TW202014443A - Photosensitive resin composition, photosensitive resin layer and electronic device - Google Patents

Abstract

Disclosed are a photosensitive resin composition including (A) an alkaline soluble resin; (B) a photosensitive diazoquinone compound; (C) a dissolution controlling agent including a first phenolic resin represented by Chemical Formula 1 and a second phenolic resin represented by Chemical Formula 2; and (D) a solvent, wherein the first phenolic resin and the second phenolic resin are included in a weight ratio of 10:90 to 30:70, a photosensitive resin layer, and an electronic device including the photosensitive resin layer.

Description

Photosensitive resin composition, photosensitive resin layer and electronic device

The present invention relates to a photosensitive resin composition, a photosensitive resin layer using the photosensitive resin composition, and an electronic device. [ Cross reference to related applications ]

This application claims the priority and rights of Korean Patent Application No. 10-2018-0117827 filed with the Korean Intellectual Property Office on October 2, 2018. The entire contents of the application are incorporated herein by reference.

Polyimide resins, polybenzoxazole resins, and the like with improved heat resistance, electrical characteristics, and mechanical characteristics have been widely used as surface protective layers and interlayers in materials for display device panels and semiconductor devices Insulation. Since these resins have low solubility in various solvents, these resins are provided as a composition in which the precursor is dissolved in the solvent.

In recent years, the emergence of environmental problems has required countermeasures against de-organic solvents, and various types of heat-resistant photosensitive resin materials that can be produced with aqueous alkaline solutions in the same manner as photoresists have been proposed.

Among them, there has been proposed a method of using a photosensitive resin composition comprising a hydroxypolyamide resin (polybenzoxazole precursor) soluble in an alkaline aqueous solution and a compound such as diazide A mixture of photoacid generators of naphthoquinone diazide compounds, the hydroxypolyamide resin being a heat-resistant resin after thermal curing.

The photosensitive mechanism of the photosensitive resin composition utilizes the exposure of the photosensitive diazoquinone compound to the naphthoquinone diazide compound (ie, the photosensitive diazoquinone compound) and polybenzoxazole in the unexposed portion ( polybenzoxazole (PBO) precursor, and thereby convert the photosensitive diazoquinone compound into an indene carboxylic acid compound to increase the dissolution rate in aqueous alkali solution. The difference pattern between the exposed portion and the unexposed portion can be used to produce a relief pattern composed of the unexposed portion.

The photosensitive resin composition can form a positive concave-convex pattern by exposure and development with an alkali aqueous solution. In addition, heat curing film characteristics can be obtained by heating.

When a cured film is applied to a semiconductor device as a surface protection layer and an interlayer insulating layer, the cured film needs to have high reliability. Although there are many indicators to assess reliability, sensitivity and residual characteristics are particularly important. In addition, the cured concave-convex pattern should have a good shape, sufficient alkali solubility, a small amount of residual film during development, and excellent close contact characteristics with the substrate.

The embodiment provides a photosensitive resin composition having improved film residual rate, sensitivity, and residual characteristics at the same time.

Another embodiment provides a photosensitive resin layer manufactured using a photosensitive resin composition.

Yet another embodiment provides an electronic device including a photosensitive resin layer.

[化學式2]

在化學式1和化學式2中， R¹ 到R³ 各自獨立地為羥基或取代或未取代的C1到C5烷基， p、q以及r各自獨立地為0到3範圍內的整數，以及 a、b以及c各自獨立地為正整數。The embodiment provides a photosensitive resin composition including: (A) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a dissolution control agent, including the first represented by Chemical Formula 1 A phenol resin and a second phenol resin represented by Chemical Formula 2; and (D) a solvent in which the first phenol resin and the second phenol resin are included in a weight ratio of 10:90 to 30:70. [Chemical Formula 1]

[Chemical Formula 2]

In Chemical Formula 1 and Chemical Formula 2, R ¹ to R ³ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C5 alkyl group, p, q and r are each independently an integer ranging from 0 to 3, and a, b and c are independently positive integers.

The second phenolic resin may be a block copolymer, a replacement copolymer, or a random copolymer.

The dissolution control agent may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of alkali-soluble resin.

The alkali-soluble resin may be polyhydroxyamide resin.

The photosensitive resin composition may be based on 100 parts by weight of the alkali-soluble resin, including 1 part by weight to 100 parts by weight of the photosensitive diazoquinone compound, 0.1 parts by weight to 20 parts by weight of the dissolution control agent, and 100 parts by weight to 500 parts by weight Parts of solvent.

The photosensitive resin composition may further include the following additives: a dissolution control agent having a different structure from the first phenolic resin and the second phenolic resin, a sensitivity enhancer, a crosslinking agent, a diacid, an alkanolamine, a leveling agent, a coupling agent , Surfactants, epoxy compounds, free radical polymerization initiators, thermal latent acid generators or combinations thereof.

Another embodiment provides a photosensitive resin layer manufactured using a photosensitive resin composition.

Another embodiment provides an electronic device including a photosensitive resin layer.

Other embodiments of the present invention are included in the following specific embodiments.

The photosensitive resin composition according to the embodiment can simultaneously improve the film residual rate, sensitivity, and residual characteristics by the dissolution control agent containing two different phenol resins mixed in a specific ratio.

Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the invention is not limited thereto and the invention is defined by the scope of patent application.

In the present invention, when no specific definition is provided otherwise, "alkyl" refers to C1 to C20 alkyl, "alkenyl" refers to C2 to C20 alkenyl, and "cycloalkenyl" refers to C3 to C20 cycloalkene Group, "heterocyclenyl" refers to C2 to C20 heterocyclenyl, "aryl" refers to C6 to C20 aryl, "aralkyl" refers to C7 to C20 aralkyl, and "extended alkyl" is Refers to C1 to C20 alkylene extension, "Aryl extension" refers to C6 to C20 extension aryl, "Alkyl extension aryl" refers to C7 to C20 alkyl extension, "Extended heteroaryl" refers to C5 to C20 extension Heteroaryl, and "extended alkoxy" refers to C1 to C20 extended alkoxy.

In this specification, when a specific definition is not otherwise provided, "substitution" refers to replacement of at least one hydrogen atom by a substituent selected from the group consisting of a halogen atom (F, Cl, Br, or I), a hydroxyl group, and a C1 to C20 alkoxy group Group, nitro group, cyano group, amine group, imino group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group , Carbamyl group (carbamyl group), thiol group, ester group, ether group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid group or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl, C6 to C20 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 To C20 heterocycloalkynyl, C5 to C20 heteroaryl or a combination thereof.

In this specification, when no specific definition is provided otherwise, "hetero" means that the chemical formula contains at least one hetero atom of N, O, S, and P.

In this specification, when no specific definition is provided otherwise, "(meth)acrylate" refers to "acrylate" and "methacrylate".

In this specification, when a definition is not otherwise provided, "combination" refers to mixing or copolymerization. In addition, "copolymerization" refers to block copolymerization, alternative copolymerization, or random copolymerization, and "copolymer" refers to block copolymer, alternative copolymer, or random copolymer.

In this specification, when a specific definition is not otherwise provided, unsaturated bonds include bonds between other atoms, such as carbonyl bonds or azo bonds, and multi-bonds between carbon-carbon atoms.

In this specification, when a definition is not otherwise provided, when a chemical bond is not drawn at a position that should be given in the chemical formula, hydrogen is bonded at the position.

In addition, in this specification, when a definition is not otherwise provided, "*" refers to a linking point with the same or different atom or chemical formula.

A photosensitive resin composition according to an embodiment includes: (A) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a dissolution control agent including a first phenolic resin and a second phenolic resin; and (D ) A solvent, in which the first phenolic resin is a polymer represented by Chemical Formula 1 and the second phenolic resin is a copolymer represented by Chemical Formula 2, and contains the first phenolic resin and the second in a weight ratio of 10:90 to 30:70 Phenolic Resin.

[化學式2]

在化學式1和化學式2中， R¹ 到R³ 各自獨立地為羥基或取代或未取代的C1到C5烷基， p、q以及r各自獨立地為0到3範圍內的整數，以及 a、b以及c各自獨立地為正整數。[Chemical Formula 1]

[Chemical Formula 2]

In Chemical Formula 1 and Chemical Formula 2, R ¹ to R ³ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C5 alkyl group, p, q and r are each independently an integer ranging from 0 to 3, and a, b and c are independently positive integers.

When used as a protective layer or an insulating layer in a semiconductor or a display device, the photosensitive resin composition according to the embodiment is applied by coating the composition, UV exposure, development, and curing the composition. Reliability, especially film residual rate, sensitivity, and residual characteristics are very important for the process material, and therefore the photosensitive resin composition according to the embodiment can use the dissolution control agent including the first phenolic resin and the second phenolic resin to improve simultaneously Sensitivity and residual characteristics, while maintaining an excellent film residual rate.

Hereinafter, each component is specifically described. ( C ) Dissolution control agent

The dissolution control agent contains two different types of phenolic resins. The phenolic resin contains a first phenolic resin represented by Chemical Formula 1 and a second phenolic resin represented by Chemical Formula 2, thereby improving sensitivity and residual characteristics while maintaining an excellent film residual rate.

In Chemical Formula 1 and Chemical Formula 2, a, b, and c refer to molar numbers and may be an integer of 1 to 1,000, for example, 1 to 500. That is, the second phenolic resin may be a copolymer in which the molar ratio of b:c contains the structural unit represented by Chemical Formula 2a and the structural unit represented by Chemical Formula 2b.

[化學式2b]

在化學式2a和化學式2b中， R² 和R³ 各自獨立地為羥基或取代或未取代的C1到C5烷基，以及 q和r獨立地為0到3範圍內的整數。[Chemical Formula 2a]

[Chemical Formula 2b]

In Chemical Formula 2a and Chemical Formula 2b, R ² and R ³ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C5 alkyl group, and q and r are independently an integer ranging from 0 to 3.

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

[化學式2-1]

在化學式1-1和化學式2-1中， R¹ 到R³ 各自獨立地為羥基或取代或未取代的C1到C5烷基， p、q以及r各自獨立地為0到3範圍內的整數，以及 a、b以及c各自獨立地為正整數。[Chemical Formula 1-1]

[Chemical Formula 2-1]

In Chemical Formula 1-1 and Chemical Formula 2-1, R ¹ to R ³ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C5 alkyl group, and p, q, and r are each independently an integer ranging from 0 to 3 , And a, b, and c are each independently a positive integer.

The first phenolic resin and the second phenolic resin are contained in a weight ratio of 10:90 to 30:70. When the first phenolic resin and the second phenolic resin in the weight ratio range are included, it is easy to control the dissolution rate of TMAH, which will be described later, and simultaneously improve sensitivity and residual characteristics while maintaining an excellent film residual rate. When the content of the first phenolic resin relative to the second phenolic resin is too small (for example, the first phenolic resin: the second phenolic resin = 5:95), the dissolution rate of TMAH becomes too fast, and the film residual rate is uncontrollable, And likewise, when the content of the first phenolic resin relative to the second phenolic resin is too large (for example, the first phenolic resin: the second phenolic resin = 35:65), the dissolution rate of TMAH is too slow, and the sensitivity is difficult to control, and Accordingly, the residue in the pattern may not be improved.

For example, the dissolution control agent may be included in an amount of 0.1 to 20 parts by weight, such as 1 to 15 parts by weight, such as 3 to 12 parts by weight, based on 100 parts by weight of alkali-soluble resin. When the dissolution control agent is within the range, it can ensure that the photosensitive resin composition has excellent sensitivity, resolution, and residue removal characteristics, and forms a high-sensitivity pattern after curing, and at the same time, the heat resistance of the insulating layer can be improved. ( A ) Alkali soluble resin

The alkali-soluble resin may be polyhydroxyamide resin, polyimide resin, bisphenol A resin, bisphenol F resin, (meth)acrylate resin, or a combination thereof.

The polyhydroxyamide resin may include the structural unit represented by Chemical Formula 4, and the polyimide resin may include the structural unit represented by Chemical Formula 5.

在化學式4中， X¹ 為取代或未取代的四價C6到C30芳族有機基團， X² 為取代或未取代的二價C6到C30芳族有機基團， Y¹ 和Y² 各自獨立地為取代或未取代的C6到C30芳族有機基團、取代或未取代的二價C1到C30脂族有機基團或取代或未取代的二價C3到C30脂環族有機基團，以及 m1是2到1000的整數，m2是0到500的整數，且m1/(m1+m2) > 0.5。[Chemical Formula 4]

In Chemical Formula 4, X ¹ is a substituted or unsubstituted tetravalent C6 to C30 aromatic organic group, X ² is a substituted or unsubstituted divalent C6 to C30 aromatic organic group, and Y ¹ and Y ² are each independent Are substituted or unsubstituted C6 to C30 aromatic organic groups, substituted or unsubstituted divalent C1 to C30 aliphatic organic groups or substituted or unsubstituted divalent C3 to C30 alicyclic organic groups, and m1 is an integer from 2 to 1000, m2 is an integer from 0 to 500, and m1/(m1+m2)> 0.5.

在化學式5中， X³ 是取代或未取代的二價C6到C30芳族有機基團、取代或未取代的二價C1到C30脂族有機基團或取代或未取代的二價C3到C30脂環族有機基團，以及 Y³ 是取代或未取代的四價C6到C30芳族有機基團、取代或未取代的四價C1到C30脂族有機基團或取代或未取代的四價C3到C30脂環族有機基團。[Chemical Formula 5]

In Chemical Formula 5, X ³ is a substituted or unsubstituted divalent C6 to C30 aromatic organic group, a substituted or unsubstituted divalent C1 to C30 aliphatic organic group or a substituted or unsubstituted divalent C3 to C30 Alicyclic organic group, and Y ³ is a substituted or unsubstituted tetravalent C6 to C30 aromatic organic group, substituted or unsubstituted tetravalent C1 to C30 aliphatic organic group or substituted or unsubstituted tetravalent C3 to C30 alicyclic organic groups.

In Chemical Formula 4, X ¹ may be an aromatic organic group and may be a moiety derived from aromatic diamine.

Examples of the aromatic diamine may be at least one selected from the group consisting of 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-di Hydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl) benzene, bis (4-Amino-3-hydroxyphenyl) ash, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2, 2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-5-tris Fluoromethylphenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2-bis(3-amino-4 -Hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis(4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis( 4-amino-3-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2-bis(4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-5-pentafluoroethylphenyl) hexafluoropropane, 2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)- 2-(3-amino-4-hydroxy-5-pentafluoroethylphenyl) hexafluoropropane, 2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-( 3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy -4-amino-6-trifluoromethylphenyl) hexafluoropropane, 2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy-4- Amino-2-trifluoromethylphenyl) hexafluoropropane, 2-(3-amino-4-hydroxy-2-trifluoromethylphenyl)-2-(3-hydroxy-4-amino- 5-trifluoromethylphenyl) hexafluoropropane and 2-(3-amino-4-hydroxy-6-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-5-tris Fluoromethylphenyl) hexafluoropropane, but not limited thereto.

An example of X ¹ may be a functional group represented by Chemical Formula 6 or Chemical Formula 7, but is not limited thereto.

[化學式7]

在化學式6和化學式7中， A¹ 為單鍵、O、CO、CR⁴⁷ R⁴⁸ 、SO₂ 或S，其中R⁴⁷ 和R⁴⁸ 各自獨立地為氫原子或取代或未取代的C1到C30烷基，具體地說C1到C30氟烷基， R⁵⁰ 到R⁵² 各自獨立地為取代或未取代的C1到C30烷基、取代或未取代的C1到C30羧基、羥基或硫醇基，以及 n10是0到2的整數，其限制條件為n11和n12各自獨立地為0到3的整數。[Chemical Formula 6]

[Chemical Formula 7]

In Chemical Formula 6 and Chemical Formula 7, A ¹ is a single bond, O, CO, CR ⁴⁷ R ⁴⁸ , SO ₂ or S, wherein R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkane Radicals, specifically C1 to C30 fluoroalkyl groups, R ⁵⁰ to R ⁵² are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxyl group or a thiol group, and n10 It is an integer from 0 to 2, and its limitation is that n11 and n12 are each independently an integer from 0 to 3.

An example of X ² may be a functional group represented by Chemical Formula 8 or Chemical Formula 10, but is not limited thereto.

[化學式10]

在化學式8和化學式10中， R⁵³ 、R⁵⁵ 和R⁵⁶ 各自獨立地為取代或未取代的C1到C30烷基， n13為0到4的整數，n15和n16各自獨立地為0到3的整數，以及 A² 為單鍵、O、CR⁴⁷ R⁴⁸ 、CO、CONH、S或SO₂ ，其中R⁴⁷ 和R⁴⁸ 各自獨立地為氫原子或取代或未取代的C1到C30烷基，具體地說C1到C30氟烷基。[Chemical Formula 8]

[Chemical Formula 10]

In Chemical Formula 8 and Chemical Formula 10, R ⁵³ , R ⁵⁵ and R ⁵⁶ are each independently a substituted or unsubstituted C1 to C30 alkyl group, n13 is an integer of 0 to 4, n15 and n16 are each independently a 0 to 3 Integer, and A ² is a single bond, O, CR ⁴⁷ R ⁴⁸ , CO, CONH, S or SO ₂ , wherein R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, specifically Said C1 to C30 fluoroalkyl.

In Chemical Formula 4, Y ¹ and Y ² may each independently be a divalent aromatic organic group, a divalent aliphatic organic group, or a divalent alicyclic organic group, and may be a part of a dicarboxylic acid or a divalent The carboxylic acid derivative part. Specifically, Y ¹ and Y ² may each independently be a divalent aromatic organic group or a divalent alicyclic organic group.

Specific examples of dicarboxylic acid derivatives may be 4,4'-oxydibenzoylchloride (4,4'-oxydibenzoylchloride), diphenyloxydicarbonyl dichloride (diphenyloxydicarbonyl dichloride), bis(phenylcarbonyl chloride ) Bis (phenylcarbonyl chloride) sulfone, bis (phenylcarbonyl chloride) ether (bis (phenylcarbonyl chloride) ether), bis (phenylcarbonyl chloride) phenyl ketone (bis (phenylcarbonyl chloride) phenone), phthaloyl dichloride (Phthaloyl dichloride), terephthaloyl dichloride, isophthaloyl dichloride, dicarbonyl dichloride, diphenyloxydicarboxylate dibenzotriazole dicarboxylate dibenzotriazole) or a combination thereof, but not limited to this.

Examples of Y ¹ and Y ² may be functional groups represented by Chemical Formula 8 to Chemical Formula 10, but are not limited thereto.

[化學式9]

[化學式10]

在化學式8到化學式10中， R⁵³ 到R⁵⁶ 各自獨立地為取代或未取代的C1到C30烷基， n13和n14各自獨立地為0到4的整數，n15和n16各自獨立地為0到3的整數，以及 A² 為單鍵、O、CR⁴⁷ R⁴⁸ 、CO、CONH、S或SO₂ ，其中R⁴⁷ 和R⁴⁸ 各自獨立地為氫原子或取代或未取代的C1到C30烷基，具體地說C1到C30氟烷基。[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

In Chemical Formula 8 to Chemical Formula 10, R ⁵³ to R ⁵⁶ are each independently a substituted or unsubstituted C1 to C30 alkyl group, n13 and n14 are each independently an integer of 0 to 4, n15 and n16 are each independently 0 to An integer of 3, and A ² is a single bond, O, CR ⁴⁷ R ⁴⁸ , CO, CONH, S, or SO ₂ , wherein R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group , Specifically C1 to C30 fluoroalkyl.

In Chemical Formula 5, X ³ is a divalent aromatic organic group, a divalent aliphatic organic group, or a divalent alicyclic organic group. Specifically, X ³ is a divalent aromatic organic group or a divalent alicyclic organic group.

Specifically, X ³ may be a moiety derived from aromatic diamine, alicyclic diamine, or silicon diamine. Herein, the aromatic diamine, alicyclic diamine, and silicon diamine may be used alone or in combination of two or more.

Examples of aromatic diamines may be 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, m-phenylene diamine, p-phenylene Diamine, 1,5-naphthalene diamine, 2,6-naphthalene diamine, bis[4-(4-aminophenoxy)phenyl] lanthanum, bis(3-aminophenoxyphenyl)碸, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)benzene or In combination, the above compound contains an aromatic ring substituted with an alkyl group or halogen, but is not limited thereto.

Examples of the alicyclic diamine may be 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, or a combination thereof, but is not limited thereto.

Examples of the silicon diamine may be bis(4-aminophenyl) dimethyl silane, bis(4-aminophenyl) tetramethyl siloxane, bis(p-amino phenyl) tetramethyl disila Oxane, bis(γ-aminopropyl)tetramethyldisilaxane, 1,4-bis(γ-aminopropyldimethylsilyl)benzene, bis(4-aminobutyl)tetramethyl Disilaxane, bis(γ-aminopropyl)tetraphenyldisilaxane, 1,3-bis(aminopropyl)tetramethyldisilaxane, or a combination thereof, but not limited thereto.

In Chemical Formula 5, Y3 is a tetravalent aromatic organic group, a tetravalent aliphatic organic group, or a tetravalent alicyclic organic group. Specifically, Y3 is a tetravalent aromatic organic group or a tetravalent alicyclic organic group.

Y3 may be a moiety derived from aromatic acid dianhydride or alicyclic acid dianhydride. Herein, the aromatic acid dianhydride and the alicyclic acid dianhydride may be used alone or in combination of two or more.

Examples of the aromatic acid dianhydride may be benzophenone tetracarboxylic dianhydride (such as pyromellitic dianhydride); benzophenone-3,3',4,4' -Tetracarboxylic dianhydride and the like; oxydiphthalic dianhydride (such as 4,4'-oxydiphthalic dianhydride); biphthalic dianhydride (biphthalic dianhydride) (such as 3,3',4,4'-biphenyltetracarboxylic dianhydride); (hexafluoroisopropylidene) diphthalic dianhydride (such as 4,4'-(hexafluoroisopropylene) diphthalide Acid anhydride); naphthalene-1,4,5,8-tetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic dianhydride (3,4,9,10-perylenetetracarboxylic dianhydride) and the like, but not Limited to this.

Examples of the alicyclic acid dianhydride may be 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 5-(2,5- Dioxatetrahydrofuranyl)-3-methyl-cyclohexane-1,2-dicarboxylic anhydride, 4-(2,5-dioxatetrahydrofuran-3-yl)-naphthalene-1,2-dicarboxyl Anhydride (4-(2,5-dioxotetrahydrofuran-3-yl)-tetralin-1,2-dicarboxylic anhydride), bicyclooctene-2,3,5,6-tetracarboxylic dianhydride, bicyclooctene-1, 2,4,5-tetracarboxylic dianhydride and the like, but not limited thereto.

For example, the alkali-soluble resin may be polyhydroxyamide resin.

The alkali-soluble resin may have a weight average molecular weight (Mw) of 3,000 g/mol to 300,000 g/mol, and specifically 5,000 to 30,000 g/mol. When the alkali-soluble resin has a weight average molecular weight (Mw) within the range, during development with an aqueous alkali solution, a sufficient film residual rate can be obtained in the non-exposed portion, and effective patterning can be performed. ( B ) Photosensitive diazoquinone compound

The photosensitive diazoquinone compound may be a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure.

The photosensitive diazoquinone compound may include at least one selected from the compounds represented by Chemical Formula 11 and Chemical Formula 13 to Chemical Formula 15, but is not limited thereto.

在化學式11中， R³¹ 到R³³ 各自獨立地為氫原子或取代或未取代的烷基，且具體地說CH₃ , D¹ 到D³ 各自獨立地為OQ，其中Q是氫、由化學式12a表示的官能基或由化學式12b表示的官能基，其限制條件為Q不能同時是氫，且 n31到n33各自獨立地為1到5的整數。[Chemical Formula 11]

In Chemical Formula 11, R ³¹ to R ³³ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group, and specifically CH ₃ , D ¹ to D ³ are each independently OQ, where Q is hydrogen, by the chemical formula The functional group represented by 12a or the functional group represented by Chemical Formula 12b has a limitation that Q cannot be hydrogen at the same time, and n31 to n33 are each independently an integer of 1 to 5.

[化學式12b]

[Chemical Formula 12a]

[Chemical Formula 12b]

在化學式13中， R³⁴ 是氫原子或取代或未取代的烷基， D⁴ 到D⁶ 各自獨立地為OQ，其中Q可與在化學式11中定義的相同，以及 n34到n36各自獨立地為1到5的整數。[Chemical Formula 13]

In Chemical Formula 13, R ³⁴ is a hydrogen atom or a substituted or unsubstituted alkyl, D ⁴ to D ⁶ are each independently OQ, where Q may be the same as defined in Chemical Formula 11, and n34 to n36 are each independently An integer from 1 to 5.

在化學式14中， A₃ 為CO或CR⁵⁰⁰ R⁵⁰¹ ，其中R⁵⁰⁰ 和R⁵⁰¹ 各自獨立地為取代或未取代的烷基， D⁷ 到D¹⁰ 各自獨立地為氫原子、取代或未取代的烷基、OQ或NHQ，其中Q與在化學式11中定義的相同， n37、n38、n39以及n40各自獨立地為1到4的整數，以及 n37+n38和n39+n40各自獨立地為低於或等於5的整數， 其限制條件為D7到D10中的至少一個為OQ，且一芳族環包含一個到三個OQ，且另一芳族環包含一個到四個OQ。[Chemical Formula 14]

In Chemical Formula 14, A ₃ is CO or CR ⁵⁰⁰ R ⁵⁰¹ , wherein R ⁵⁰⁰ and R ⁵⁰¹ are each independently a substituted or unsubstituted alkyl group, and D ⁷ to D ¹⁰ are each independently a hydrogen atom, substituted or unsubstituted Alkyl, OQ, or NHQ, where Q is the same as defined in Chemical Formula 11, n37, n38, n39, and n40 are each independently an integer of 1 to 4, and n37+n38 and n39+n40 are each independently lower than or An integer equal to 5, with the restriction that at least one of D7 to D10 is OQ, and one aromatic ring contains one to three OQs, and the other aromatic ring contains one to four OQs.

在化學式15中， R₃₅ 到R₄₂ 各自獨立地為氫原子或取代或未取代的烷基， n41和n42各自獨立地為1到5，且具體地說2到4的整數，以及 Q與在化學式11中定義的相同。[Chemical Formula 15]

In Chemical Formula 15, R ₃₅ to R ₄₂ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group, n41 and n42 are each independently an integer of 1 to 5, and specifically an integer of 2 to 4, and Q and The same is defined in Chemical Formula 11.

The photosensitive diazoquinone compound may be included in an amount of 1 part by weight to 100 parts by weight, for example, 5 parts by weight to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the photosensitive diazoquinone compound within the above range is included, a pattern is formed well without residue from exposure, and a film thickness loss during development can be prevented and thus a good pattern can be obtained. ( D ) Solvent

The photosensitive resin composition may contain a solvent capable of easily dissolving each of the following components: an alkali-soluble resin, a photosensitive diazoquinone compound, a dissolution control agent containing a first phenolic resin and a second phenolic resin, and the like.

The solvent may be an organic solvent, specifically N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethyl sulfoxide, diglyme, diglyme Alcohol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-extension Butyl glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate or a combination thereof, but not Limited to this.

The solvent can be appropriately selected according to the process of forming the photosensitive resin layer (such as spin coating, slit die coating, and the like).

The solvent may be included in an amount of 100 parts by weight to 500 parts by weight, for example, 100 parts by weight to 400 parts by weight based on 100 parts by weight of alkali-soluble resin. When a solvent within the above range is included, the coating layer may have a sufficient thickness, and excellent solubility and coating characteristics are improved. ( F ) Other additives

The photosensitive resin composition according to the embodiment may further contain other additives.

The photosensitive resin composition may include the following additives: a dissolution control agent having a different structure from the first phenolic resin and the second phenolic resin, a sensitivity enhancer, a crosslinking agent, a diacid (such as malonic acid), and an alkanolamine (such as 3-amino-1,2-propanediol), leveling agent, coupling agent, surfactant, epoxy compound, free radical polymerization initiator, thermal latent acid generator or a combination thereof in order to prevent the film during coating To improve the leveling characteristics or to prevent residues caused by non-development. The amount of additives used can be controlled depending on the desired characteristics.

For example, the coupling agent may have reactive substituents, such as vinyl groups, carboxyl groups, methacryloyloxy groups, isocyanate groups, epoxy groups, and the like, to improve close contact characteristics with the substrate.

Examples of the coupling agent may be trimethoxysilyl benzoic acid, γ-methacryl propyl propyl trimethoxy silane, vinyl triethoxy silane, vinyl trimethoxy silane, γ-isocyanate propyl Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like, and can be used alone or in two or Use in the form of a mixture of more than two.

The coupling agent may be used in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When a coupling agent within the above range is included, intimate contact characteristics, storage capacity, and similar characteristics are improved.

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

Examples of the fluorine-based surfactant may be commercially available fluorine-based surfactants, such as BM-1000 ^® and BM-1100 ^{® of} BM Chemie Inc.; Dainippon Ink Kagaku Kogyo Co., Ltd's MEGAFACE F 142D ^® , McFee F 172 ^® , McFee F 173 ^® , McFee F 183 ^® and McFee F 554 ^® ; Sumitomo 3M Co., Ltd.'s FULORAD FC-135 ^® , Fullerard FC-170C ^® , Fullerard FC-430 ^® and Fullerard FC- 431 ^® ; Asahi Glass Co., Ltd.'s SURFLON S-112 ^® , Solon S-113 ^® , Solon S-131 ^® , Solon S-141 ^® and Solon S -145 ^® ; Toray Silicone Co., Ltd. (Toray Silicone Co., Ltd.) SH-28PA ^® , SH-190 ^® , SH-193 ^® , SZ-6032 ^® and SF-8428 ^® , and the like.

The silicone surfactant may be BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052 and BYK Chem. , BIK-053, BIK-067A, BIK-077, BIK-301, BIK-322, BIK-325 and the like.

The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When a surfactant within the above range is included, coating uniformity can be ensured, strain may not be generated and wetting on the ITO substrate or glass substrate is improved.

The photosensitive resin composition may further contain an epoxy compound and the like for improving intimate contact force as additives. The epoxy compound may be epoxy novolac propylene carboxylate resin, o-cresol novolac epoxy resin, phenol novolac epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A epoxy resin, alicyclic epoxy resin Or a combination thereof.

When the epoxy compound is further contained, it may further contain a radical polymerization initiator, such as a peroxide initiator or an azo-bis-type initiator.

The epoxy compound may 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 within the range is included, the storage capacity, close contact force, and other characteristics can be improved.

The photosensitive resin composition may further contain a thermal latent acid generator. Examples of the thermal latent acid generator may be: arylsulfonic acid, such as p-toluenesulfonic acid or benzenesulfonic acid; perfluoroalkylsulfonic acid, such as trifluoromethanesulfonic acid or trifluorobutanesulfonic acid; alkylsulfonic acid, Such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid; or a combination thereof, but not limited thereto.

The thermal latent acid generator is a catalyst for the dehydration reaction and cyclization reaction of polybenzoxazole precursors (that is, polyamide containing phenolic hydroxyl groups), and therefore, even if the curing temperature is lowered, the cyclization reaction can proceed smoothly.

In addition, unless the characteristics are degraded, the photosensitive resin composition according to the embodiment may further contain a predetermined amount of other additives, such as antioxidants, stabilizers, and the like.

Another embodiment provides a photosensitive resin layer manufactured by exposing, developing, and curing the aforementioned photosensitive resin composition.

Another embodiment provides an electronic device including a photosensitive resin layer.

The electronic device may be a semiconductor device.

The method of manufacturing the photosensitive resin layer is as follows.

(1) Coating and layer formation

Using a spin coating or slot coating method, a roll coating method, a screen printing method, an applicator method, and the like, a photosensitive resin composition having a desired thickness is coated on a substrate subjected to a predetermined pretreatment, such as a glass substrate Or ITO substrate. Subsequently, the coated substrate is heated at a temperature ranging from 70°C to 150°C for 1 minute to 10 minutes, thereby removing the solvent and forming a layer.

(2) Exposure

After placing a mask having a predetermined shape to form a desired pattern, the obtained photosensitive resin layer is irradiated with active rays of 200 nm to 500 nm. The radiation is performed by using a light source such as a mercury lamp with a low pressure, a high pressure, or an ultra high pressure, a metal halide lamp, an argon laser, and the like. X-rays, electron beams, and the like can also be used as needed.

The exposure dose varies depending on the type of each component of the composition, its combination ratio, and dry film thickness, but when using a high-pressure mercury lamp, the exposure dose is less than or equal to 500 millijoules/cm ² (mJ/cm ² ) ( According to 365 nanometer sensor).

(3) Development

In the development method, after the exposure step, the exposed portion is dissolved and removed by using a developing solution to leave only the non-exposed portion to obtain a pattern.

(4) Post-process process

The image pattern obtained by development in the above process is post-heated in order to obtain a pattern having improved heat resistance, light resistance, intimate contact characteristics, crack resistance, chemical resistance, high strength, and storage stability. For example, after development, the pattern may be heated at 250°C for 1 hour in a convection oven.

In the following, the invention is explained in more detail with reference to examples. However, these examples should not be construed as limiting the scope of the present invention in any sense. (Example) (Synthesis of alkali soluble resin)

Dissolve 12.4 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane in 125 g of N-methyl in a four-necked flask In N-2-methylpyrrolidone (N-methyl-2-pyrrolidone; NMP), the flask is equipped with a stirrer, a temperature controller, a nitrogen injector, and a condenser, while nitrogen is passed therethrough.

When the solid is completely dissolved, 4.2 g of pyridine is added to it as a catalyst, and, when the temperature is maintained at 0°C to 5°C, by dissolving 9.4 g of 4,4'-oxydibenzoyl chloride in 100 The solution prepared in grams of NMP was slowly added dropwise to it for 30 minutes. When the addition is completed, the obtained mixture is reacted at 0°C to 5°C for 1 hour, and after increasing the temperature to room temperature, the reaction is performed for one hour.

Subsequently, 1.1 g of 5-norbornene-2,3-dicarboxyl anhydride (5-norbornene-2,3-dicarboxyl anhydride) was added thereto, and the obtained mixture was stirred at 70°C for 24 hours to complete the reaction . The reaction mixture was put into a solution of water/methanol = 10/1 (volume ratio) to produce a precipitate, and the precipitate was filtered, washed thoroughly, and dried under vacuum at 80° C. for greater than or equal to 24 hours, thereby Polyhydroxyamide resin was obtained. (Polymerization of dissolution control agent)

Polymerization Example 1: First phenolic resin

At 70°C, add 1.00 mol of m-cresol, 1.50 mol of p-cresol, 1.25 mol of salicylic acid, 0.002 mol of p-toluenesulfonic acid monohydrate, and 100 grams of propylene glycol monomethyl ether in Mix and stir in a 1.0 liter flask to obtain a mixed solution (reaction solution). The obtained reaction solution was heated to 120°C in an oil bath. The reaction solution was continuously stirred at 120°C for 5 hours and then cooled to 60°C. When the reaction is complete, a mixture of water and methanol is used to remove the acid.

Polymerization Example 2: Second phenolic resin

At 70°C, 1.00 mol of m-cresol, 1.50 mol of p-cresol, 0.50 mol of salicylic acid, 0.75 mol of formaldehyde, 0.002 mol of p-toluenesulfonic acid monohydrate and 100 g of Propylene glycol monomethyl ether was mixed and stirred in a 1.0 liter flask to dissolve solids and obtain a mixed solution (reaction solution). The obtained reaction solution was heated to 120°C in an oil bath. The reaction solution was continuously stirred at 120°C for 5 hours and then cooled to 60°C. When the reaction is complete, a mixture of water and methanol is used to remove the acid. (Preparation of photosensitive resin composition) Examples 1 to 4 and Comparative Examples 1 to 4

100 grams of polyhydroxyamide resin was dissolved in 300 grams of gamma (gamma) butyrolactone (GBL) solvent, and 30 grams of photosensitive diazoquinone compound (MIPHOTO TPD425, Miwon Commercial Co., Ltd.) Co., Ltd.)), the first phenol resin and the second phenol resin in the weight ratio shown in Table 1 are dissolved therein, and then stirred until the solution becomes uniform under yellow light. Next, the resulting solution was filtered using a 0.20 micron fluororesin screening program to obtain a photosensitive resin composition.

評估 [Table 1]

Assessment

The photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 4 were coated on aluminum-deposited wafers, respectively, and heated (cured) on a 120° C. hot plate for 4 minutes to form 10 μm thick Cured film. The film residual rate, sensitivity, and residual characteristics of the cured film were evaluated, and the results are shown in Table 2.

(Evaluation 1: membrane residual rate)

The thickness difference before/after development is calculated as% to obtain the film residual rate.

(Evaluation 2: Sensitivity)

After development, the exposure dose showing a 7 micron pattern size was calculated as the sensitivity.

(Evaluation 3: Residue (scum)) O: After development, no composition remains in the perforation pattern. X: After development, there is a composition remaining in the perforation pattern.

[Table 2]

Referring to Table 1, a photosensitive resin composition according to an embodiment of the present invention can be used as a predetermined ratio using a first phenol resin containing a structural unit represented by Chemical Formula 1 and a second phenol resin containing a structural unit represented by Chemical Formula 2 as Dissolution control agent to improve both sensitivity and residual characteristics, as well as maintain excellent film residual rate.

Although the present invention has been described in conjunction with what is currently regarded as a practical exemplary embodiment, it should be understood that the present invention is not limited to the disclosed embodiments, but on the contrary, the present invention is intended to cover the spirit and spirit contained in the appended claims. Various modifications and equivalent arrangements within the scope. Therefore, the above-mentioned embodiments should be understood as exemplary but do not limit the present invention in any way.

no.

no.

Claims (8)

A photosensitive resin composition, including: (A) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a dissolution control agent, including a first phenolic resin represented by Chemical Formula 1 and a second resin represented by Chemical Formula 2 Diphenol resin; and (D) a solvent, wherein the first phenol resin and the second phenol resin are contained in a weight ratio of 10:90 to 30:70: [Chemical Formula 1]

[Chemical Formula 2]

Wherein, in Chemical Formula 1 and Chemical Formula 2, R ¹ to R ³ are each independently a hydroxyl group or a substituted or unsubstituted C1 to C5 alkyl group, p, q and r are each independently an integer ranging from 0 to 3, and a, b, and c are each independently a positive integer. The photosensitive resin composition as described in item 1 of the patent application range, wherein the second phenolic resin is a block copolymer, a substitute copolymer, or a random copolymer. The photosensitive resin composition as described in item 1 of the patent application range, wherein the dissolution control agent is contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin. The photosensitive resin composition as described in item 1 of the patent application range, wherein the alkali-soluble resin is a polyhydroxyamide resin. The photosensitive resin composition as described in item 1 of the patent application scope, wherein the photosensitive resin composition includes Based on 100 parts by weight of the alkali-soluble resin, 1 part by weight to 100 parts by weight of the photosensitive diazoquinone compound, 0.1 parts by weight to 20 parts by weight of the dissolution control agent, and 100 parts by weight to 500 parts by weight of the solvent. The photosensitive resin composition as described in item 1 of the patent application range, wherein the photosensitive resin composition further includes the following additives: a dissolution control agent having a different structure from the first phenolic resin and the second phenolic resin , Sensitivity enhancer, crosslinking agent, diacid, alkanolamine, leveling agent, coupling agent, surfactant, epoxy compound, free radical polymerization initiator, thermal latent acid generator or a combination thereof. A photosensitive resin layer manufactured using the photosensitive resin composition as described in any one of claims 1 to 6. An electronic device includes a photosensitive resin layer as described in item 7 of the patent application.