KR101711918B1 - Positive photosensitive resin composition, photosensitive resin film prepared by using the same and display device - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기의 정의는 명세서에 기재된 바와 같다.)(A) an alkali-soluble resin represented by the following formula (1); (B) a photosensitive diazoquinone compound; (C) a thermal acid generator; And (D) a solvent, a photosensitive resin film produced using the positive photosensitive resin composition, and a display device.
[Chemical Formula 1]

(In the above formula (1), the definition of each substituent is as described in the specification.)

Description

TECHNICAL FIELD [0001] The present invention relates to a positive photosensitive resin composition, a photosensitive resin film and a display element,

The present invention relates to a positive photosensitive resin composition, a photosensitive resin film produced using the positive photosensitive resin composition, and a display element comprising the photosensitive resin film.

BACKGROUND ART [0002] Heat resistant resins such as polyimide and polybenzoxazole are widely used as an interlayer insulating film or a planarizing film of an organic EL device, a display device such as an LCD, or the like. Recently, a photosensitive polyimide and a photosensitive polybenzoxazole have been widely used for the purpose of securing reliability of an OLED element in forming an interlayer insulating film of an organic light emitting diode (OLED). Photosensitive polyimide and polybenzoxazole are excellent in physical properties such as heat resistance and mechanical strength and have excellent electric properties such as low dielectric constant and high insulation and also have a good planarization property of the coating surface and a content of impurities It is advantageous in that it is easy to make a fine shape. Particularly, the positive type photosensitive polyimide and polybenzoxazole can be patterned and have a pattern precision applicable to the formation of a pattern of an insulating film and a planarizing film of an organic light emitting device , The use of these photosensitive resins is very advantageous in terms of processability and economy.

Organic EL devices have the advantage of self-emission, wide viewing angle, and thin film type, and are attracting attention as a next generation display. However, the organic EL devices generally have a short life due to rapid aging of the device due to moisture. To overcome these shortcomings, we are taking measures to prevent water and outgassing from chemical substances used in the process as well as the manufacturing process.

Particularly, in the case of an organic EL device, in the formation of microstructures such as an insulating film and a planarizing film, a phenomenon that a pattern collapses at the time of thermosetting often occurs. Accordingly, efforts have been made to develop positive photosensitive resin compositions excellent in sensitivity, reliability, storage stability, and photosensitive resin films capable of being fired at low temperatures using the same.

One embodiment is to provide a positive photosensitive resin composition excellent in sensitivity, reliability, storage stability and the like.

Another embodiment is to provide a process for producing a photosensitive resin film using the positive photosensitive resin composition.

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

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

(A) an alkali-soluble resin represented by the following formula (1); (B) a photosensitive diazoquinone compound; (C) a thermal acid generator; And (D) a solvent.

[Chemical Formula 1]

In Formula 1,

E ¹ and E ² are each independently a hydrogen atom or a residue of a derivative derived from a compound represented by the following formula 2, provided that E ¹ and E ² are not hydrogen atoms at the same time,

X ¹ and Y ¹ are each independently a substituted or unsubstituted aromatic organic group, a substituted or unsubstituted divalent to octavalent aliphatic organic group or a combination thereof,

R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 To C20 heteroaryl group,

o and p are each independently an integer of 0 to 4, provided that o + p > 0,

q and r are each independently an integer of 0 to 2, provided that q + r? 0,

(2)

In Formula 2,

R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group or a substituted or unsubstituted C6 to C20 aryl group,

R ³ and R ⁴ may combine with each other to form a ring,

L ¹ is a single bond, -O- or -OL'O- (L 'is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group)

n is an integer of 0 or 1;

The formula (2) may be represented by any one of the following formulas (3) to (6).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above Chemical Formulas 3 to 5,

R ⁵ to R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group or a substituted or unsubstituted C6 to C20 aryl group,

L ² and L ³ are each independently a single bond, -O- or -OL'O- (L 'is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group).

The alkali-soluble resin may have a weight average molecular weight of 3,000 g / mol to 300,000 g / mol.

The thermal acid generator may be represented by the following general formula (7) or (8).

(7)

[Chemical Formula 8]

In the above formulas (7) and (8)

R ⁹ to R ¹³ each independently represents a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkoxy group, C6 < / RTI > to C20 aryl group.

The thermal acid generator may decompose at a temperature of 120 ° C to 200 ° C to generate an acid.

The positive photosensitive resin composition may further include a dissolution regulator, a crosslinking agent, or a combination thereof.

The dissolution controlling agent may be represented by the following general formula (9).

[Chemical Formula 9]

In the above formula (9)

R ¹⁴ to R ²³ each independently represent a hydrogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkoxy group, C6 < / RTI > to C20 aryl group,

Provided that at least one of R ¹⁴ to R ¹⁸ and at least one of R ¹⁹ to R ²³ is a hydroxy group,

L ⁴ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

(A) 5 to 100 parts by weight of a photosensitive diazoquinone compound (B) relative to 100 parts by weight of an alkali-soluble resin; And (C) 1 to 50 parts by weight of a thermal acid generator; and (D) the solvent may be included in an amount of 3% by weight to 30% by weight based on the total solid content of the positive photosensitive resin composition.

The positive photosensitive resin composition may further include an additive selected from the group consisting of a surfactant, a reviling agent, a silane coupling agent, and a combination thereof.

In another embodiment, the positive photosensitive resin composition is coated on a substrate, and the applied positive photosensitive resin composition is dried, heated, exposed and developed. After the development, the positive photosensitive resin composition is cured Post-baking) of the photosensitive resin film.

The post-development curing step may be conducted at a temperature of 150 ° C or higher and 230 ° C or lower.

Another embodiment provides a photosensitive resin film produced using the positive photosensitive resin composition.

Another embodiment provides a display device comprising the photosensitive resin film.

The positive photosensitive resin composition according to one embodiment of the present invention is capable of curing at a low temperature and maintaining a net taper without collapsing the pattern during low temperature curing and having low outgas from the coating film after curing at low temperature, Excellent chemical resistance. In addition, the photosensitive resin film prepared using the above composition has no risk of deterioration in performance due to out gas, or bad light emission such as dark spot or pixel shrinkage.

1 to 8 are photographs showing taper shapes of the composition patterns according to Examples 1 to 8, respectively.
Figs. 9 to 14 are photographs showing taper shapes of the composition patterns according to Comparative Examples 1 to 6. Fig.

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, Br, Cl or I), a hydroxy group, a nitro group, a cyano group, an amino group NH _2, NH (R ^300), or ^{N (R 301) (R 302} ) , wherein R ^300, R ³⁰¹ and R ³⁰² are the same or different, each independently represent a C1 to C10 alkyl group), an amidino group, A substituted or unsubstituted 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 aryl group, And a substituted or unsubstituted heterocyclic group substituted with at least one substituent selected from the group consisting of 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 " "Heterocyclic group" means a C2 to C30 cycloalkyl 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 cycloalkyl Means a C2 to C30 cycloalkenyl group, a C2 to C30 cycloalkenylene group, a C2 to C30 cycloalkynyl group, a C2 to C30 cycloalkynylene group, a C2 to C30 heteroaryl group, or a C2 to C30 heteroarylene group, Specifically, C2 to C15 cycloalkyl groups 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 C15 A C2 to C15 cycloalkenyl group, a C2 to C15 cycloalkynylene group, a C2 to C15 cycloalkynylene group, a C2 to C15 heteroaryl group, or a C2 to C15 heteroarylene group, it means.

As used herein, unless otherwise defined, "combination" means mixing or copolymerization. "Copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

In the present specification, "*" means the same or different atom or part connected to a chemical formula.

The positive photosensitive resin composition according to one embodiment comprises (A) an alkali-soluble resin represented by the following formula (1); (B) a photosensitive diazoquinone compound; (C) a thermal acid generator; And (D) a solvent.

[Chemical Formula 1]

In Formula 1,

E ¹ and E ² are each independently a hydrogen atom or a residue of a derivative derived from a compound represented by the following formula 2, provided that E ¹ and E ² are not hydrogen atoms at the same time,

X ¹ and Y ¹ are each independently a substituted or unsubstituted aromatic organic group, a substituted or unsubstituted divalent to octavalent aliphatic organic group or a combination thereof,

R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 To C20 heteroaryl group,

o and p are each independently an integer of 0 to 4, provided that o + p > 0,

q and r are each independently an integer of 0 to 2, provided that q + r? 0,

(2)

In Formula 2,

R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group or a substituted or unsubstituted C6 to C20 aryl group,

R ³ and R ⁴ may combine with each other to form a ring,

L ¹ is a single bond, -O- or -OL'O- (L 'is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group)

n is an integer of 0 or 1;

Conventional alkali-soluble resins used in positive-working photosensitive resin compositions generally include polybenzoxazole precursors, polyimide precursors, combinations thereof, etc. The ends of these conventional alkali-soluble resins have a high temperature And reacted with various additives and the like around the high reactivity due to the high temperature to form a precipitate. As a result, there has been a problem that the film characteristics of the photosensitive resin film produced using the conventional alkali-soluble resin are deteriorated.

The alkali-soluble resin according to one embodiment includes a residue of a derivative derived from a carbonate compound represented by the formula (2) at at least one end thereof, and the residue is removed at a low temperature, for example, 150 ° C or more and 250 ° C or less, Deg.] C or less, for example, at a temperature of 150 [deg.] C or more and 200 [ When the residue is decomposed, the amine group is exposed at the terminal of the alkali-soluble resin, and the amine group at the terminal forms a bridge with the terminal of another alkali-soluble resin having an amine group at the terminal. As a result, the photosensitive resin film or the like manufactured using the alkali-soluble resin according to an embodiment has excellent film properties such as film shrinkage ratio.

Hereinafter, each component of the positive photosensitive resin composition according to this embodiment will be described in detail.

(A) an alkali-soluble resin

The positive photosensitive resin composition according to one embodiment is represented by the formula (1), and at least one of the terminals of the formula (1) includes a residue of a derivative derived from the compound represented by the formula (2).

In Formula 1, X ¹ may be a substituted or unsubstituted aromatic organic group, a substituted or unsubstituted divalent to octavalent aliphatic group, or a combination thereof, which may be an aromatic diamine or a residue of silicon diamine.

Examples of the aromatic diamine include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'- (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, Bis (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene and the like, and the silicone diamine (P-aminophenyl) tetramethyldisiloxane, bis (gamma -aminopropyl) tetramethyldisiloxane, 1 (aminophenyl) tetramethyldisiloxane, Bis (? - aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (? - aminopropyl) tetraphenyldisiloxane, And the like Roxanne.

For example, X ¹ may be 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis Amino-4-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, 1,1,1,3,3,3-hexafluoropropane, and combinations thereof.

Specifically, X ¹ may be represented by any one of the following formulas (1-1) to (1-6), but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

In Formula 1, Y ¹ may be a residue of a dicarboxylic acid derivative as a substituted or unsubstituted aromatic organic group, a substituted or unsubstituted divalent to octavalent aliphatic organic group, or a combination thereof.

Examples of the dicarboxylic acid derivative include active compounds that are activated ester derivatives in which chloride or 1-hydroxy-1,2,3-benzotriazole is reacted in advance, and for example, diphenyloxydicarboxylic acid chloride , Bis (phenylcarboxylic acid chloride) sulfone, bis (phenylcarboxylic acid chloride) ether, bis (phenylcarboxylic acid chloride) phenone, phthalic carboxylic acid dichloride, terephthalic acid dichloride, isophthalic carboxylic acid dichloride, A compound selected from the group consisting of carboxylic acid dichloride, diphenyloxydicarboxylate benzotriazole, and combinations thereof.

Specifically, Y ¹ may be represented by any one of the following formulas 1-7 to 1-10, but is not limited thereto.

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

In the above formulas 1-10, L '' represents -O-, -CH ₂ -, -C (CF ₃ ) ₂ -, -C (═O) -, -C (═O) NH-, -SO ₂ - or -C (CH ₃ ) ₂ -.

In Formula 1, E ¹ and E ² are each independently a hydrogen atom or a residue of a derivative derived from the compound represented by Formula 2, provided that E ¹ and E ² are not hydrogen atoms at the same time.

The above-mentioned formula (2) is a carbonate compound, wherein the residue of the derivative derived from the compound represented by the formula (2) is at a low temperature, for example, at a temperature of 150 ° C or more and 250 ° C or less, for example 150 ° C or more and 230 ° C or less, And the amine group is exposed at the terminal of the alkali-soluble resin. Specifically, a thermal acid generator to be described later is decomposed to generate an acid, and the acid is decomposed at a low temperature, for example, at a temperature of 150 ° C to 250 ° C, for example, 150 ° C to 230 ° C, Attacking carbonyl carbon causes a nucleophilic acyl substitution and separates the residue of the derivative derived from the compound represented by formula (2), which was bonded to the nitrogen atom, to expose the amine group.

The formula (2) may be represented, for example, by any one of the following formulas (3) to (6).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above Chemical Formulas 3 to 5,

R ⁵ to R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group or a substituted or unsubstituted C6 to C20 aryl group,

L ² and L ³ are each independently a single bond, -O- or -OL'O- (L 'is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group).

Specifically, the above-mentioned formula (2) may be used in combination with an organic solvent such as methyl carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl 2,5-dioxahexanedioate, Allyl methyl carbonate, di-tert-butyl dicarbonate, diethyl 2,5-dioxahexanedioate, bis (2-chloro- (2-chloroethyl) carbonate), chloromethyl isopropyl carbonate, allyl ethyl carbonate, 1-chloroethyl ethyl carbonate, di- di-tert-amyl Dicarbonate, Diallyl Dicarbonate, Vinylene Carbonate, Ethylene Carbonate, Diphenyl Carbonate, 1-Chloroethyl Cyclohexyl Carbonate, Propylene Carbonate, tert-Butyl Phenyl Carbonate, 4,5-dimethyl-1,3 1,3-dioxol-2-one, 1,3-dioxan-2-one, 1,2-dioxan- 1-butylene carbonate, dibenzyl carbonate, 4-vinyl-1,3-dioxolan-2-one, Glycerol 1,2-Carbonate, Dibenzyl Dicarbonate, Allyl Phenyl Carbonate, Benzyl Phenyl Carbonate, Bis (4-nitrophenyl) carbonate, (4-nitrophenyl) carbonate, 4- (4-ethoxyphenoxycarbonyl) phenyl ethyl carbonate, butyl 4-carboxyphenyl carbonate, Carbonate), amyl 4- (4 (4-Ethoxyphenoxycarbonyl) phenyl Carbonate, Di-2-pyridyl Carbonate, 4- [2- (trimethylsilyl) ethoxy (4- [2- (Trimethylsilyl) ethoxycarbonyloxy] nitrobenzene), and the like.

More specifically, the formula (2) may be represented by any one of the following formulas (2-1) to (2-15) and (6), but is not limited thereto.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

[Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

[Chemical Formula 2-9]

[Chemical Formula 2-10]

[Chemical Formula 2-11]

[Formula 2-12]

[Chemical Formula 2-13]

[Chemical Formula 2-14]

[Chemical Formula 2-15]

[Chemical Formula 6]

The alkali-soluble resin may have a weight average molecular weight of 3,000 g / mol to 300,000 g / mol. When the weight average molecular weight of the alkali-soluble resin is less than 3,000 g / mol, sufficient physical properties can not be obtained, which is not preferable. When the weight-average molecular weight is more than 300,000 g / mol, solubility in a solvent becomes low and handling becomes very difficult.

(B) Photosensitive Diazoquinone  compound

The positive photosensitive resin composition according to one embodiment includes a photosensitive diazoquinone compound. The photosensitive diazoquinone compound may be a compound having 1,2-benzoquinone diazide or 1,2-naphthoquinone diazide structure, which is disclosed in U.S. Patent Nos. 2,772,975, 2,797,213, 3,669,658 . Examples of the photosensitive diazoquinone compound include compounds represented by the following formulas (21) to (25).

[Chemical Formula 21]

[Chemical Formula 22]

(In the above formula (22), R ¹⁰¹ is a hydrogen atom or CH ₃ )

(23)

(In the above formula (23), R ¹⁰² is a hydrogen atom or OQ.)

≪ EMI ID =

(In the formula (24), each of R ¹⁰³ to R ¹⁰⁹ independently represents a hydrogen atom, OQ or NHQ.)

(25)

In the above Chemical Formulas 21 to 25,

또는

이고, 단 Q 및 Q¹ 내지 Q³ 가 동시에 수소 원자는 아니다.Q and Q ¹ to Q ³ are each independently a hydrogen atom,

or

, With the proviso that Q and Q ¹ to Q ³ Is not a hydrogen atom at the same time.

The amount of the photosensitive diazoquinone compound in the positive photosensitive resin composition according to one embodiment may be 5 to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the photosensitive diazoquinone compound is within the above range, the pattern is well formed without residue during exposure, and a good pattern can be obtained without loss of film thickness during development.

(C) Thermal acid generator

The thermal acid generators included in the positive photosensitive resin composition according to one embodiment are those capable of decomposing by heat to generate an acid, and examples thereof include conventional thermal acid generators such as a compound represented by the following Chemical Formula 7 or 8, Can be used.

(7)

[Chemical Formula 8]

In the above formulas (7) and (8)

R ⁹ to R ¹³ each independently represents a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkoxy group, C6 < / RTI > to C20 aryl group.

The thermal acid generator helps smooth the ring-closing reaction of the alkali-soluble resin even at a low temperature. For example, the thermal acid generator may decompose at a temperature of 120 ° C to 200 ° C to generate an acid.

Specifically, the thermal acid generator may be represented by the following formulas (36a) to (36c).

[Chemical Formula 36a]

(36b)

[Chemical Formula 36c]

In the above formula (36a), m1 and m2 are each independently an integer of 0 to 10, for example, an integer of 0 to 6, m3 is an integer of 1 to 5, and ^R201 and ^R202 are each independently CF ₃ , a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C3 to C20 cycloalkyl group. In the formula (36c), m4 and m5 are each independently an integer of 0 to 10, for example, an integer of 0 to 6.

The formulas (36a), (36b) and (36c) may each independently be represented by any one of the following formulas (38) to (44).

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

The thermal acid generator may be represented by any one of the following Chemical Formulas 45 to 48, although it is not included in Chemical Formulas 36a to 36c.

[Chemical Formula 45]

(46)

(47)

(48)

The content of the thermal acid generator is 1 part by weight to 50 parts by weight, for example, 3 parts by weight to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin. If the content of the thermal acid generator is less than 1 part by weight, sufficient cyclization of the insulating film may not occur, resulting in deterioration of thermal and mechanical properties as an insulating film, resulting in defective display elements. If the content exceeds 50 parts by weight, There is a fear that the sensitivity may be deteriorated in the exposure process and the thermal acid generator remnant remains in the insulating film after curing, resulting in a large amount of outgas, which may lead to defective display elements. The thermal acid generators may be selected according to the curing temperature conditions, and may be used alone or in combination of two or more.

On the other hand, perfluoroalkylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid and fluorobutanesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid may be used instead of the thermal acid generator have. The thermal acid generator can prevent the dehydration reaction of the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor and lowering the degree of cyclization even when the curing temperature is lowered as a catalyst for cyclization.

(D) Solvent

As the solvent contained in the positive photosensitive resin composition according to one embodiment, a solvent included in a usual photosensitive resin composition may be used. The solvent is used for the purpose of helping the alkali-soluble resin, the photosensitive diazoquinone compound, the thermal acid generator, etc. to be homogeneously mixed in the composition, and for controlling the viscosity so that the composition can be easily applied on the substrate .

Particularly, the solvent has a function of improving film uniformity at the time of coating, preventing coating unevenness, and forming a uniform pattern by preventing pin stain.

The solvent includes, for example, alcohols such as methanol, ethanol, benzyl alcohol, and hexyl alcohol; Ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; Ethylene glycol alkyl ether propionates such as ethylene glycol methyl ether propionate and ethylene glycol ethyl ether propionate; Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Ethers; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate; and propylene glycol alkyl ether acetate such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and the like Propylene glycol alkyl ether propionates, propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Dipropylene glycol alkyl ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether; Butylene glycol monomethyl ether, butylene glycol monomethyl ether and butylene glycol monoethyl ether; And dibutylene glycol alkyl ethers such as dibutylene glycol dimethyl ether and dibutylene glycol diethyl ether.

The solvent may be contained in an amount of 3% by weight to 30% by weight, for example, 5% by weight to 30% by weight based on the total solid content of the positive photosensitive resin composition according to one embodiment. When the solvent is contained in an amount of less than 3% by weight based on the total solid content of the composition, the thickness of the coating is reduced and the flatness of the coating is lowered. When the solvent is contained in an amount exceeding 30% by weight, There is a problem that the coating equipment can be overloaded.

(E) a dissolution modifier and Cross-linking agent

The positive photosensitive resin composition according to one embodiment may further include a dissolution regulator, a crosslinking agent, or a combination thereof.

The dissolution controlling agent may be represented by the following general formula (9).

[Chemical Formula 9]

In the above formula (9)

R ¹⁴ to R ²³ each independently represent a hydrogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkoxy group, C6 < / RTI > to C20 aryl group,

Provided that at least one of R ¹⁴ to R ¹⁸ and at least one of R ¹⁹ to R ²³ is a hydroxy group,

L ⁴ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

For example, the dissolution controlling agent may be represented by any one of the following formulas (29) to (34).

[Chemical Formula 29]

(In Formula 29, R28 is a hydrogen atom or CH _3, and, R29 to R33 each independently represent a hydrogen atom, OH or CH _3.)

(30)

(In Formula 30, R34 to R39 are the same or independently, a hydrogen atom, OH or CH _3.)

(31)

(In Formula 31, R40 to R45 are each independently, a hydrogen atom, OH or CH _3, R46 and R47 are, each independently, a hydrogen atom or CH _3).

(32)

(33)

(Wherein R48 to R52 each independently represent a hydrogen atom or OH).

(34)

(35)

The amount of the dissolution regulator is preferably 1 part by weight to 30 parts by weight per 100 parts by weight of the alkali-soluble resin. When the content of the dissolution controlling agent is within the above range, the dissolution rate and sensitivity of the exposed portion can be increased upon development with an alkaline aqueous solution, and the resist can be patterned at high resolution without developing residue (scum) at the time of development.

The crosslinking agent may be a thermal crosslinking agent. The thermal crosslinking agent accelerates the curing reaction of the alkali-soluble resin at a low temperature to increase heat resistance and chemical resistance. In particular, outgas and dark spots from the film can be suppressed after low-temperature heat firing. By further including a crosslinking agent, the film shrinkage after curing is greatly reduced.

The thermal cross-linking agent may be a cross-linking agent containing a phenolic hydroxyl group or a melamine cross-linking agent.

The molecular weight of the cross-linking agent comprising the phenolic hydroxyl group may be from 200 g / mol to 2,000 g / mol, such as from 300 g / mol to 1,000 g / mol. When the molecular weight of the crosslinking agent containing a phenolic hydroxyl group is within the above range, it is possible to improve the solubility and sensitivity of the alkali aqueous solution, and improve the heat resistance and chemical resistance.

The content of the crosslinking agent containing a phenolic hydroxyl group may be 1 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the crosslinking agent containing a phenolic hydroxyl group is contained in an amount of 1 part by weight or more based on 100 parts by weight of the alkali-soluble resin, the coating property is improved. When the crosslinking agent is contained in an amount of 50 parts by weight or less, developability and sensitivity are improved. On the other hand, when it is contained in an amount of less than 1 part by weight, crosslinking is lowered during curing. If the amount of the crosslinking agent is more than 50 parts by weight, outgas increases.

The melamine-based crosslinking agent promotes the crosslinking reaction of the alkali-soluble resin to significantly reduce the outgas, as well as greatly improving the chemical resistance and chemical resistance.

The melamine-based crosslinking agent includes, for example, an alkoxyalkylmethanolamine compound such as a methoxymethylamine compound, a hexamethoxymethylamine compound, an alkoxyalkylmethanolmelamine compound, or a carboxymethylmelamine compound, Can be used.

The content of the melamine-based crosslinking agent may be 1 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the melamine-based crosslinking agent is contained in an amount of 1 part by weight or more based on 100 parts by weight of the alkali-soluble resin, the alkali resistance is increased and the residual film ratio of the unexposed portion can be increased. On the other hand, when the amount of the photo-initiator is less than 1 part by weight, the photo-speed is lowered. When the amount of the photo-initiator is more than 50 parts by weight, storage stability is deteriorated.

(F) Other additives

The positive photosensitive resin composition according to one embodiment may further contain (F) other additives in addition to the components (A) to (D) or the components (A) to (E).

As other additives, a suitable surfactant or levifying agent may be further used as an additive in order to prevent unevenness in film thickness or to improve developability. Further, a silane coupling agent may be further used as an adhesion promoting agent for enhancing adhesion with a substrate.

Wherein the surfactant comprises a siloxane surfactant or a surfactant having a fluorine atom and the total amount of the surfactant is 0.005 parts by weight or more and 0.3 parts by weight or less based on the total amount of the photosensitive resin composition. When the surfactant is contained in an amount of less than 0.005 part by weight based on the total amount of the photosensitive resin composition, the uniformity of the film is lowered, the unevenness easily occurs, and the photosensitive resin liquid coated on the end portion of the substrate is dried into the substrate. Also, when the surfactant is contained in an amount of more than 0.3 part by weight based on the total amount of the photosensitive resin composition, whitening occurs in which the coated surface is whitened at the time of coating the composition, and the whitening phenomenon becomes worse at the time of development. This is because the coating surface becomes extremely hydrophobic, and water or the like adheres to the coating surface to cause scattering.

The siloxane-based surfactant has a large effect of suppressing defects such as unevenness of the coating film of the photosensitive resin composition and improving the coating property. The surfactant having a fluorine atom has a pin- The effect of suppressing generation of cells and the like is great.

The siloxane-based surfactant is, for example, BYK series manufactured by BYK, Germany. Examples of the surfactant having a fluorine atom include "Mega Face series" of Dainippon Ink and Chemicals, But is not limited thereto.

On the other hand, when a silane coupling agent is used as the adhesion promoting agent, adhesion with the substrate can be improved. The silane coupling agent includes, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (? -Methoxyethoxy) silane; Or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldi Ethoxysilane; Carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy [3- (phenylamino) propyl] silane, and the like, but are not limited thereto.

Another embodiment provides a method for producing a photosensitive resin film using the positive photosensitive resin composition.

The method for producing a photosensitive resin film according to this embodiment is characterized in that the positive photosensitive resin composition is coated on a substrate, and the applied positive photosensitive resin composition is dried, heated, exposed, and developed, And post-baking at a temperature of 250 DEG C or less.

Conventional photosensitive resin films have problems such as post-baking at a temperature exceeding 250 캜 after development, resulting in deterioration of film shrinkage and outgas.

However, according to the process for producing a photosensitive resin film according to the above embodiment, the derivative derived from the compound represented by the above-mentioned formula (2) is included at the terminal of the alkali-soluble resin, and thus the resin is cured at a temperature of 150 ° C or higher and 250 ° C or lower, Thus, a photosensitive resin film having excellent film properties such as film shrinkage ratio can be produced.

The post-development curing step may be performed at a temperature of 150 ° C or more and 230 ° C or less, for example, 150 ° C or more and 200 ° C or less.

Specifically, the step of preparing a patterned photosensitive resin film 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; A step of developing the exposed positive photosensitive resin composition film with an aqueous alkaline solution; And a step of performing heat treatment at a temperature of 150 ° C or more and 250 ° C or less, for example, 150 ° C or more and 230 ° C or less, for example, 150 ° C or more and 200 ° C or less after the development. Process conditions such as coating, exposure, and development of the composition are well known in the art, and a detailed description thereof will be omitted herein.

Another embodiment provides a display element comprising the photosensitive resin film. The display device may be, for example, a liquid crystal display (LCD) or an organic light emitting diode (OLED), but is not limited thereto. That is, the positive photosensitive resin composition according to one embodiment may be useful for forming an insulating film, a planarizing film, a passivation layer, an interlayer insulating layer, or the like in a display device.

Example

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.

(Synthesis of alkali-soluble resin)

[ Synthetic example  1] Synthesis of alkali-soluble resin 1

(3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-tetra-naphthalene-2-carboxylate was obtained by passing nitrogen through a four-necked flask equipped with a stirrer, a temperature controller, 36.626 g of 3-hexafluoropropane was placed, and 146.5 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. In the obtained solution, the solid content was 20% by weight.

When the solid was completely dissolved, 13.447 g of pyridine was added, and 6.548 g of di-tert-butyl dicarbonate was added thereto while keeping the temperature at 50 to 80 캜, (NMP), and then slowly dropped for 10 minutes. After the dropwise addition, the mixture was allowed to react for about 3 hours to convert ditert-butyl dicarbonate into 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3- hexafluoropropane Amine. Thereafter, the reaction temperature was lowered to 0 ° C to 5 ° C, 13.45g of pyridine was dissolved in 6.6g of NMP, and the mixture was immediately added. Thereafter, a solution prepared by dissolving 147.1 g of N-methyl-2-pyrrolidone (NMP) in 25.1 g of 4,4'-oxydibenzoyl chloride was slowly dropped for 60 minutes. After the dropwise addition, the reaction was carried out at a temperature of 0 ° C to 5 ° C for 3 hours to complete the reaction.

Water corresponding to 5 times the amount of the reaction mixture was prepared, and the reaction mixture was slowly added dropwise to water to form a precipitate. The precipitate was filtered, sufficiently washed with water, and then dried under a vacuum of 80 캜 And proceeded for 24 hours or longer to prepare an alkali-soluble resin 1.

[ Synthetic example  2] Synthesis of alkali-soluble resin 2

Except that diethyl 2,5-dioxahexanedioate was used in place of di-tert-butyl dicarbonate in Synthesis Example 1, Resin 2 was prepared.

[ Synthetic example  3] Synthesis of alkali-soluble resin 3

An alkali-soluble resin 3 was prepared in the same manner as in Synthesis Example 1 except for using diethyl carbonate instead of di-tert-butyl dicarbonate.

[ Synthetic example  4] Synthesis of alkali-soluble resin 4

An alkali-soluble resin 4 was prepared in the same manner as in Synthesis Example 1, except that vinylene carbonate (Vinylene Carbonate) was used instead of di-tert-butyl dicarbonate.

[ Synthetic example  5] Synthesis of alkali-soluble resin 5

(3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-tetra-naphthalene-2-carboxylate was obtained by passing nitrogen through a four-necked flask equipped with a stirrer, a temperature controller, 36.626 g of 3-hexafluoropropane was placed, and 146.5 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. In the obtained solution, the solid content was 20% by weight.

When the solid was completely dissolved, 13.447 g of pyridine was added, and 6.548 g of di-tert-butyl dicarbonate was added thereto while keeping the temperature at 50 to 80 캜, (NMP), and then slowly dropped for 10 minutes. After the dropwise addition, the mixture was allowed to react for about 3 hours to convert ditert-butyl dicarbonate into 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Amine. Thereafter, the reaction temperature was lowered to 0 ° C to 5 ° C, 13.45g of pyridine was dissolved in 6.6g of NMP, and the mixture was immediately added. Thereafter, a solution prepared by dissolving 15.05 g of 4,4'-oxydibenzoyl chloride and 6.9 g of isophthaloyl chloride in 135 g of N-methyl-2-pyrrolidone (NMP) was slowly added dropwise for 60 minutes. After the dropwise addition, the reaction was carried out at a temperature of 0 ° C to 5 ° C for 3 hours to complete the reaction.

Water in an amount corresponding to 5 times the amount of the reaction mixture was prepared, and the reaction mixture was slowly added dropwise to water to form a precipitate. The precipitate was filtered and sufficiently washed with water, followed by drying under a vacuum of 80 캜 And proceeded for 24 hours or longer to prepare an alkali-soluble resin 5.

[ Synthetic example  6] Synthesis of alkali-soluble resin 6

Except that diethyl 2,5-dioxahexanedioate was used in place of di-tert-butyl dicarbonate, the same procedure as in Synthesis Example 5 was carried out except that di- Resin 6 was prepared.

[ Synthetic example  7] Synthesis of alkali-soluble resin 7

An alkali-soluble resin 7 was prepared in the same manner as in Synthesis Example 5, except that diethyl carbonate (Diethyl Carbonate) was used instead of di-tert-butyl dicarbonate.

[ Synthetic example  8] Synthesis of alkali-soluble resin 8

An alkali-soluble resin 8 was prepared in the same manner as in Synthesis Example 5 except that vinylene carbonate (Vinylene Carbonate) was used instead of di-tert-butyl dicarbonate.

[ Comparative Synthetic Example  1] Synthesis of alkali-soluble resin 9

(3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-tetra-naphthalene-2-carboxylate was obtained by passing nitrogen through a four-necked flask equipped with a stirrer, a temperature controller, 36.626 g of 3-hexafluoropropane was placed, and 146.5 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. In the obtained solution, the solid content was 20% by weight.

When the solids were completely dissolved, 13.447 g of pyridine was added, and 4.93 g of 5-norbornene-2,3-dicarboxyanhydride was added thereto while maintaining the temperature at 50 to 80 ° C in N-methyl-2-pyrrolidone (NMP), and then slowly dropped for 10 minutes. After the dropwise addition, the mixture was allowed to react for about 3 hours to react the 5-norbornene-2,3-dicarboxyanhydride with 2,2-bis (3-amino-4-hydroxyphenyl) 3, - hexafluoropropane was reacted with one amine. Thereafter, the reaction temperature was lowered to 0 ° C to 5 ° C, 13.45g of pyridine was dissolved in 6.6g of NMP, and the mixture was immediately added. Thereafter, a solution prepared by dissolving 25.09 g of 4,4'-oxydibenzoyl chloride in 135 g of N-methyl-2-pyrrolidone (NMP) was slowly dropped for 60 minutes. After the dropwise addition, the reaction was carried out at a temperature of 0 to 5 ° C for 3 hours to complete the reaction.

Water in an amount corresponding to 5 times the amount of the reaction mixture was prepared, and the reaction mixture was slowly added dropwise to water to form a precipitate. The precipitate was filtered and sufficiently washed with water, followed by drying under a vacuum of 80 캜 And proceeded for 24 hours or longer to prepare an alkali-soluble resin 9.

[ Comparative Synthetic Example  2] Synthesis of alkali-soluble resin 10

(3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-tetra-naphthalene-2-carboxylate was obtained by passing nitrogen through a four-necked flask equipped with a stirrer, a temperature controller, 36.626 g of 3-hexafluoropropane was placed, and 146.5 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. In the obtained solution, the solid content was 20% by weight.

When the solid was completely dissolved, 13.447 g of pyridine was added, and 15.82 g of pyridine was dissolved in 14.2 g of NMP while keeping the temperature at 0 캜 to 5 캜, and the mixture was immediately added. Thereafter, a solution prepared by dissolving 29.51 g of 4,4'-oxydibenzoyl chloride in 167.21 g of N-methyl-2-pyrrolidone (NMP) was rapidly added for 5 minutes. After the addition, the reaction was carried out at a temperature of 0 to 5 ° C for 3 hours to complete the reaction.

Water in an amount corresponding to 5 times the amount of the reaction mixture was prepared, and the reaction mixture was slowly added dropwise to water to form a precipitate. The precipitate was filtered and sufficiently washed with water, followed by drying under a vacuum of 80 캜 And proceeded for 24 hours or longer to prepare an alkali-soluble resin 10.

[ Comparative Synthetic Example  3] Synthesis of alkali-soluble resin 11

(3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-tetra-naphthalene-2-carboxylate was obtained by passing nitrogen through a four-necked flask equipped with a stirrer, a temperature controller, 36.626 g of 3-hexafluoropropane was placed, and 146.5 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. In the obtained solution, the solid content was 20% by weight.

When the solids were completely dissolved, 13.447 g of pyridine was added, and 4.93 g of 5-norbornene-2,3-dicarboxyanhydride was added thereto while maintaining the temperature at 50 to 80 ° C in N-methyl-2-pyrrolidone (NMP), and then slowly dropped for 10 minutes. After the dropwise addition, the mixture was allowed to react for about 3 hours to react the 5-norbornene-2,3-dicarboxyanhydride with 2,2-bis (3-amino-4-hydroxyphenyl) 3-hexafluoropropane was reacted with one amine. Thereafter, the reaction temperature was lowered to 0 ° C to 5 ° C, 13.45g of pyridine was dissolved in 6.6g of NMP, and the mixture was immediately added. Thereafter, a solution prepared by dissolving 15.05 g of 4,4'-oxydibenzoyl chloride and 6.9 g of isophthaloyl chloride in 135 g of N-methyl-2-pyrrolidone (NMP) was slowly added dropwise for 60 minutes. After the dropwise addition, the reaction was carried out at a temperature of 0 to 5 ° C for 3 hours to complete the reaction.

Water in an amount corresponding to 5 times the amount of the reaction mixture was prepared, and the reaction mixture was slowly added dropwise to water to form a precipitate. The precipitate was filtered and sufficiently washed with water, followed by drying under a vacuum of 80 캜 And proceeded for 24 hours or longer to prepare an alkali-soluble resin 11.

Table 1 shows the main chain structure and end-capping agent used in the production of the alkali-soluble resins of Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 3.

Alkali-soluble resin Backbone structure End sealant Synthesis Example 1 One

2-8 Synthesis Example 2 2

2-5 Synthesis Example 3 3

(2-3) Synthesis Example 4 4

6 Synthesis Example 5 5

2-8 Synthesis Example 6 6

2-5 Synthesis Example 7 7

(2-3) Synthesis Example 8 8

6 Comparative Synthesis Example 1 9

5-norbornene-2,3-dicarboxyanhydride Comparative Synthesis Example 2 10

- Comparative Synthesis Example 3 11

5-norbornene-2,3-dicarboxyanhydride

(Production of positive-type photosensitive resin composition)

[Example 1]

15 g of the alkali-soluble resin of Synthesis Example 1, 5.55 g of the photosensitive diazoquinone represented by the following Formula A, 0.75 g of the thermal acid generator of Formula 38, 2.25 g of the dissolution control agent represented by the following Formula B, propylene glycol monomethyl ether Butyllolactone (boiling point: 205 占 폚) and 0.00365 g of fluorine leveling agent F-554 were stirred, and then 0.45 占 퐉 of a fluororesin And filtered through a filter to obtain a positive photosensitive resin composition.

ITO was coated on the glass substrate patterned in the same manner as the slit coating process, and the solvent was removed in the reduced pressure drying process, followed by drying using a hot plate to obtain a 4 탆 coating film. Subsequently, pattern exposure was performed using an appropriate light energy capable of forming a pattern using a mask using a broadband exposure apparatus at room temperature (23 ° C), and an aqueous alkaline developing solution (TMAH: 2.38% ) For 90 seconds, and then cured in a high-temperature curing oven under the temperature of 150 DEG C, 200 DEG C, 230 DEG C, 250 DEG C and a nitrogen stream, respectively.

After the exposure / development process, the residual film ratio and sensitivity were evaluated. After the curing process, the film shrinkage rate was evaluated. Further, the taper shape was measured through V-SEM, / MS to evaluate the amount of outgassing.

(A)

이고, 단 모두 수소 원자는 아니다.)(In the above formula (A), Q ¹ to Q ³ each independently represents a hydrogen atom or

And not both hydrogen atoms.)

(38)

[Chemical Formula B]

[Example 2]

A positive-type photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin 2 of Synthesis Example 2 was used instead of the alkali-soluble resin 1 of Synthesis Example 1.

[Example 3]

A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that the alkali-soluble resin 3 of Synthesis Example 3 was used instead of the alkali-soluble resin 1 of Synthesis Example 1.

[Example 4]

A positive-type photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin 4 of Synthesis Example 4 was used instead of the alkali-soluble resin 1 of Synthesis Example 1.

[Example 5]

A positive-type photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin 5 of Synthesis Example 5 was used instead of the alkali-soluble resin 1 of Synthesis Example 1.

[Example 6]

A positive-type photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin 6 of Synthesis Example 6 was used instead of the alkali-soluble resin 1 of Synthesis Example 1.

[Example 7]

A positive-type photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin 7 of Synthesis Example 7 was used instead of the alkali-soluble resin 1 of Synthesis Example 1.

[Example 8]

A positive-type photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin 8 of Synthesis Example 8 was used instead of the alkali-soluble resin 1 of Synthesis Example 1.

[Comparative Example 1]

A positive-type photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin 9 of Comparative Synthesis Example 1 was used instead of the alkali-soluble resin 1 of Synthesis Example 1.

[Comparative Example 2]

A positive-type photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin 10 of Comparative Synthesis Example 2 was used instead of the alkali-soluble resin 1 of Synthesis Example 1.

[Comparative Example 3]

A positive-type photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin 11 of Comparative Synthesis Example 3 was used instead of the alkali-soluble resin 1 of Synthesis Example 1.

[Comparative Example 4]

A positive-type photosensitive resin composition was obtained in the same manner as in Comparative Example 1, except that 0.75 g of a crosslinking agent represented by the following formula (C) was further contained.

≪ RTI ID = 0.0 &

[Comparative Example 5]

A positive photosensitive resin composition was obtained in the same manner as in Comparative Example 2, except that 0.75 g of the crosslinking agent represented by the above-mentioned formula (C) was further added.

[Comparative Example 6]

A positive photosensitive resin composition was obtained in the same manner as in Comparative Example 3, except that 0.75 g of the crosslinking agent represented by the above-mentioned formula (C) was further contained.

(evaluation)

Residual film ratio  And sensitivity evaluation

The positive photosensitive resin compositions according to Examples 1 to 8 and Comparative Examples 1 to 6 were coated on a glass substrate having ITO patterned thereon by the same method as in the slit coating process and the solvent was removed in a vacuum drying step, And dried to obtain a coating film having a thickness of 4 탆. Subsequently, pattern exposure was performed using an appropriate light energy capable of forming a pattern using a mask using a broadband exposure apparatus at room temperature (23 ° C), and an aqueous alkaline developing solution (TMAH 2.38%) at room temperature (23 ° C) For 90 seconds and rinsed with water.

1. Residual film ratio evaluation: thickness after development / initial (before development) thickness X 100

2. Sensitivity evaluation: Exposure of pattern formation according to exposure energy and measurement of distance between pattern and pattern by optical microscope after development

Reliability evaluation

The sample used in the above sensitivity evaluation was cured in a high-temperature curing oven at 150 ° C, 200 ° C, 230 ° C, 250 ° C and a nitrogen stream.

1. Film shrinkage: 100 - (thickness after curing / thickness before curing X 100)

2. Outgas: measured with TD-GC / MS

3. Decomposition temperature: measured by TGA

4. taper shape: measured by V-SEM

Storage stability evaluation

The viscosity was measured immediately after the preparation of the sample used in the above sensitivity evaluation by using a rookfield viscometer viscometer and after standing for 1 week at room temperature, respectively, and the storage stability was evaluated.

1. Initial viscosity: Viscosity immediately after preparation of photosensitive resin composition

2. Viscosity at room temperature 1 week: Viscosity after the above photosensitive resin composition was allowed to stand at room temperature for 1 week

The results of evaluation of the residual film ratio, sensitivity, reliability and storage stability are shown in Tables 2, 3 and 1 to 14 below.

Residual film ratio, sensitivity evaluation Storage stability evaluation Remaining film ratio (%) Sensitivity
(mJ / cm ² ) Initial viscosity
(cP) One week viscosity at room temperature
(cP) Thickness change
(DELTA m) Example 1 86 160 11.66 11.62 0 Example 2 84 170 11.56 11.55 0 Example 3 85 165 11.7 11.7 0 Example 4 87 172 11.7 11.9 0 Example 5 87 100 11.6 11.8 0 Example 6 91 90 11.8 11.8 0 Example 7 84 95 11.4 11.3 0 Example 8 90 100 11.9 11.4 0 Comparative Example 1 77 186 11.2 11.8 0.4 Comparative Example 2 84 191 11.4 20.2 2.6 Comparative Example 3 82 200 11.0 12.1 0.5 Comparative Example 4 68 189 10.9 11.4 One Comparative Example 5 66 95 11.2 21.5 3 Comparative Example 6 55 90 11.2 12.06 0.8

Reliability evaluation Hardening
Temperature 150 ℃ 200 ℃ 230 ℃ 250 ℃ evaluation
Item Film shrinkage factor out
gas decomposition
Temperature Film shrinkage factor out
gas decomposition
Temperature Film shrinkage factor out
gas decomposition
Temperature Film shrinkage factor out
gas decomposition
Temperature unit % ng / cm ² ℃ % ng / cm ² ℃ % ng / cm ² ℃ % ng / cm ² ℃ Example 1 10 4 300 10 2 310 11 One 330 12 0 350 Example 2 9 6 305 10 4 320 11 One 340 11 One 355 Example 3 11 7 310 10 5 330 13 One 350 12 0 370 Example 4 9 6 295 9 3 315 12 2 330 13 One 340 Example 5 10 6 305 10 3 350 12 2 370 14 0 380 Example 6 10 8 310 10 4 330 12 One 350 13 0 372 Example 7 11 6 300 11 3 320 12 2 340 14 0 360 Example 8 10 6 305 11 3 330 12 2 350 14 One 370 Comparative Example 1 15 1000 200 19 500 250 20 420 270 27 350 300 Comparative Example 2 14 1150 190 21 600 220 22 400 250 31 360 295 Comparative Example 3 16 1200 210 25 550 245 30 420 270 41 365 290 Comparative Example 4 20 1200 210 25 510 240 30 430 270 38 300 290 Comparative Example 5 18 950 220 20 600 250 31 395 275 39 315 295 Comparative Example 6 18 990 250 22 410 270 28 300 290 33 250 316

As can be seen from Tables 2 and 3 and FIGS. 1 to 14, when the positive photosensitive resin compositions of Examples 1 to 8 were used, the amount of outgas was significantly reduced as compared with the compositions of Comparative Examples 1 to 6, The film ratio and the film shrinkage ratio are also greatly improved.

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, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (13)

(A) an alkali-soluble resin represented by the following formula (1);
(B) a photosensitive diazoquinone compound;
(C) a thermal acid generator; And
(D) Solvent
A positive photosensitive resin composition comprising:
[Chemical Formula 1]

In Formula 1,
E ¹ and E ² are each independently a hydrogen atom or a residue of a derivative derived from a compound represented by the following formula 2, provided that E ¹ and E ² are not hydrogen atoms at the same time,
X ¹ and Y ¹ are each independently a substituted or unsubstituted aromatic organic group, a substituted or unsubstituted divalent to octavalent aliphatic organic group or a combination thereof,
R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 To C20 heteroaryl group,
o and p are each independently an integer of 0 to 4, provided that o + p > 0,
q and r are each independently an integer of 0 to 2, provided that q + r? 0,
(2)

In Formula 2,
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group or a substituted or unsubstituted C6 to C20 aryl group,
R ³ And R < ⁴ > may be bonded to each other to form a ring,
L1 is a single bond, -O- or -OL'O- (L 'is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group)
n is an integer of 0 or 1;
The method according to claim 1,
Wherein the formula (2) is a positive photosensitive resin composition represented by any one of the following formulas (3) to (6)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above Chemical Formulas 3 to 5,
R ⁵ to R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group or a substituted or unsubstituted C6 to C20 aryl group,
L ² and L ³ are each independently a single bond, -O- or -OL'O- (L 'is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group).
The method according to claim 1,
Wherein the alkali-soluble resin has a weight-average molecular weight of 3,000 g / mol to 300,000 g / mol.
The method according to claim 1,
Wherein the thermal acid generator is a positive photosensitive resin composition represented by the following general formula (7) or (8)
(7)

[Chemical Formula 8]

In the above formulas (7) and (8)
R ⁹ to R ¹³ each independently represents a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkoxy group, C6 < / RTI > to C20 aryl group.
5. The method of claim 4,
Wherein the thermal acid generator is decomposed at a temperature of 120 ° C to 200 ° C to generate an acid.
The method according to claim 1,
Wherein the positive photosensitive resin composition further comprises a dissolution controlling agent, a crosslinking agent, or a combination thereof.
The method according to claim 6,
Wherein the dissolution controlling agent is a positive photosensitive resin composition represented by the following formula (9): < EMI ID =
[Chemical Formula 9]

In the above formula (9)
R ¹⁴ to R ²³ each independently represent a hydrogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkoxy group, C6 < / RTI > to C20 aryl group,
Provided that at least one of R ¹⁴ to R ¹⁸ and at least one of R ¹⁹ to R ²³ is a hydroxy group,
L ⁴ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.
The method according to claim 1,
The positive photosensitive resin composition
(A) 100 parts by weight of an alkali-soluble resin,
(B) 5 to 100 parts by weight of a photosensitive diazoquinone compound and
(C) 1 to 50 parts by weight of a thermal acid generator
/ RTI >
(D) the solvent is contained in an amount of 3% by weight to 30% by weight based on the total solid content of the positive photosensitive resin composition.
The method according to claim 1,
Wherein the positive photosensitive resin composition further comprises an additive selected from the group consisting of a surfactant, a levallizing agent, a silane coupling agent, and a combination thereof.
A positive type photosensitive resin composition according to any one of claims 1 to 9,
The applied positive photosensitive resin composition is dried, heated, exposed and developed,
Post-baking at a temperature of 150 ° C or more and 250 ° C or less after the development,
By weight based on the total weight of the photosensitive resin composition.
11. The method of claim 10,
Wherein the step of curing after development proceeds at a temperature of 150 ° C or more and 230 ° C or less.
A photosensitive resin film produced by using the positive photosensitive resin composition according to any one of claims 1 to 9.
A display device comprising the photosensitive resin film of claim 12.

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