N-methyl-2-pyrrolidone (NMP) was added and dissolved. When the solid was completely dissolved, 34.91 g of pyridine was added, and a mixture of 33.2 g of isophthaloyl chloride (IPC) and 160 g of NMP was slowly added dropwise over 60 minutes while maintaining the temperature at 0 to 5 °C. After dropping, the reaction was carried out at 5°C for 2 hours. Here, 15.83 g of methyl chloroformate (MECF) was added at 5° C. for 30 minutes, and the reaction was terminated by stirring at room temperature for 2 hours.

The reaction solution was precipitated/purified in water to obtain a polymer (U-3; Mw 9520 g/mol) in which 20% of terminals and side chains were sealed with OH.

Production Example 4

2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3, 67.3 g of 3,-hexafluoropropane (6FAP) was added, and 380 g of N-methyl-2-pyrrolidone (NMP) was added and dissolved. When the solid is completely dissolved, 29.07 g of pyridine is added, and 16.6 g of isophthaloyl chloride (IPC), 24.13 g of 4,4'-oxybisbenzoyl chloride (ODBC), and 160 g of NMP are added while maintaining the temperature at 0 to 5 ° C. The mixed solution was slowly dripped over 60 minutes. After dropping, the reaction was carried out at 5°C for 2 hours. Here, 5.6 g of methyl chloroformate (MECF) was added at 5° C. for 30 minutes, and the reaction was terminated by stirring at room temperature for 2 hours.

The reaction solution was precipitated/purified in water to obtain a polymer (U-4; Mw 8500 g/mol) in which 20% of terminals and side chains were sealed with OH.

Preparation Example 5

2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3, 67.3 g of 3,-hexafluoropropane (6FAP) was added, and 380 g of N-methyl-2-pyrrolidone (NMP) was added and dissolved. When the solid was completely dissolved, 29.07 g of pyridine was added, and a mixture of 47.45 g of 4,4'-oxybisbenzoyl chloride (ODBC) and 400 g of NMP was slowly added dropwise over 60 minutes while maintaining the temperature at 0 to 5 °C. After dropping, the reaction was carried out at 5°C for 2 hours. 4.99 g of ethyl chloroformate (ECF) was added thereto at 5° C. for 30 minutes, and the reaction was terminated by stirring at room temperature for 2 hours.

The reaction solution was subjected to "precipitation/purification" in "water" to obtain a polymer (U-5; Mw 11000 g/mol) in which 0% of "terminal" and "side chain" OH was encapsulated.

Comparative Preparation Example 1

2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3, 67.3 g of 3,-hexafluoropropane (6FAP) was added, and 380 g of N-methyl-2-pyrrolidone (NMP) was added and dissolved. When the solid was completely dissolved, 25.44 g of pyridine was added, and a mixture of 47.45 g of 4,4'-oxybisbenzoyl chloride (ODBC) and 400 g of NMP was slowly added dropwise over 60 minutes while maintaining the temperature at 0 to 5 °C. After dropping, the reaction was carried out at 5°C for 2 hours. Here, 7.50 g of norbornanediamine (NBDA) was added at 5° C. for 30 minutes, and the reaction was terminated by stirring at room temperature for 2 hours to obtain a polymer (R-1; Mw 11600 g/mol).

Comparative Preparation Example 2

2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3, 67.3 g of 3,-hexafluoropropane (6FAP) was added, and 380 g of N-methyl-2-pyrrolidone (NMP) was added and dissolved. When the solid was completely dissolved, 26.83 g of pyridine was added, and a mixture of 34.44 g of isophthaloyl chloride (IPC) and 86.09 g of NMP was slowly added dropwise over 60 minutes while maintaining the temperature at 0 to 5 °C. After dropping, the reaction was carried out at 5°C for 2 hours. Here, 4.64 g of norbornanediamine (NBDA) was added at 5° C. for 30 minutes and stirred at room temperature for 2 hours to complete the reaction, thereby obtaining a polymer (R-2; Mw 13000 g/mol).

Evaluation 1: Confirmation of cyclic urethane structure after heating

In order to confirm structural changes before and after heating of each of the prepared alkali-soluble resins (Preparation Examples 1 to 5, Comparative Preparation Example 1 and Comparative Preparation Example 2), FT-IR before and after heating was confirmed. As a result, all of the alkali-soluble resins according to Preparation Examples 1 to 5, Comparative Preparation Example 1 and Comparative Preparation Example 2 were found to have an absorption peak derived from carbonate at 1770 cm ^-1 before heating, and after heat treatment at 220 ° C. It was confirmed that the absorption peak was shifted to 1755 cm ^-1 only in the alkali-soluble resins according to Examples 1 to 5. From this, it can be inferred that the alkali-soluble resins according to Preparation Examples 1 to 5 have cyclic urethane structures formed at both ends after curing at a low temperature of 220 °C. (See Figures 1 and 2)

(Preparation of photosensitive resin composition)

Example 1

To 10 g of the alkali-soluble resin according to Preparation Example 1, 1.5 g of a photosensitive diazoquinone compound having a structure of Formula A and 0.8 g of a compound having a structure of Formula B were added, stirred at room temperature for 3 hours, and then 0.45 μm of poly It filtered with a propylene resin filter to obtain a positive photosensitive resin composition.

[Formula A]

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

, and the other is a hydrogen atom.)

[Formula B]

Example 2

It was the same as Example 1 except that the alkali-soluble resin according to Preparation Example 2 was used instead of the alkali-soluble resin according to Preparation Example 1.

Example 3

It was the same as in Example 1 except that the alkali-soluble resin according to Preparation Example 3 was used instead of the alkali-soluble resin according to Preparation Example 1 and benzyl alcohol was additionally used.

Example 4

Except for using the alkali-soluble resin according to Preparation Example 4 instead of the alkali-soluble resin according to Preparation Example 1, Example 3 was the same.

Example 5

It was the same as in Example 3 except that the alkali-soluble resin according to Preparation Example 5 was used instead of the alkali-soluble resin according to Preparation Example 1 and p-xylylene glycol was additionally used.

Comparative Example 1

The alkali-soluble resin according to Comparative Preparation Example 1 was used instead of the alkali-soluble resin according to Preparation Example 1, and the same as in Example 1 was performed except that the compound represented by Formula B was not used.

Comparative Example 2

Except for using the alkali-soluble resin according to Comparative Preparation Example 1 instead of the alkali-soluble resin according to Preparation Example 5, it was the same as in Example 5.

Comparative Example 3

It was the same as Comparative Example 2 except that the alkali-soluble resin according to Comparative Preparation Example 2 was used instead of the alkali-soluble resin according to Comparative Preparation Example 1.

(Evaluation 2: Sensitivity and resolution evaluation)

The photosensitive resin composition according to Examples 1 to 5 and Comparative Examples 1 to 3 was coated on a silicon wafer using a spin coater, and then heated on a hot plate at 130 ° C. for 2 minutes to form a 10 μm thick coating film. After exposure with an i-line exposure machine (UX-1200SM-AKS02, Ushio Co.) using a mask with a pattern engraved on the coating film, 2 puddles in 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution at room temperature for 50 seconds ( After dissolving and removing the exposed area through a puddle, it was washed with pure water for 30 seconds. Sensitivity and resolution were evaluated under the condition of "normally formed" pattern, and the results are shown in Table 1 below.

(Evaluation 3: Chemical resistance evaluation)

The photosensitive resin composition according to Examples 1 to 5 and Comparative Examples 1 to 3 was coated on a silicon wafer using a spin coater, and then heated on a hot plate at 130 ° C. for 2 minutes to form a 10 μm thick coating film. Thereafter, without exposure, the cured film was cured for 1 hour using an oven as it is under nitrogen conditions and temperature conditions (220° C. and 320° C.) respectively. The "appearance" and "thickness change" when the cured film was immersed in NMP at room temperature for 15 minutes were investigated, and the results are shown in Table 1 below.

Criteria for evaluating chemical resistance

O: thickness change is 1 μm or less

X: thickness change exceeds 1 μm

(Evaluation 4: elongation (mechanical property) evaluation)

The photosensitive resin composition according to Examples 1 to 5 and Comparative Examples 1 to 3 was coated on a silicon wafer using a spin coater, and then heated on a hot plate at 130 ° C. for 2 minutes to form a 10 μm thick coating film. Thereafter, exposure and development were performed using a photomask on which a 1 cm wide stripe pattern was engraved. After that, curing was performed for 1 hour under "nitrogen" conditions using "oven" at each "temperature" condition (220°C 320°C) to obtain a cured film. The cured film was peeled off from the silicon wafer, and the elongation was measured using UTM analysis in accordance with ASTM D-882-88 evaluation method. The results are shown in Table 1 below.

Development time (sec) Sensitivity (mJ/cm ² ) Resolution (μm) chemical resistance Elongation (%) 320℃ hardening 220℃ hardening 320℃ hardening 220℃ hardening Example 1 120 450 5 O O 40 36 Example 2 110 450 5 O O 42 38 Example 3 100 400 5 O O 42 36 Example 4 110 400 5 O O 40 37 Example 5 100 450 5 O O 44 38 Comparative Example 1 100 450 5 O X 52 8 Comparative Example 2 100 450 5 O X 49 12 Comparative Example 3 100 800 >10 O X 40 10

From Table 1, the photosensitive resin composition according to one embodiment has physical properties equivalent to or higher than those of conventional alkali-soluble resins in terms of sensitivity and resolution, and at the same time, high temperature (320 ° C.) curing properties as well as low temperature (220 ° C.) curing properties. It can be seen that the characteristics are also very good.

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 with Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting.

Claims (12)

Before heating, it has a structural unit represented by Formula 1, and at the same time does not have a condensed ring at both ends,
After heating, an alkali-soluble resin having a structure represented by Formula 2 below at least one of the both ends:
[Formula 1]

R ¹ to R ³ are each independently a hydrogen atom, a hydroxyl group, *-O(C=O)R'(R' is a C1 to C10 alkyl group, a C1 to C10 alkoxy group or a C6 to C20 aryl group), *-C ( =O)OR″ (R″ is a C1 to C10 alkyl group or a C6 to C20 aryl group), a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C6 to C20 aryl group,
n is an integer of 1 or 2;
L ¹ and L ² are each independently a substituted or unsubstituted C6 to C20 aromatic organic group;
[Formula 2]

In Formula 2,
A is a C3 to C20 cycloalkane ring or a C6 to C20 aromatic ring;
R ⁴ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group;
L ³ and L ⁴ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
According to claim 1,
The A is an alkali-soluble resin that is a benzene ring.
According to claim 1,
Wherein R ⁴ is a hydrogen atom, and L ³ and L ⁴ are each independently a single bond.
According to claim 1,
The structural unit represented by Formula 1 is an alkali-soluble resin represented by Formula 1-1 or Formula 1-2 below after heating:
[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,
R ³ is a hydrogen atom, a hydroxyl group, *-O(C=O)R'(R' is a C1 to C10 alkyl group, a C1 to C10 alkoxy group, or a C6 to C20 aryl group), *-C(=O)OR'' (R″ is a C1 to C10 alkyl group or a C6 to C20 aryl group), a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted Or an unsubstituted C6 to C20 aryl group,
L ¹ is a substituted or unsubstituted C6 to C20 arylene group;
L ² is an unsubstituted C6 to C20 arylene group, a C6 to C20 arylene group substituted with a C1 to C20 alkoxy group, or a C6 to C20 arylene group substituted with a C6 to C20 aryl group.
(A) the alkali-soluble resin of any one of claims 1 to 4;
(B) a photosensitive diazoquinone compound; and
(C) Solvent
Photosensitive resin composition comprising a.
According to claim 5,
The photosensitive resin composition,
Based on 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 800 parts by weight of the solvent.
According to claim 5,
The photosensitive resin composition further comprises a compound represented by Formula 3 below:
[Formula 3]

In Formula 3,
R ⁵ is a divalent to tetravalent organic group having at least 2 or more carbon atoms;
R ⁶ to R ⁸ are each independently a substituted or unsubstituted C1 to C10 alkyl group;
p is an integer from 2 to 4;
According to claim 7,
The photosensitive resin composition comprises 1 part by weight to 50 parts by weight of the compound represented by Formula 3 based on 100 parts by weight of the alkali-soluble resin.
According to claim 7,
R ⁵ is a photosensitive resin composition represented by Formula 4-1 or Formula 4-2:
[Formula 4-1]

[Formula 4-2]

In Formula 4-1 and Formula 4-2,
L ⁶ is a hetero atom;
L ⁵ and L ⁷ are each independently a substituted or unsubstituted C6 to C20 arylene group.
According to claim 5,
The photosensitive resin composition further comprises an additive of an alcohol compound, a diacid, an alkanolamine, a leveling agent, a silane coupling agent, a surfactant, an epoxy compound, a radical polymerization initiator, or a combination thereof.
A photosensitive resin film prepared using the photosensitive resin composition of claim 5.
A display device comprising the photosensitive resin film of claim 11 .

Images