KR102815446B1 - Photosensitive resin composition, photosensitive resin layer and electronic device using the same - Google Patents

Abstract

(A) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a solvent comprising a first solvent and a second solvent, wherein the first solvent is gamma-butyrolactone, the second solvent comprises a compound having a different structure from the first solvent, and the second solvent is contained in an amount of 3 to 10 parts by weight based on the total amount of the first solvent and the second solvent, wherein the second solvent comprises a moiety-containing compound represented by the following chemical formula 1 and/or a compound represented by the following chemical formula 2; a photosensitive resin composition manufactured using the same; and an electronic device comprising the photosensitive resin film are provided.
[Chemical Formula 1]

[Chemical formula 2]

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

Description

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

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

Polyimide resins and polybenzoxazole resins, which have excellent heat resistance, electrical properties, mechanical properties, etc., have been widely used as materials for display device panels and surface protective films and interlayer insulating films used in semiconductor devices. Since these resins have low solubility in various solvents, they are often provided as compositions dissolved in solvents in the form of precursors.

However, due to the recent increase in environmental issues, measures to remove organic solvents are being demanded, and, like photoresists, proposals are being made for heat-resistant photosensitive resin materials that can be developed with alkaline aqueous solutions.

Among these, a method is proposed to use a photosensitive resin composition in which an alkaline aqueous solution-soluble polyamic acid resin or polyhydroxyamide resin that becomes a heat-resistant resin after heat curing is mixed with a photoacid generator such as a naphthoquinone diazide compound.

These alkali-soluble resins are high-viscosity thick-film materials. When using a filter to control defects during a process, there is a limit to reducing the filter pore size due to the high viscosity of the alkali-soluble resin. Therefore, research into methods for improving the solubility of the alkali-soluble resin is continuously ongoing.

One embodiment is to provide a photosensitive resin composition capable of improving the solubility of a high viscosity alkali-soluble resin by using a solvent having a specific composition.

Another embodiment is to provide a photosensitive resin film manufactured 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) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; and (C) a solvent comprising a first solvent and a second solvent, wherein the first solvent is gamma-butyrolactone, the second solvent comprises a compound having a different structure from the first solvent, and the second solvent is comprised in an amount of 3 wt% to 10 wt% based on the total amount of the first solvent and the second solvent.

The second solvent may include a compound containing a moiety represented by the following chemical formula 1 and/or a compound represented by the following chemical formula 2.

[Chemical Formula 1]

[Chemical formula 2]

In the above chemical formulas 1 and 2,

X ¹ is a carbon atom or a sulfur atom,

X ² is *-CR ¹ R ² -* or *-NR ³ -* (wherein, R ¹ to R ³ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group),

X ³ is an oxygen atom or a sulfur atom,

X ⁴ and X ⁵ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

m is an integer from 1 to 5.

The moiety-containing compound represented by the above chemical formula 1 can be represented by any one of the following chemical formulas 1-1 to 1-3.

[Chemical Formula 1-1]

[Chemical Formula 1-2]

[Chemical Formula 1-3]

In the above chemical formulas 1-1 to 1-3,

R ^a to R ^c are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

The compound represented by the above chemical formula 2 can be represented by the following chemical formula 2-1.

[Chemical Formula 2-1]

In the above chemical formula 2-1,

R ^d is a substituted or unsubstituted C1 to C20 alkyl group.

The above alkaline-soluble resin may include a polyamic acid resin or a polyhydroxyamide resin. The polyamic acid resin or the polyhydroxyamide resin may include a structural unit represented by the following chemical formula 3.

[Chemical Formula 3]

In the above chemical formula 3,

^Y1 and ^Y4 are residues derived from a diamine monomer,

Y ² is a residue derived from a dianhydride monomer,

^Y3 is a residue derived from diacid,

R ⁴ and R ⁵ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclic group.

In the above chemical formula 3, the diacid derivative may be a derivative of 4,4'-oxybisbenzoyl chloride or 4,4'-oxybisbenzoic acid.

The photosensitive resin composition may contain 1 to 50 parts by weight of the photosensitive diazoquinone compound and 100 to 300 parts by weight of the solvent, based on 100 parts by weight of the alkali-soluble resin.

The above photosensitive resin composition may further include an additive selected from the group consisting of diacid, alkanolamine, surfactant, silane coupling agent, dissolution regulator, epoxy compound, curing agent, photoacid generator, radical polymerization initiator, thermal latent acid generator, or a combination thereof.

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

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

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

A photosensitive resin composition according to one embodiment can improve the solubility of a high-viscosity alkali-soluble resin by using a solvent having a specific composition.

Figure 1 is a diagram explaining the principle of the solubility evaluation method.

Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples, and the present invention is not limited thereby, and the present invention is defined only by the scope of the claims described below.

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, "heteroarylene group" means a C3 to C20 heteroarylene group, and "alkoxylene group" means a C1 It refers to a C20 alkoxylene group.

Unless otherwise specified herein, "substitution" means that at least one hydrogen atom is substituted with 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, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 It means substituted with a C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

Additionally, unless otherwise specifically stated herein, “hetero” means that the chemical formula contains at least one heteroatom of at least one of N, O, S, and P.

Additionally, unless otherwise specifically stated herein, “(meth)acrylate” means both “acrylate” and “methacrylate”.

Unless otherwise defined herein, "combination" means a mixture or copolymerization. In addition, "copolymerization" means a block copolymerization, an alternating copolymerization or a random copolymer, and "copolymer" means a block copolymer, an alternating copolymer or a random copolymer.

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

Unless otherwise defined in the chemical formulas herein, if a chemical bond is not drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded at that position.

Unless otherwise defined herein, “＊” means a moiety that is connected to the same or different atoms or chemical formulas.

A photosensitive resin composition according to one embodiment comprises: (A) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; and (C) a solvent comprising a first solvent and a second solvent, wherein the first solvent is gamma-butyrolactone, the second solvent comprises a compound having a different structure from the first solvent, and the second solvent is contained in an amount of 3 wt% to 10 wt% based on the total amount of the first solvent and the second solvent.

In general, alkali-soluble resins used in photosensitive resin compositions perform functions such as passivation, insulation, and alpha-ray shield as packaging materials such as protective films or insulating layers in semiconductor or display devices, and the photosensitive resin composition is coated, exposed to UV light, and then developed and cured for application. The alkali-soluble resins used in photosensitive resin compositions are manufactured by polymerization of a dianhydride monomer or a diacid derivative and a diamine monomer, but by-products generated from the dianhydride monomer or a diacid derivative are discharged during the polymerization reaction, which reduces the solubility of the alkali-soluble resin, causing problems. Accordingly, attempts have been made to improve the solubility of the alkali-soluble resin by adjusting the ratio of the alkali-soluble resin, changing its structure, or adding other additives, but the inventors of the present application have confirmed that, unlike the means attempted in the past, the solubility of the alkali-soluble resin can be improved by only changing the composition of the solvent, even when an alkali-soluble resin having a structure in which the by-product is discharged is used, and thus the present invention has been completed.

Each component is described in detail below.

(C) Solvent

The photosensitive resin composition comprises two solvents having different structures, namely, a first solvent and a second solvent. Specifically, the first solvent is gamma-butyrolactone, and the second solvent comprises a compound having a different structure from gamma-butyrolactone, wherein the second solvent is comprised in an amount of 3 wt% to 10 wt% based on the total amount of the first solvent and the second solvent.

Although there have been attempts in the past to employ a composition in which gamma-butyrolactone and other solvents having different structures are used together, in most cases, the relative content of solvents having structures other than gamma-butyrolactone with respect to the total amount of solvent was too high, and there has been no research or consideration on whether such a solvent composition can improve the solubility of alkali-soluble resins, particularly alkali-soluble resins having a structure in which by-products cannot be avoided from dianhydride monomers or diacid derivatives.

If the second solvent is included in an amount less than 3 wt% based on the total amount of the first solvent and the second solvent, the content of the second solvent is too small, which inevitably leads to a problem of reduced solubility of the byproduct of the alkali-soluble resin. If the second solvent is included in an amount greater than 10 wt% based on the total amount of the first solvent and the second solvent, which inevitably leads to a problem of reduced processability due to increased thickness, uncoating, or miscoating.

For example, the second solvent may include a compound containing a moiety represented by the following chemical formula 1 and/or a compound represented by the following chemical formula 2.

[Chemical Formula 1]

[Chemical formula 2]

In the above chemical formulas 1 and 2,

X ¹ is a carbon atom or a sulfur atom,

X ² is *-CR ¹ R ² -* or *-NR ³ -* (wherein, R ¹ to R ³ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group),

X ³ is an oxygen atom or a sulfur atom,

X ⁴ and X ⁵ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

m is an integer from 1 to 5.

For example, the moiety-containing compound represented by the chemical formula 1 may be a compound having a chain structure or a compound having a ring structure.

For example, the compound having the chain structure can be represented by the following chemical formula 1A or chemical formula 1B.

[Chemical Formula 1A]

[Chemical Formula 1B]

In the above chemical formulas 1A and 1B,

X ¹ is a carbon atom or a sulfur atom,

R ⁶ to R ⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

For example, the compound having the above cyclic structure can be represented by the following chemical formula 1C.

[Chemical Formula 1C]

In the above chemical formula 1C,

X ¹ is a carbon atom or a sulfur atom,

R ⁶ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

For example, the moiety-containing compound represented by the chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-3, but is not necessarily limited thereto.

[Chemical Formula 1-1]

[Chemical Formula 1-2]

[Chemical Formula 1-3]

In the above chemical formulas 1-1 to 1-3,

R ^a to R ^c are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

For example, the compound represented by the chemical formula 2 may be represented by the following chemical formula 2-1, but is not necessarily limited thereto.

[Chemical Formula 2-1]

In the above chemical formula 2-1,

R ^d is a substituted or unsubstituted C1 to C20 alkyl group.

In addition to the first and second solvents described above, another type of solvent may be appropriately selected and used depending on the process for forming a photosensitive resin film, such as spin coating or slit die coating.

The above solvent is preferably used in an amount of 100 to 300 parts by weight, for example, 100 to 250 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 an appropriate thickness that is neither too thin nor too thick can be coated, and the solubility and coatability can be excellent.

(A) Alkali soluble resin

Alkali-soluble resins used in the photosensitive resin composition according to one embodiment include polybenzoxazole precursors, polyimide precursors (polyamic acid resins), novolac resins, bisphenol A resins, bisphenol F resins, (meth)acrylate resins, or combinations thereof. Specifically, polybenzoxazole precursors, polyimide precursors (polyamic acid resins), or combinations thereof can be used as the alkali-soluble resin, but the type of the alkali-soluble resin is not necessarily limited thereto.

For example, the alkali-soluble resin may be a polyamic acid precursor resin or a polybenzoxazole precursor resin.

The above alkaline soluble resin may include a structural unit represented by the following chemical formula 3. By including the structural unit represented by the following chemical formula 3, the resin can be cured quickly during high-temperature curing, thereby improving thermal properties.　

[Chemical Formula 3]

In the above chemical formula 3,

^Y1 and ^Y4 are residues derived from a diamine monomer,

Y ² is a residue derived from a dianhydride monomer,

^Y3 is a residue derived from diacid,

R ⁴ and R ⁵ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclic group.

For example, in the chemical formula 3, the diacid derivative may be a derivative of 4,4'-oxybisbenzoyl chloride or 4,4'-oxybisbenzoic acid.

That is, in the chemical formula 3, when Y ¹ is a residue derived from 4,4'-oxybisbenzoic acid, the alkali-soluble resin produced therefrom discharges a byproduct represented by the chemical formula 4 below, derived from the structure of the 4,4'-oxybisbenzoic acid, into the photosensitive resin composition, which becomes a major cause of reduced solubility of the alkali-soluble resin.

[Chemical Formula 4]

For example, the byproduct represented by the chemical formula 4 may be included in the photosensitive resin composition according to one embodiment at 5 ppm or more, for example, 5 ppm to 5,000 ppm.

In the past, in order to prevent the generation of by-products represented by the chemical formula 4 above, attempts were made to use methods such as modifying the structure of the diacid monomer, changing the input ratio or order, or adding new additives. However, when the structure of the diacid monomer was modified, the structure of the alkali-soluble resin also changed, which further reduced the solubility or caused problems other than solubility (such as processability). In addition, when the ratio or order was changed, the molecular weight changed, and even when new additives were added, the effect of improving solubility was minimal or the solution did not form well.

However, according to one embodiment, even if a byproduct represented by the chemical formula 4 is generated in the photosensitive resin composition through the solvent composition described above, the solubility of an alkali-soluble resin including a structural unit represented by the chemical formula 3 can be improved.

The above alkali-soluble resin can have a weight average molecular weight (M _w ) of 3,000 g/mol to 300,000 g/mol. When the weight average molecular weight of the above alkali-soluble resin is within the above range, sufficient physical properties can be obtained, and the solubility in an organic solvent is excellent, making handling easy.

Meanwhile, the dianhydride monomers include a monomer represented by the following chemical formula 5, a monomer represented by the following chemical formula 6, a monomer represented by the following chemical formula 7, and butanetetracarboxylic dianhydride.

(butanetetracarboxylic dianhydride), pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicyclohexanetetracarboxylic dianhydride, cyclopropanetetracarboxylic dianhydride, methylcyclohexanetetracarboxylic dianhydride

(methylcyclohexanetetracarboxylic dianhydride), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4,9,10-perylenetetracaboxylic dianhydride, 4,4-sulfonyldiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracaboxylic dianhydride dianhydride), 2,3,6,7-naphthalenetetracaboxylic dianhydride, 1,4,5,8-naphthalene tetracaboxylic dianhydride, 2,3,5,6-pyridinetetracaboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracaboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracaboxylic dianhydride, 4,4-Oxydiphthalic di

4,4-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenoxy)phenylpropanedianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenoxy)phenylpropanedianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenoxy)phenylpropane dianhydride, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propanedianhydride, Examples thereof include 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, and 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride. However, it is not necessarily limited thereto. For example, the Y ² may be a tetravalent functional group derived from the acid dianhydride of the dianhydride monomer.

[Chemical Formula 5]

[Chemical formula 6]

[Chemical formula 7]

For example, the alkali-soluble resin may further include a polymerizable functional group represented by Chemical Formula 9 to Chemical Formula 13-1 at at least one of both terminals, and the polymerizable functional group may be crosslinked during the process.　

[Chemical formula 9]

[Chemical Formula 9-1]

(In the above chemical formula 9 and chemical formula 9-1, R ₁₆ is H, CH ₂ COOH or CH ₂ CHCHCH _3. )

[Chemical Formula 10]

[Chemical Formula 10-1]

(In the above chemical formula 10 and chemical formula 10-1, R ₁₇ and R ₁₈ are each independently H or CH _3. )

[Chemical Formula 11]

[Chemical Formula 11-1]

[Chemical Formula 12]

[Chemical Formula 12-1]

(In the above chemical formula 12 and chemical formula 12-1, R ₁₉ is H or CH ₃ , and R ₂₀ is *-CH ₂ -* or an oxygen atom.)

[Chemical Formula 13]

[Chemical Formula 13-1]

(In the above chemical formula 13 and chemical formula 13-1, R ₂₁ and R ₂₂ are each independently H, CH ₃ or OCOCH _3. )

(B) Photosensitive diazoquinone compound

As the above-mentioned 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 compounds include, but are not limited to, compounds represented by the following chemical formulas 71 and 73 to 75.

[Chemical formula 71]

In the above chemical 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 can each independently be OQ, and Q can be a hydrogen atom, a functional group represented by the following chemical formula 72a, or a functional group represented by the following chemical formula 72b, wherein Q cannot be a hydrogen atom at the same time.

n31 to n33 can each independently be an integer from 1 to 5.

[Chemical formula 72a]

[Chemical formula 72b]

[Chemical formula 73]

In the above chemical formula 73,

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

D ⁴ to D ⁶ can each independently be OQ, and Q is the same as defined in the chemical formula 71,

n34 to n36 can each independently be an integer from 1 to 5.

[Chemical formula 74]

In the above chemical 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, and Q is the same as defined in the chemical formula 71.

n37, n38, n39 and n40 can each independently be an integer from 1 to 4,

n37+n38 and n39+n40 can each independently be an integer less than or equal to 5,

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

[Chemical formula 75]

In the above chemical formula 75,

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

n41 and n42 can each independently be an integer from 1 to 5, specifically an integer from 2 to 4,

Q is the same as defined in the above chemical formula 71.

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, a pattern is formed well without residue by exposure, there is no loss of film thickness during development, and a good pattern can be obtained.

(D) Other additives

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

The above photosensitive resin composition may contain additives such as a diacid (e.g., malonic acid), an alkanolamine (e.g., 3-amino-1,2-propanediol), a surfactant, a silane coupling agent, a solubility regulator, an epoxy compound, a curing agent, a photoacid generator, a radical polymerization initiator, a thermal latent acid generator, or a combination thereof, in order to prevent stains or spots during coating, to achieve leveling properties, or to prevent the generation of residues due to non-development. The amount of these additives used may be easily adjusted depending on the desired 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 to improve adhesion to a substrate.

Examples of the above silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc., and these may be used alone or in combination of two or more.

The above silane coupling agent may be included in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included within the above range, adhesion, storability, etc. may be excellent.

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

Examples of the above fluorinated surfactants include BM Chemie's BM- ^1000® , BM- ^1100® , etc.; Dainippon Ink Chemical Industry Co., Ltd.'s Mecapac F ^142D® , Mecapac F ^172® , Mecapac F 173®, Mecapac F ^183® , Mecapac F ^554® , etc ^.; Sumitomo Reum Co., Ltd.'s Prorad FC- ^135® , Prorad FC- ^170C® , Prorad FC- ^430® , Prorad FC- ^431® , etc.; Asahi Glass Co., Ltd.'s Saffron S- ^112® , Saffron S- ^113® , Saffron S- ^131® , Saffron S- ^141® , Saffron S-145® ^, etc.; Toray Silicone Co., Ltd.'s SH- ^28PA® , SH- ^190® , SH- ^193® , SZ- ^6032® , SF- ^8428®, etc. can be used.

As the above silicone-based surfactant, those commercially available from BYK Chem under the names BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, BYK-325, BYK-378, etc. can be used.

The above surfactant can be used in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the photosensitive resin composition. When the above surfactant is included within the above range, coating uniformity is secured, no staining occurs, and wetting for an ITO substrate or glass substrate can be excellent.

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

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

The above epoxy compound can be used in an amount of 0.01 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 properties, adhesion, and other properties can be improved.

In addition, the photosensitive resin composition may further include a thermal latent acid generator. Examples of the thermal latent acid generator include, but are not limited to, arylsulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, and the like; 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 combinations thereof.

The photosensitive resin composition according to one embodiment may further include a dissolution regulator. The dissolution regulator increases the dissolution speed and sensitivity of an exposed portion when developed with an alkaline aqueous solution, and helps to enable high-resolution patterning. For example, a phenol-based compound, specifically a resorcinol-based compound, may be used as the dissolution regulator, but is not necessarily limited thereto. It may be preferable that the dissolution regulator be used in an amount of 1 part by weight to about 50 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the dissolution regulator is within the above range, it is preferable that a good pattern is obtained by appropriately increasing the dissolution speed of an unexposed portion without causing a decrease in sensitivity when developed, and also that excellent storage stability is exhibited because precipitation does not occur when stored in a freezer.

In addition, other additives such as antioxidants and stabilizers may be added in a certain amount to the photosensitive resin composition as long as the physical properties are not impaired.

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

The method for manufacturing the photosensitive resin film is as follows.

(1) Application and film formation stage

The photosensitive resin composition is applied to a desired thickness on a glass substrate or ITO substrate, Si wafer, SiNx wafer, or the like, which has undergone a predetermined pretreatment, using a method such as spin or slit coating, roll coating, screen printing, or applicator, and then heated at 70°C to 150°C for 1 to 10 minutes to remove the solvent, thereby forming a coating film.

(2) Exposure stage

In order to form a necessary pattern on the photosensitive resin film obtained above, a mask is interposed, and then an active line of 200 nm to 500 nm is 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. can be used, and in some cases, X-rays, electron beams, etc. can also be used.

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

(3) Phenomenon stage

In the developing method, following the above exposure step, the exposed portion is dissolved and removed using a developing solution, thereby leaving only the unexposed portion, thereby obtaining a pattern.

(4) Post-processing step

In the above process, there is a post-heating process to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, and storage stability from the image pattern obtained by development. For example, after development, it can be heated in a nitrogen atmosphere in an oven at 350°C for 1 hour.

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

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

(Example)

(Alkali soluble resin synthesis)

Manufacturing example 1

While passing nitrogen into a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injection device, and a condenser, 216 g of Bis-APAF (2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane) was dissolved in 690 g of NMP ( N -Methyl-2-pyrrolidone). Then, 83 g of pyridine was added, and the temperature was maintained below 3°C. A solution of 154 g of ODBC (4,4'-Oxybisbenzochloride) dissolved in 630 g of NMP was added dropwise over 40 minutes and stirred for 4 hours. Thereafter, the temperature was changed to room temperature, 25 g of NBDA (5-Norbornene-2,3-dicarboxylic Anhydride) was added, and the reaction was terminated by stirring at 70°C for 24 hours. The reaction mixture was poured into a solution of water/methanol = 10/1 (volume ratio) to generate a precipitate, which was filtered and thoroughly washed with water. Then, the precipitate was dried under vacuum at 80°C for more than 24 hours to produce a polybenzoxazole precursor having a weight average molecular weight of 11,300 g/mol.

(Manufacture of photosensitive resin composition)

Example 1

30 g of the alkali-soluble resin of the above Manufacturing Example 1 was added to 53 g of a solvent (a mixture of gamma-butyrolactone and the compound represented by the chemical formula 1-1 in a weight ratio of 97:3) and dissolved, then 4.5 g of a photosensitive diazoquinone compound, a 4-naphthoquinonediazide (4-NQD) photosensitive agent, 3.0 g of 4-butylresorcinol as a solubility regulator, 0.6 g of a silane coupling agent (KBM-573; Shin-Etsu), 0.01 g of a silicone surfactant (BYK-378; BYK Chem), and 3.0 g of a curing agent (PD1174) were added and dissolved, and then filtered through a 0.45 μm fluororesin filter to obtain a photosensitive resin composition.

[Chemical Formula 1-1]

Example 2

The same procedure as in Example 1 was followed, except that a solvent containing gamma-butyrolactone and a compound represented by the chemical formula 1-1 was used in a weight ratio of 95:5.

Example 3

The same procedure as in Example 1 was followed, except that a solvent containing gamma-butyrolactone and a compound represented by the chemical formula 1-1 mixed in a weight ratio of 90:10 was used.

Example 4

The same procedure as in Example 1 was followed, except that the compound represented by Chemical Formula 2-1 (R ^d is an unsubstituted C1 alkyl group) was used instead of the compound represented by Chemical Formula 1-1.

Example 5

The same procedure as in Example 2 was followed, except that the compound represented by Chemical Formula 2-1 (R ^d is an unsubstituted C1 alkyl group) was used instead of the compound represented by Chemical Formula 1-1.

Example 6

The same procedure as in Example 3 was followed, except that the compound represented by Chemical Formula 2-1 (R ^d is an unsubstituted C1 alkyl group) was used instead of the compound represented by Chemical Formula 1-1.

Example 7

The same procedure as in Example 1 was followed, except that a compound represented by Chemical Formula 1C (m is an integer of 2, X ¹ is a carbon atom, and R ⁶ is an unsubstituted C1 alkyl group) was used instead of the compound represented by Chemical Formula 1-1.

Example 8

The same procedure as Example 2 was followed, except that a compound represented by Chemical Formula 1C (m is an integer of 2, X ¹ is a carbon atom, and R ⁶ is an unsubstituted C1 alkyl group) was used instead of the compound represented by Chemical Formula 1-1.

Example 9

The same procedure as Example 3 was followed, except that a compound represented by Chemical Formula 1C (m is an integer of 2, X ¹ is a carbon atom, and R ⁶ is an unsubstituted C1 alkyl group) was used instead of the compound represented by Chemical Formula 1-1.

Example 10

The same procedure as in Example 1 was followed, except that a compound represented by Chemical Formula 1B (X ¹ is a carbon atom, R ⁶ to R ⁸ are unsubstituted C1 alkyl groups) was used instead of the compound represented by Chemical Formula 1-1.

Example 11

The same procedure as in Example 2 was followed, except that a compound represented by Chemical Formula 1B (X ¹ is a carbon atom, R ⁶ to R ⁸ are unsubstituted C1 alkyl groups) was used instead of the compound represented by Chemical Formula 1-1.

Example 12

The same procedure as in Example 3 was followed, except that a compound represented by Chemical Formula 1B (X ¹ is a carbon atom, R ⁶ to R ⁸ are unsubstituted C1 alkyl groups) was used instead of the compound represented by Chemical Formula 1-1.

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Comparative Example 1

The same procedure as in Example 1 was followed, except that a solvent containing gamma-butyrolactone and a compound represented by the chemical formula 1-1 was used in a weight ratio of 98:2.

Comparative Example 2

The same procedure as in Example 1 was followed, except that a solvent containing gamma-butyrolactone and a compound represented by the chemical formula 1-1 was used in a weight ratio of 89:11.

Comparative Example 3

The same procedure as Comparative Example 1 was followed, except that a compound represented by Chemical Formula 2-1 (R ^d is an unsubstituted C1 alkyl group) was used instead of the compound represented by Chemical Formula 1-1.

Comparative Example 4

The same procedure as Comparative Example 2 was followed, except that the compound represented by Chemical Formula 2-1 (R ^d is an unsubstituted C1 alkyl group) was used instead of the compound represented by Chemical Formula 1-1.

Comparative Example 5

The same procedure as Comparative Example 1 was followed, except that a compound represented by Chemical Formula 1C (m is an integer of 2, X ¹ is a carbon atom, and R ⁶ is an unsubstituted C1 alkyl group) was used instead of the compound represented by Chemical Formula 1-1.

Comparative Example 6

The same procedure as Comparative Example 2 was followed, except that a compound represented by Chemical Formula 1C (m is an integer of 2, X ¹ is a carbon atom, and R ⁶ is an unsubstituted C1 alkyl group) was used instead of the compound represented by Chemical Formula 1-1.

Comparative Example 7

The same procedure as Comparative Example 1 was followed, except that a compound represented by Chemical Formula 1B (X ¹ is a carbon atom, R ⁶ to R ⁸ are unsubstituted C1 alkyl groups) was used instead of the compound represented by Chemical Formula 1-1.

Comparative Example 8

The same procedure as Comparative Example 2 was followed, except that a compound represented by Chemical Formula 1B (X ¹ is a carbon atom, R ⁶ to R ⁸ are unsubstituted C1 alkyl groups) was used instead of the compound represented by Chemical Formula 1-1.

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Comparative Example 11

The procedure of Example 1 was the same, except that gamma-butyrolactone was used as the sole solvent.

Comparative Example 12

The same procedure as Example 1 was followed, except that the compound represented by Chemical Formula 1-1 was used as the sole solvent.

Comparative Example 13

The same procedure as in Example 1 was followed, except that a compound represented by Chemical Formula 2-1 (R ^d is an unsubstituted C1 alkyl group) was used as the sole solvent.

Comparative Example 14

The same procedure as in Example 1 was followed, except that a compound represented by chemical formula 1C (wherein m is an integer of 2, X ¹ is a carbon atom, and R ⁶ is an unsubstituted C1 alkyl group) was used as the sole solvent.

Comparative Example 15

The same procedure as in Example 1 was followed, except that a compound represented by chemical formula 1B (X ¹ is a carbon atom, R ⁶ to R ⁸ are unsubstituted C1 alkyl groups) was used as the sole solvent.

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Comparative Example 17

The same procedure as in Example 1 was followed, except that a compound represented by the following chemical formula C-1 was used as a solvent instead of the compound represented by the chemical formula 1-1.

[Chemical Formula C-1]

Evaluation 1: Solubility Evaluation

The photosensitive resin compositions according to Examples 1 to 12 and Comparative Examples 1 to 8, Comparative Examples 11 to 15 and Comparative Example 17 were subjected to ACF (Auto Correlation Function) verification through PSA (Particle Size Analyzer), and the principle is as shown in Fig. 1. The fact that the time required for injected light to transmit through when insoluble particles are present was utilized, and the evaluation results are shown in Table 1 below.

Evaluation 2: Defect Evaluation

The photosensitive resin compositions according to Examples 1 to 12 and Comparative Examples 1 to 8, Comparative Examples 11 to 15 and Comparative Example 17 were spin-coated on an 8-inch wafer, and then heated at 120°C for 4 minutes to form a film with a thickness of 10 μm. Thereafter, five wafers were measured with a KLA SP1 facility to check for defects after SOB (soft baking or prebaking) of 1 μm or more in size, and wafers with a thickness of 10 μm were separately produced and developed in a 2.38 wt% TMAH solution for 100 seconds (Double Puddle each for 50 seconds), and five wafers were measured with the SP1 facility to check for defects after Dev. (development) of 1 μm or more in size. The defects were measured, and the evaluation results are shown in Table 1 below.

(unit: %) Solubility@ACF(uSec) Defect after SOB (ea/wafer) Dev. Defect(ea/wafer) Example 1 10 5 5 Example 2 11 5 3 Example 3 11 3 3 Example 4 10 3 3 Example 5 10 3 3 Example 6 11 3 3 Example 7 10 5 5 Example 8 10 3 3 Example 9 10 3 3 Example 10 11 5 5 Example 11 10 3 3 Example 12 11 3 3 Comparative Example 1 70,000 50 52 Comparative Example 2 70,000 60 60 Comparative Example 3 70,000 60 55 Comparative Example 4 80,000 55 52 Comparative Example 5 80,000 62 68 Comparative Example 6 80,000 55 58 Comparative Example 7 70,000 65 68 Comparative Example 8 80,000 55 60 Comparative Example 11 100,000 55 60 Comparative Example 12 100,000 64 7 Comparative Example 13 100,000 66 67 Comparative Example 14 70,000 64 65 Comparative Example 15 70,000 64 62 Comparative Example 17 80,000 52 55

Through the above Table 1, it can be confirmed that the photosensitive resin composition according to one embodiment can significantly improve the solubility of an alkali-soluble resin by using a solvent of a specific composition.

The present invention is not limited to the above embodiments, but can be manufactured in various different forms, and a person having ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing the technical idea or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (10)

(A) Alkali-soluble resin;
(B) Photosensitive diazoquinone compound;
(C) a solvent comprising a first solvent and a second solvent;
Including,
The first solvent is gamma-butyrolactone,
The second solvent comprises a compound having a different structure from the first solvent,
The second solvent is included in an amount of 3 wt% to 10 wt% based on the total amount of the first solvent and the second solvent,
The second solvent is a photosensitive resin composition comprising a compound represented by any one of the following chemical formulas 1A to 1C and 2-1:
[Chemical Formula 1A]

[Chemical Formula 1B]

[Chemical Formula 1C]

In the above chemical formulas 1A to 1C,
X ¹ is a carbon atom or a sulfur atom,
R ⁶ to R ⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
m is an integer from 1 to 5,
[Chemical Formula 2-1]

In the above chemical formula 2-1,
R ^d is a substituted or unsubstituted C1 to C20 alkyl group.
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The above alkaline-soluble resin is a photosensitive resin composition containing a polyamic acid resin.
In paragraph 4,
The above polyamic acid resin is a photosensitive resin composition containing a structural unit represented by the following chemical formula 3:
[Chemical Formula 3]

In the above chemical formula 3,
^Y1 and ^Y4 are residues derived from a diamine monomer,
Y ² is a residue derived from a dianhydride monomer,
^Y3 is a residue derived from diacid,
R ⁴ and R ⁵ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclic group.
In paragraph 5,
A photosensitive resin composition wherein the above-mentioned diacid derivative is a derivative of 4,4'-oxybisbenzoyl chloride or 4,4'-oxybisbenzoic acid.
In the first paragraph,
The above photosensitive resin composition,
For 100 parts by weight of the above alkaline soluble resin
Containing 1 to 50 parts by weight of the photosensitive diazoquinone compound,
A photosensitive resin composition containing 100 to 300 parts by weight of the above solvent.
In the first paragraph,
The photosensitive resin composition further comprises an additive selected from the group consisting of diacid, alkanolamine, surfactant, silane coupling agent, dissolution regulator, epoxy compound, curing agent, photoacid generator, radical polymerization initiator, thermal latent acid generator, or a combination thereof.
A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1 and 4 to 8.
An electronic device comprising a photosensitive resin film according to claim 9.