KR20140086733A

KR20140086733A - Positive photosensitive resin composition, insulating film using the same, and display device including the insulating film

Info

Publication number: KR20140086733A
Application number: KR1020120157573A
Authority: KR
Inventors: 권지윤; 강진희; 김대윤; 김상권; 김상수; 김용태; 노건배; 박은비; 송재환; 윤은경; 이종화; 이진영; 홍충범; 황은하; 황인철
Original assignee: 제일모직주식회사
Priority date: 2012-12-28
Filing date: 2012-12-28
Publication date: 2014-07-08

Abstract

(A) an alkali-soluble resin comprising a polybenzoxazole precursor, a polyamic acid, a polyimide, or a combination thereof; (B) a photosensitive diazoquinone compound; (C) an acrylic binder containing a repeating unit derived from a dioxolane-based compound represented by the following formula (10); And (D) a solvent, an insulating film using the same, and a display device including the same.
[Chemical formula 10]

(Wherein each substituent is as defined in the specification).

Description

FIELD OF THE INVENTION [0001] The present invention relates to a positive photosensitive resin composition, an insulating film using the positive photosensitive resin composition, and a display device including the insulating film. &Lt; Desc / Clms Page number 1 >

The present invention relates to a positive photosensitive resin composition, an insulating film using the same, and a display device including the insulating film.

BACKGROUND ART Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, and mechanical properties have been used as surface protective films and interlayer insulating films of semiconductor devices. Such a polyimide resin has recently been used in the form of a photosensitive polyimide precursor composition and is easy to apply. After coating the polyimide precursor composition on a semiconductor device, patterning with ultraviolet rays, development, thermal imidization treatment, A protective film, an interlayer insulating film and the like can be easily formed. Accordingly, the process time can be shortened compared with the conventional non-photosensitive polyimide precursor composition.

The photosensitive polyimide precursor composition has a positive type in which the exposed portion is dissolved by development and a negative type in which the exposed portion is cured, and in the case of the positive type, a non-toxic alkaline aqueous solution can be used as a developer. The positive photosensitive polyimide precursor composition includes polyamic acid which is a polyimide precursor, diazonaphthoquinone which is a photosensitive material, and the like. However, the positive photosensitive polyimide precursor composition has a problem that a desired pattern can not be obtained because the solubility of the carboxylic acid of the polyamic acid used in the alkali is too high.

In order to solve this problem, a material obtained by mixing a polyazooxazole precursor with a diazonaphthoquinone compound has attracted attention recently. However, when the polybenzoxazole precursor composition is actually used, the film thickness of the unexposed portion at the time of development is large. Patterns are difficult to obtain. If the molecular weight of the polybenzoxazole precursor is increased, the amount of decrease in the film thickness of the unexposed portion is reduced. However, a phenomenon (scum) is generated in the exposure portion during development, resulting in poor resolution and a longer development time of the exposed portion have.

To solve this problem, it has been reported that by adding a specific phenol compound to the polybenzoxazole precursor composition, the amount of reduction of the film in the unexposed portion at the time of development is suppressed. However, this method has insufficient effect of suppressing the amount of reduction of the unexposed portion, and therefore, there is a continuing need for research to increase the effect of inhibiting the film reduction without generating a developing residue (scum). In addition, since the phenolic compound used for controlling the solubility causes problems such as decomposition at a high temperature during thermal curing or side reaction, resulting in a large damage to the mechanical properties of the cured film, a dissolution inhibitor Research is also required.

Such a polyimide precursor composition or polybenzoxazole precursor composition has a limitation in adhesion with a metal interface or the like. In addition, the polybenzoxazole precursor composition having a low viscosity has a problem in that it exhibits excellent developability and sensitivity but exhibits brittle fracture due to a decrease in the elasticity of the thin film. Therefore, there is a need for research on a method for improving the adhesion and complementing the embrittlement.

One embodiment of the present invention is to provide a positive photosensitive resin composition having excellent heat resistance and adhesion and improved brittleness.

Another embodiment of the present invention is to provide an insulating film using the above positive photosensitive resin composition.

Another embodiment of the present invention is to provide a display device including the insulating film.

One embodiment of the present invention is directed to a composition comprising: (A) an alkali-soluble resin comprising a polybenzoxazole precursor, a polyamic acid, a polyimide, or a combination thereof; (B) a photosensitive diazoquinone compound; (C) an acrylic binder containing a repeating unit derived from a dioxolane-based compound represented by the following formula (10); And (D) a solvent.

[Chemical formula 10]

In Formula 10,

R ¹ and R ² are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, Or a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, Or a cyclic hydrocarbon in which R < ¹ > and R < ² > are linked together to form a cyclic hydrocarbon,

R ³ and R ⁴ are the same or different and are each independently hydrogen or a substituted or unsubstituted C 1 to C 20 alkyl group, R ⁵ is hydrogen or a methyl group, and n is an integer of 1 to 5.

The acrylic binder (C) may further include a repeating unit derived from an unsaturated carboxylic acid compound.

The acrylic binder (C) may further include at least one of a repeating unit derived from an epoxy group-containing unsaturated compound and a repeating unit derived from a phenylmaleimide-based compound.

The content of the acrylic binder (C) may be 5 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

The content of the acrylic binder (C) may be 5 to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

Wherein the positive photosensitive resin composition comprises 5 to 100 parts by weight of the photosensitive diazoquinone compound (B) per 100 parts by weight of the alkali-soluble resin (A); 5 to 30 parts by weight of the (C) acrylic binder; And 100 to 900 parts by weight of the above (D) solvent.

The positive photosensitive resin composition may further include a silane compound.

The positive photosensitive resin composition may further comprise a phenol compound.

Another embodiment of the present invention provides an insulating film using the positive photosensitive resin composition.

According to another embodiment of the present invention, there is provided a display device including the insulating film.

The positive-working photosensitive resin composition according to one embodiment of the present invention is excellent in heat resistance and adhesiveness and is complemented with brittle brittleness, and is suitable for application to a photosensitive resin film and a display device containing the same.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Means that at least one hydrogen atom of the functional group of the present invention is substituted with a halogen atom (-F, -Cl, -Br or -I), a hydroxy group, a nitro group, An amino group (NH ₂ , NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ) in which R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other and are each independently a Cl to C10 alkyl group) A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, A substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group.

Unless otherwise specified in the specification, "alkyl group" means C1 to C30 alkyl group, specifically C1 to C15 alkyl group, "cycloalkyl group" means C3 to C30 cycloalkyl group, specifically C3 Refers to a C1 to C30 alkoxy group, specifically, a C1 to C18 alkoxy group, and an "aryl group" means a C6 to C30 aryl group, specifically, a C6 to C30 aryl group, C18 aryl group, "alkenyl group" means C2 to C30 alkenyl group, specifically C2 to C18 alkenyl group, "alkylene group" means C1 to C30 alkylene group, specifically C1 Means a C6 to C30 arylene group, and specifically refers to a C6 to C16 arylene group.

Unless otherwise specified in the present specification, the term "aliphatic organic group" means a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C1 to C30 alkylene group, a C2 to C30 alkenylene group, Means a C1 to C15 alkyl group, a C2 to C15 alkenyl group, a C2 to C15 alkynyl group, a C1 to C15 alkylene group, a C2 to C15 alkenylene group, or a C2 to C15 alkynylene group, Means a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, a C3 to C30 cycloalkynyl group, a C3 to C30 cycloalkylene group, a C3 to C30 cycloalkenylene group, or a C3 to C30 cycloalkynylene group. C3 to C15 cycloalkenyl groups, C3 to C15 cycloalkynyl groups, C3 to C15 cycloalkylene groups, C3 to C15 cycloalkenylene groups, Means a C6 to C30 aryl group or a C6 to C30 arylene group, specifically, a C6 to C16 aryl group or a C6 to C16 arylene group, and the term " aromatic hydrocarbon group " The "heterocyclic group" means a C2 to C30 heterocycloalkyl group containing 1 to 3 hetero atoms selected from the group consisting of O, S, N, P, Si and combinations thereof in one ring, C2 to C30 hetero A C2 to C30 heterocycloalkenyl group, a C2 to C30 heterocycloalkenylene group, a C2 to C30 heterocycloalkynyl group, a C2 to C30 heterocycloalkynylene group, a C2 to C30 heteroaryl group, or a C2 to C30 hetero Means an arylene group, and specifically includes 1 to 3 hetero atoms selected from the group consisting of O, S, N, P, Si, and combinations thereof in one ring A C2 to C15 heterocycloalkylene group, a C2 to C15 heterocycloalkylene group, a C2 to C15 heterocycloalkenyl group, a C2 to C15 heterocycloalkenylene group, a C2 to C15 heterocycloalkynyl group, a C2 to C15 heterocycloalkynylene group, a C2 to C15 heterocycloalkylene group, To C15 heteroaryl groups, or C2 to C15 heteroarylene groups.

One embodiment of the present invention is directed to a composition comprising: (A) an alkali-soluble resin comprising a polybenzoxazole precursor, a polyamic acid, a polyimide, or a combination thereof; (B) a photosensitive diazoquinone compound; (C) an acrylic binder containing a repeating unit derived from a dioxolane-based compound represented by the general formula (10); And (D) a solvent.

The positive photosensitive resin composition includes, for example, 5 to 100 parts by weight of the photosensitive diazoquinone compound (B) per 100 parts by weight of the alkali-soluble resin (A) 5 to 30 parts by weight of the (C) acrylic binder; And 100 to 900 parts by weight of the above (D) solvent.

Hereinafter, each constitution of the positive photosensitive resin composition will be described in detail.

(A) an alkali-soluble resin

The alkali-soluble resin (A) comprises a polybenzoxazole precursor containing a repeating unit represented by the formula (1), a polyamic acid containing a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula At least one selected from polyimide can be used.

Polybenzoxazole Precursor

[Chemical Formula 1]

Wherein X ¹ is a substituted or unsubstituted C6 to C30 aromatic organic group, Y ¹ is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic Or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group.

In the above formula (1), X ¹ is an aromatic organic group and may be a residue derived from an aromatic diamine.

Examples of the aromatic diamine include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2- Hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2- (3-amino-4-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis , 2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2- rope (4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis Phenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- 2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- 2- (3-amino-4-amino-6-trifluoromethylphenyl) hexafluoropropane, 2- 2-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-2-trifluoromethylphenyl) Methylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane and 2- Hydroxy-6-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane may be used, It is not.

In formula (1), Y ¹ is an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent alicyclic group, and may be a residue of a dicarboxylic acid or a residue of a dicarboxylic acid derivative. Specifically, Y ¹ may be an aromatic organic group, or a divalent to hexavalent alicyclic organic group.

Examples of the dicarboxylic acids may be mentioned Y ¹ (COOH) ₂ (where Y ¹ is the same as Y ¹ in the formula (1)).

Examples of the di-carboxylic acid derivatives is Y ¹ (COOH) ₂ of the carbonyl halide derivative, or Y ¹ (COOH) ₂ and 1-hydroxy-1,2,3-benzotriazole-active ester derivative by reacting a sol such as the active compounds may be mentioned (wherein Y ¹ is the same hereinafter as Y ¹ in the formula (1)).

Specific examples of the dicarboxylic acid derivative include 4,4'-oxydibenzoyl chloride, diphenyloxydicarbonyldichloride, bis (phenylcarbonyl chloride) sulfone, bis (phenylcarbonyl chloride) ether, bis (phenylcarbonyl chloride ) Phenone, phthaloyldichloride, terephthaloyldichloride, isophthaloyldichloride, dicarbonyldichloride, diphenyloxydicarboxylate dibenzotriazole, or combinations thereof, but is not limited thereto.

The polybenzoxazole precursor may have a thermally polymerizable functional group derived from a reactive end blocking monomer on either or both of the branched chain terminals. The reactive end blocking monomer is preferably a monoamine having a carbon-carbon double bond or a monoanhydride, or a combination thereof. Examples of the monoamines include, but are not limited to, toluidine, dimethyl aniline, ethyl aniline, aminophenol, aminobenzyl alcohol, aminoindan, aminoacetone phenone, and combinations thereof.

Polyamic acid And polyimide

(2)

(3)

X ² and X ³ are each independently a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, a substituted or unsubstituted A divalent to hexavalent C3 to C30 alicyclic organic group, or an organosilane group.

Specifically, in the formulas (2) and (3), X ² and X ³ may each independently be a residue derived from an aromatic diamine, an alicyclic diamine, or a silicone diamine. At this time, the aromatic diamine, alicyclic diamine and silicon diamine may be used singly or in combination of one or more thereof.

Examples of the aromatic diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine , Bis [4- (4-aminophenoxy) phenyl] sulfone, bis (4-aminophenoxy) ] Ether, 1,4-bis (4-aminophenoxy) benzene, a compound in which the aromatic ring thereof is substituted with an alkyl group or a halogen atom, or a combination thereof, but is not limited thereto.

Examples of the alicyclic diamine include, but are not limited to, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, or a combination thereof.

Examples of the silicon diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p- aminophenyl) tetramethyldisiloxane, Bis (? -Aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (? -Aminopropyl) tetraphenyldisiloxane, 1,3- Methyldisiloxane, or combinations thereof, but are not limited thereto.

Y ² and Y ³ are each independently a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted quadrivalent to hexavalent C1 to C30 aliphatic group, Is a C4 to C20 alicyclic organic group.

Y ² and Y ³ may each independently be an aromatic acid dianhydride or a residue derived from an alicyclic acid anhydride. At this time, the aromatic acid dianhydride and the alicyclic acid dianhydride may be used alone or in admixture of at least one thereof.

Examples of the aromatic acid dianhydride include pyromellitic dianhydride; Benzophenone tetracarboxylic dianhydride such as benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3'4,4'-tetracarboxylic dianhydride, ; Oxydiphthalic dianhydride such as 4,4'-oxydiphthalic dianhydride; Biphthalic dianhydride such as 3,3 ', 4,4'-biphthalic dianhydride (3,3', 4,4'-biphthalic dianhydride); (Hexafluoroisopropylidene) diphthalic dianhydride such as 4,4 '- (hexafluoroisopropylidene) diphthalic dianhydride (4,4' - (hexafluoroisopropylidene) diphthalic dianhydride) ; Naphthalene-1,4,5,8-tetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic dianhydride, and the like, but the present invention is not limited thereto.

Examples of the alicyclic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexane-1,2-dicarboxylic acid dianhydride (5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexane-1,2-dicarboxylic anhydride), 4- (2,5- dioxotetrahydrofuran-3-yl) -tetralin- (2,5-dioxotetrahydrofuran-3-yl) -tetralin-1,2-dicarboxylic anhydride, bicyclooctene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5,6-tetracarboxylic dianhydride, bicyclooctene-1,2,4,5-tetracarboxylic dianhydride, and the like. But is not limited thereto.

The alkali-soluble resin may have a weight average molecular weight (Mw) of 5,000 to 20,000 g / mol, and specifically a weight average molecular weight (Mw) of 6,000 to 10,000 g / mol. When the weight average molecular weight (Mw) is within the above range, a sufficient residual film ratio can be obtained in an unexposed area at the time of development with an aqueous alkali solution, and patterning can be efficiently 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 be at least one selected from compounds represented by the following formulas (4) and (6) to (8), but is not limited thereto.

[Chemical Formula 4]

In the general formula (4), R ⁶⁰ to R ⁶² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, and specifically may be a methyl group.

In Formula 4, R ⁶³ to R ⁶⁵ are each independently OQ, and Q is a hydrogen atom, a functional group represented by the following Formula 5a or a functional group represented by the following Formula 5b, wherein Q can not be hydrogen at the same time.

In Formula 4, n ²⁰ to n ²² may each be an integer of 0 to 5.

[Chemical Formula 5a]

[Chemical Formula 5b]

[Chemical Formula 6]

Wherein R ⁶⁶ is a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, R ⁶⁷ to R ⁶⁹ are each independently OQ, Q is the same as defined above, n ²³ To n ²⁵ each may be an integer of 0 to 5.

(7)

In Formula 7, A ³ is CO or CR ⁷⁴ R ⁷⁵ , R ⁷⁴ And R ⁷⁵ are each independently a substituted or unsubstituted C1 to C30 alkyl group.

In Formula 7, R ⁷⁰ to R ⁷³ each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, OQ or NHQ, and Q is the same as defined above.

N ²⁶ to n ²⁹ are each an integer of 0 to 4, and n ²⁶ + n ²⁷ and n ²⁸ + n ²⁹ are an integer of 5 or less, respectively.

Provided that at least one of R ⁷⁰ and R ⁷¹ is OQ, one to three OQs may be contained in one aromatic ring, and one to four OQs may be contained in another aromatic ring.

[Chemical Formula 8]

In Formula 8,

And R ⁷⁴ to R ⁸¹ is a C1 to C30 alkyl groups each independently represent a hydrogen atom or a substituted or unsubstituted, and n ³⁰ and n ³¹ is an integer from 1 to 5, respectively, the same as that of Q are defined above.

The photosensitive diazoquinone compound may be included in the positive photosensitive resin composition in an amount of 5 to 100 parts by weight, specifically 10 to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When it is included in the above range, the pattern can be formed well with no residue by exposure, and a good pattern can be obtained without loss of film thickness upon development.

(C) Acrylic binder

The positive photosensitive resin composition according to one embodiment includes an acrylic binder (C). The acrylic binder includes a repeating unit derived from a dioxolane-based compound represented by the following general formula (10). In this case, the positive photosensitive resin composition can secure excellent heat resistance, improve adhesion, and improve brittleness.

[Chemical formula 10]

In Formula 10,

R ¹ and R ² are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, Or a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, Or a cyclic hydrocarbon in which R < ¹ > and R < ² > are linked to each other to form a ring.

For example, R ¹ and R ² may each be a C1 to C10 chain alkyl group.

In another example, R ¹ and R ² may be connected to each other to form a cyclic hydrocarbon having a ring, such as pentagonal, hexagonal, and hexagonal, and may be a C3 to C10 cycloalkyl group.

The acrylic binder forms a three-dimensional network structure after thermosetting, and thus can properly entangle with the main chain of the alkali-soluble resin (A) to function as a crosslinking agent. This makes it possible to compensate for brittle fracture.

The acrylic binder (C) may further include a repeating unit derived from an unsaturated carboxylic acid compound. In this case, the positive photosensitive resin composition can improve the adhesiveness and can effectively compensate the brittleness.

The unsaturated carboxylic acid-based compounds include, for example, unsaturated monocarboxylic acids of acrylic acid or methacrylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; Unsaturated dicarboxylic acid anhydrides; Or a combination thereof.

The content of the repeating unit derived from the unsaturated carboxylic acid compound may be 5 to 60 wt%, preferably 10 to 30 wt%, based on the total amount of the acrylic binder (C). In the above range, the positive photosensitive resin composition can improve the adhesiveness and effectively compensate the brittleness.

The acrylic binder (C) may further contain a repeating unit derived from an epoxy group-containing unsaturated compound. In this case, the positive-working photosensitive resin composition can improve the adhesiveness and improve the heat resistance.

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethylacrylate, glycidyl? -N-propyl acrylate, glycidyl? -N-butyl acrylate, ? -methyl glycidyl, methacrylic acid -? - methyl glycidyl, acrylic acid? - ethyl glycidyl, or methacrylic acid -? - ethyl glycidyl acrylate; Vinylbenzyl glycidyl ethers of acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, or p-vinylbenzyl glycidyl ether; Or a combination thereof.

The content of the repeating unit derived from the epoxy group-containing unsaturated compound may be 5 to 60% by weight, specifically 5 to 30% by weight based on the total amount of the acrylic binder (C). In the above range, the adhesive property and the heat resistance can be improved. 　

The tacky acrylic binder (C) may further include at least one of repeating units derived from a phenylmaleimide-based compound. In this case, the positive photosensitive resin composition can secure excellent heat resistance and coloring property.

The phenylmaleimide compound may specifically be a compound represented by the following formula (11).

(11)

In Formula 11,

R ⁶ is a hydroxyl group or a carboxyl group, and n 1 is an integer of 1 to 5.

Specific examples of the phenylmaleimide-based compound include 4-hydroxyphenylmaleimide or 4-carboxyphenylmaleimide. The content of the repeating unit derived from the phenylmaleimide-based compound may be 5 to 60% by weight, specifically 5 to 30% by weight based on the total amount of the acrylic binder (C). In this case, the chemical resistance and heat resistance of the developer of the acrylic binder (C) are improved.

The acrylic binder (C) may be contained in the positive photosensitive resin composition in an amount of 5 to 30 parts by weight, specifically 5 to 10 parts by weight, based on 100 parts by weight of the alkali-soluble resin. In this case, the positive photosensitive resin composition can secure balance of physical properties such as heat resistance, improve adhesion and improve brittleness.

(D) Solvent

The positive photosensitive resin composition may include a solvent capable of easily dissolving each component.

Specific examples of the solvent include -methyl-2-pyrrolidone, -butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di Butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate and the like. These solvents may be used alone or in combination of two or more.

The solvent may be included in the positive photosensitive resin composition in an amount of 100 to 900 parts by weight, specifically 200 to 700 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When it is contained within the above range, it is possible to coat a film of sufficient thickness and have good solubility and coating properties.

Specifically, the solvent may be used so that the solid content of the positive photosensitive resin composition is 3 to 50% by weight, specifically 5 to 30% by weight.

(E) Silane compound

The display device positive type resin composition may further include a silane compound. The silane compound can improve adhesion between the positive photosensitive resin composition and the substrate.

Examples of the silane compound include compounds represented by the following general formulas (12) to (14); Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (? -Methoxyethoxy) silane; 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- - methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; And carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy [3- (phenylamino) propyl] silane, but are not limited thereto.

[Chemical Formula 12]

In formula (12), R ²⁰ is a vinyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and specifically, 3- (meth) acryloxypropyl, ) &Lt; / RTI > profile.

In Formula 12, R < ²¹ > To R ²³ are each independently a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, or a halogen, where R ²¹ To R ²³ At least one of them is an alkoxy group or halogen, specifically, the alkoxy group may be a C1 to C8 alkoxy group, and the alkyl group may be a C1 to C20 alkyl group.

[Chemical Formula 13]

Wherein R ²⁴ is -NH ₂ or -CH ₃ CONH, and R ²⁵ to R ²⁷ are each independently a substituted or unsubstituted C 1 to C 20 alkoxy group, specifically, the alkoxy group is OCH ₃ or OCH ₂ CH ₃ , and n ₃₄ may be an integer of 1 to 5.

[Chemical Formula 14]

In Formula 14, R < ²⁸ > To R ³¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 unsubstituted alkoxy groups, specifically, CH ₃ or OCH ₃ Lt; / RTI >

In the above formula (14), R ³² and R ³³ may each independently be a substituted or unsubstituted amino group, and specifically may be NH ₂ or CH ₃ CONH. And n ₃₅ and n ₃₆ may be an integer of 1 to 5, respectively.

The silane compound may be used in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the alkali-soluble resin.

When it is used within the above range, the adhesion to the upper and lower film layers is excellent, and the remaining film is not left after development, and the mechanical properties such as tensile strength, elongation and the like as well as optical characteristics such as transmittance can be improved.

(F) Phenol compound

The positive photosensitive resin composition may further comprise a phenol compound. The phenolic compound can increase the dissolution rate and sensitivity of the exposed portion when developing with an alkaline aqueous solution to form a pattern with the photosensitive resin composition, and can perform patterning at high resolution without developing residue at the time of development.

Examples of the phenol compound include, but are not limited to, compounds represented by the following general formulas (15) to (21).

[Chemical Formula 15]

In Formula 15,

R ₈₂ to R ₈₇ are each independently hydrogen, a hydroxyl group (OH), a C1 to C8 substituted or non-substituted of unsubstituted alkyl group, a C1 to alkoxyalkyl or -OCO-R ₈₈ of C8, R ₈₈ is a substituted C1 to C8 or And at least one of R ₈₂ to R ₈₇ is a hydroxyl group, and not all of them are hydroxyl groups.

[Chemical Formula 16]

In Formula 16,

R ₉₉ to R ₁₀₁ are each independently hydrogen or a substituted or unsubstituted alkyl group having from 1 to 8 carbon atoms, and R ₁₀₂ And to R ₁₀₆ are each independently H, OH, or substituted or unsubstituted alkyl group of C1 to C8, specifically, the alkyl group may be CH _3, n ₆₈ is an integer from 1 to 5.

[Chemical Formula 17]

In Formula 17,

R ₁₀₇ to R ₁₁₂ are each independently H, OH, or a C1 to C8 substituted or unsubstituted alkyl group; A ₃ is CR ₂₀₅ R ₂₀₆ or a single bond; and R ₂₀₅ and R ₂₀₆ are each independently hydrogen, or a C1 to a substituted or unsubstituted alkyl group of C8, specifically, the alkyl group may be _{CH 3, n 69 + n 70} + n 71 And n ₇₂ + n ₇₃ + n ₇₄ are each independently an integer of 5 or less.

[Chemical Formula 18]

In Formula 18,

Each of R < ₁₁₃ > to R < ₁₁₅ > is independently hydrogen or a C1 to C8 substituted or unsubstituted alkyl group; _n75 , _n76 and _n79 are each independently an integer of 1 to 5; _n77 and _n78 are Independently, an integer of 0 to 4;

[Chemical Formula 19]

In the above formula (19)

R ₁₁₆ To R &_lt; ₁₂₁ _> are each independently hydrogen, OH, or a C1 to C8 substituted or unsubstituted alkyl group, and n ₈₀ To n ₈₃ are each independently an integer of 1 to 4; Provided that n ₈₀ + n ₈₂ and n ₈₁ + n ₈₃ are each independently an integer of 5 or less.

[Chemical Formula 20]

In the above formula (20)

R ₁₂₂ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, specifically, CH ₃ , R ₁₂₃ to R ₁₂₅ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and n ₈₄ , n ₈₆ and n ₈₈ are each independently an integer of 1 to 5, and n ₈₅ , n ₈₇ and n ₈₉ are each independently an integer of 0 to 4. Provided that n ₈₄ + n ₈₅ , n ₈₆ + n ₈₇ and n ₈₈ + n ₈₉ each independently represent an integer of 5 or less.

[Chemical Formula 21]

In Formula 21,

R ₁₂₆ to R ₁₂₈ are each independently a substituted or unsubstituted C1 to C8 alkyl group, specifically, CH ₃ , and R ₁₂₉ to R ₁₃₂ are each independently hydrogen or a substituted or unsubstituted C1 to C8 alkyl group, is an alkyl _group, n _90, n ₉₂ and n ₉₄ are each independently in integer of 1 to 5, n _91, n ₉₃ and n ₉₅ are each independently an integer of 0 to 4, n ₉₆ is an integer from 1 to 4 to be. Provided that n ₉₀ + n ₉₁ , n ₉₂ + n ₉₃ and n ₉₄ + n ₉₅ are independently an integer of 5 or less.

Specific examples of the phenol compound include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6- diacetoxymethyl- However, the present invention is not limited thereto.

The amount of the phenol compound may be about 1 to about 30 parts by weight based on 100 parts by weight of the alkali-soluble resin. 　 When the content of the phenol compound is within the above range, a good pattern can be obtained by appropriately increasing the dissolution rate of the unexposed portion without inducing a decrease in sensitivity during development. Further, since the precipitation does not occur during freezing storage, have.

(G) Other additives

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

The positive photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid to prevent spots, spots, leveling, 3-amino-1,2-propanediol; A silane-based coupling agent having a vinyl group or (meth) acryloxy group; And the like. The amount of these additives to be used can be easily controlled depending on the desired physical properties.

The positive-working photosensitive resin composition may further contain an epoxy compound as an additive for the purpose of improving adhesion and the like. Examples of the epoxy compound include epoxy novolac acrylate carboxylate resin, orthocresol novolak epoxy resin, phenol novolak epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, or a combination thereof .

When the epoxy compound is further included, it may further include a radical polymerization initiator such as a peroxide initiator or an azobis-based 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 positive photosensitive resin composition. When the epoxy compound is contained within the above range, the adhesion and other properties can be improved in terms of storage stability and economy.

The method of producing the positive photosensitive resin composition is not particularly limited, but specifically, a positive photosensitive resin composition is prepared by mixing the above-mentioned dye, acrylic binder resin, photopolymerization initiator, photopolymerizable monomer, solvent and optional additives .

Other additives include thermal latent acid generators. Examples of the thermal latent acid generator include arylsulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid and the like; Perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid, trifluorobutanesulfonic acid and the like; Methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid and the like; Or combinations thereof, but are not limited thereto.

The thermal latent acid generator is a catalyst for the dehydration reaction of the phenolic hydroxyl group-containing polyamide of the polybenzoxazole precursor and the cyclization reaction, and the cyclization reaction can proceed smoothly even if the curing temperature is lowered.

Further, a suitable surfactant or leveling agent may be further used as an additive in order to prevent unevenness in film thickness or to improve developability.

The step of forming a pattern using the positive photosensitive resin composition includes a step of applying a positive photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing or the like; Drying the applied positive photosensitive resin composition to form a positive photosensitive resin composition film; Exposing the positive photosensitive resin composition film; Developing the exposed positive photosensitive resin composition film with an alkali aqueous solution to produce an insulating film; And a step of heat-treating the insulating film. The conditions of the process for forming the pattern, and the like are well known in the art, so that detailed description thereof will be omitted herein.

According to another embodiment, there is provided an insulating film produced using the positive photosensitive resin composition.

According to another embodiment, there is provided a display device including the insulating film. The display device may be a liquid crystal display, a light emitting diode, a plasma display, or an organic light emitting diode.

The positive photosensitive resin composition may be useful for forming an insulating film, a passivation layer or a buffer coating layer in a display device. That is, the positive photosensitive resin composition can be usefully used for forming a surface protective film and an interlayer insulating film of a display device.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples and comparative examples are for illustrative purposes only and are not intended to limit the present invention.

Synthetic example One : Polybenzoxazole Preparation of precursor

Bis [[[5- [1- (amino-4-hydroxyphenyl) -2,2,2-trichloroethoxysilane] was added to a four necked flask equipped with a stirrer, a temperature controller, 41.1 g of 2-trifluoro-1- (trifluoromethyl) ethyl] -2-hydroxyphenyl] amino] methyl] -4-methylphenol was dissolved in 280 g of N-methyl-2-pyrrolidone . When the solid is completely dissolved, 9.9 g of pyridine is added to the above solution, and 13.3 g of 4,4'-oxydibenzoyl chloride is added to 142 g of N-methyl-2-pyrrolidone (NMP) Was slowly added dropwise for 30 minutes. After the dropwise addition, the reaction was carried out at 0 to 5 ° C for 1 hour, the temperature was raised to room temperature, and the reaction was terminated by stirring for 1 hour.

To this was added 1.6 g of 5-norbornene-2,3-dicarboxyanhydride and the mixture was stirred at 70 ° C for 24 hours to complete the reaction. The reaction mixture was poured into a solution of water / methanol = 10/1 (by volume) to form a precipitate, and the precipitate was filtered and sufficiently washed with water. And dried at a temperature of 80 캜 under vacuum for at least 24 hours to prepare a polybenzoxazole precursor having a weight average molecular weight of 9,500.

Synthetic example 2: Synthesis of acrylic binder (C-1)

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 2-ethyl-2-methyl- 45 parts by weight of 1,3-dioxolan-4-yl-methylacrylate, 15 parts by weight of methacrylic acid, 20 parts by weight of glycidyl methacrylate and 20 parts by weight of 4-hydroxyphenylmaleimide, RTI ID = 0.0 > C / 5h < / RTI > In order to remove unreacted monomers, 100 parts by weight of the polymer solution was poured into 1,000 parts by weight of an ether bean solvent to precipitate and filtered to remove unreacted reactants. Thereafter, it was vacuum-dried at 30 DEG C or less to prepare an acrylic binder (C-1) having a weight average molecular weight of 9,500 g / mol. The weight average molecular weight is an average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[Chemical Formula 22]

Synthetic example 3: Synthesis of acrylic binder (C-2)

Methyl-1,3-dioxolan-4-yl-methyl acrylate instead of 2-ethyl-2-methyl- (C-2) having a weight average molecular weight of 10,200 g / mol was prepared in the same manner as in Synthesis Example 2, except that methyl acrylate was used.

(23)

Synthetic example 4: Synthesis of acrylic binder (C-3)

Dioxaspiro [4,5] -dec-2-yl-methyl acrylate instead of 2-ethyl-2-methyl- Acrylic binder (C-3) having a weight average molecular weight of 9,800 g / mol was prepared in the same manner as in Synthesis Example 2, except that methyl acrylate was used.

&Lt; EMI ID =

Example 1 to 12 and Comparative Example One

Each component was mixed with the composition shown in Table 1 below to prepare a positive photosensitive resin composition. Specifically, the photosensitive diazoquinone compound (B), the acrylic binder (C), the silane compound (E) and the phenol compound (F) are added to the solvent (D) after dissolving the alkali- , And filtered through a 0.45 占 퐉 fluorine resin filter to prepare a positive photosensitive resin composition.

division Example Comparative Example One 2 3 4 5 6 7 8 9 10 11 12 One (A) an alkali-soluble resin 100 100 100 100 100 100 100 100 100 100 100 100 100 (B) Photosensitive diazoquinone compound 10 10 10 10 10 10 10 10 10 10 10 10 10 (C) Acrylic binder (C-1) 5 10 15 30 - - - - - - - - - (C-2) - - - - 5 10 15 30 - - - - - (C-3) - - - - - - - - 5 10 15 30 - (D) Solvent (D-1) 100 100 100 100 100 100 100 100 100 100 100 100 100 (D-2) 250 250 250 250 250 250 250 250 250 250 250 250 250 (E) Silane compound 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (F) Phenol compound 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5

In Table 1, the content units of (B) to (F) are parts by weight added to 100 parts by weight of (A).

Hereinafter, the specifications of the components used in the above examples are as follows.

(A) an alkali-soluble resin

The polybenzoxazole precursor prepared in Synthesis Example 1 was used.

(B) Photosensitive Diazoquinone compound

A photosensitive diazoquinone represented by the following formula (25) was used.

(25)

In formula (25), two of Q are substituted by the following formula (26), and the other is hydrogen.

(26)

(C) Acrylic binder

(C-1) The acrylic binder prepared in Synthesis Example 2 was used.

(C-2) The acrylic binder prepared in Synthesis Example 3 was used.

(C-3) The acrylic binder prepared in Synthesis Example 4 was used.

(D) Solvent

(D-1)? -Butyrolactone

(D-2) Propylene glycol monomethyl ether (PGME)

(E) Silane compound

A triethoxy [3- (phenylamino) propyl] silane represented by the following formula (27)

(27)

(F) Phenol compound

A phenol compound represented by the following formula (28)

(28)

Preparation of insulating film

The positive photosensitive resin compositions prepared in Examples 1 to 12 and Comparative Example 1 were applied to ITO glass using a spin coater and then heated on a hot plate at 130 占 폚 for 2 minutes to form a coating film.

The film thus obtained was exposed to light using an exposure apparatus (I-line stepper, Nikon Corporation, NSR i10C) using a predetermined pattern mask, and then exposed to 2.38% aqueous tetramethylammonium hydroxide solution at room temperature for 40 seconds, ), Followed by washing with distilled water for 30 seconds. Subsequently, the obtained pattern was cured at 250 DEG C for 60 minutes at an oxygen concentration of 1000 ppm or less by using an electric furnace to obtain a patterned film.

Evaluation example

The film thickness and adhesiveness after curing were evaluated for the patterned film by the following method. The results are shown in Table 2 below.

An ITO glass substrate having a length of 100 mm and a length of 100 mm was coated with a spin coater (1H-DX2) made by Mikasa and applied on a hot plate at 120 DEG C for 2 minutes to form an insulating film. The insulating film was thermally cured at 250 DEG C for 1 hour by using an electric furnace to prepare a thin film. The film thickness was measured using a ST4000-DLX instrument manufactured by KMAC. Metal deposition was performed by depositing a metal thin film having a thickness of 200 nm on the film using titanium (Ti), copper (Cu), and aluminum (Al) targets in a sputter chamber . Only the metal surface deposited 1 mm in width and height was cut and then peeled off using 3M tape, and the remaining film pieces were counted.

The PCT condition was a pressure vessel having 121 ° C / 2 atm / 100% relative humidity, and a change in the adhesive force was observed after 168 hours from the deposition of the metal film deposited within the above conditions.

division Thickness after curing
(탆) Number of residual patterns / total number of patterns (PTC 168h) Ti substrate Cu substrate Al substrate Comparative Example 1 3.0 91/100 90/100 70/100 Example 1 3.0 93/100 93/100 75/100 Example 2 3.0 94/100 95/100 78/100 Example 3 3.0 95/100 95/100 80/100 Example 4 3.1 98/100 100/100 90/100 Example 5 3.0 94/100 94/100 80/100 Example 6 3.0 95/100 95/100 83/100 Example 7 3.0 96/100 96/100 86/100 Example 8 3.1 100/100 100/100 95/100 Example 9 3.0 93/100 95/100 75/100 Example 10 3.0 94/100 96/100 80/100 Example 11 3.0 95/100 96/100 87/100 Example 12 3.2 100/100 100/100 95/100

It can be seen from Table 2 that the positive type thermoplastic resin compositions of Examples 1 to 12 and the insulating film using the positive type thermoplastic resin compositions have improved adhesion to various metal substrates. This is thought to result from the introduction of a functional group capable of forming a hydrogen bond with the hydroxyl group on the surface of the metal substrate.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, and that various changes and modifications may be made without departing from the scope of the invention. It is natural to belong.

Claims

(A) an alkali-soluble resin comprising a polybenzoxazole precursor, a polyamic acid, a polyimide, or a combination thereof;
(B) a photosensitive diazoquinone compound;
(C) an acrylic binder containing a repeating unit derived from a dioxolane-based compound represented by the following formula (10); And
(D) Solvent
A positive photosensitive resin composition comprising:
[Chemical formula 10]

In Formula 10,
R ¹ and R ² are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, Or a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, C6 to C30 heteroaryl group, or R < ¹ > and R < ² > are cyclic hydrocarbons linked together to form a ring,
R ³ and R ⁴ are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,
R < ⁵ > is hydrogen or a methyl group,
n is an integer of 1 to 5;

The method of claim 1,
Wherein the acrylic binder (C) further comprises a repeating unit derived from an unsaturated carboxylic acid compound.

The method of claim 1,
Wherein the acrylic binder (C) further comprises at least one of a repeating unit derived from an epoxy group-containing unsaturated compound and a repeating unit derived from a phenylmaleimide-based compound.

The method of claim 1,
Wherein the content of the acrylic binder (C) is 5 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

The method of claim 1,
Wherein the content of the acrylic binder (C) is 5 to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

The method of claim 1,
The positive photosensitive resin composition
With respect to 100 parts by weight of the alkali-soluble resin (A)
5 to 100 parts by weight of the photosensitive diazoquinone compound (B);
5 to 30 parts by weight of the (C) acrylic binder; And
100 to 900 parts by weight of the solvent (D)
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

The method of claim 1,
Wherein the positive photosensitive resin composition further comprises a silane compound.

The method of claim 1,
Wherein the positive photosensitive resin composition further comprises a phenol compound.

An insulating film using the positive photosensitive resin composition according to any one of claims 1 to 8.

A display device comprising an insulating film according to claim 9.