KR20130078782A - Positive type photosensitive resin composition - Google Patents

Abstract

PURPOSE: A positive photosensitive resin composition is provided to be able to show an excellent cyclization rate by a low temperature curing reaction, and, therefore, to be able to manufacture a photosensitive resin film with an excellent mechanical property and insulation property. CONSTITUTION: A positive photosensitive resin composition comprises (A) alkali soluble resin selected from a polybenzoxazole precursor, and a polyimide precursor or their combination; (B) a photosensitive diazoquinone compound; (B) a thermoacid generator with a decomposition temperature of 150-200deg.C; and (D) a solvent. The polybenzoxazole precursor includes a repeating unit represented by Chemical formula 1, or both repeating units of Chemical formulas 1 and 2, and has a thermally polymerizable functional group on at least one terminal end.

Description

Positive type photosensitive resin composition {POSITIVE TYPE PHOTOSENSITIVE RESIN COMPOSITION}

A positive photosensitive resin composition and a cured film, an insulating film, a semiconductor device, and a display device using the same.

Photosensitive polyimide and polybenzoxazole resins have excellent thermal and mechanical properties, and have been applied to semiconductor protective films or interlayer insulating films. In particular, due to its heat resistance, low dielectric constant and insulation properties, it has been applied to display devices and the like as insulating films and electrode protective films of organic EL devices. The photosensitive polyimide and polybenzoxazole, which are applied as an insulating film of an organic light emitting device, also have good flattening properties of the coating surface, a very low content of impurities deteriorating the reliability of the device, and an advantage of making a fine shape easy. have.

However, in display devices such as organic EL devices, the reliability improvement of the insulating film is urgently required, and the minimization of the device process and the good shape of the insulating film are required. Particularly, when the process temperature of the insulating film is 250 ° C. or more and the curing process is performed for 1 hour or more, the display device exhibits a decrease in adhesion between the lower and upper substrates of the insulating film and the edge portion of the electrode due to continuous exposure at high temperatures. Insulation breakdown and leakage current may occur. Therefore, in order not to cause display defects in a display element, the manufacturing process which hardens reaction at low temperature is calculated | required.

Accordingly, the present inventors solve the problem that the defective rate of the display device is generated by increasing the closing rate of the polybenzoxazole precursor at low temperature and short process time, and the photosensitive resin composition which does not inhibit the mechanical properties of the photosensitive resin after curing. Developed to complete the present invention.

One embodiment of the present invention is to provide a positive photosensitive resin composition having excellent mechanical properties and insulation properties in the production of a photosensitive resin film by having a good ring-closure rate even by a low temperature curing reaction.

Another embodiment of the present invention is to provide an insulating film to which the positive photosensitive resin composition is applied and a display device including the same.

One embodiment of the present invention is an alkali-soluble resin selected from (A) polybenzoxazole precursor, polyimide precursor or a combination thereof, (B) photosensitive diazoquianone compound, (C) decomposition temperature of 150 ℃ to 200 ℃ It provides a positive photosensitive resin composition comprising a thermal acid generator having a (D) solvent.

The polybenzoxazole precursor may include a repeating unit represented by the following Formula 1 or may include both repeating units of the following Formulas 1 and 2.

[Formula 1]

[Formula 2]

In the above Formulas 1 and 2,

X ₁ is an aromatic organic group or a 4-6 valent aliphatic organic group,

Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group or a 2 to 6-valent aliphatic organic group,

X ₂ is an aromatic organic group, a 2-6 valent aliphatic organic group, a 2-6 valent alicyclic organic group, or an organic group having a structure represented by the following general formula (3),

(3)

In Formula 3,

R ₂₃ to R ₂₆ are the same or different from each other, and each independently, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxy group,

R ₂₇ and R ₂₈ are the same or different, and each independently, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, k is an integer of 1 to 50.

The polyimide precursor may include repeating units represented by Formula 50 and Formula 51.

(50)

(51)

In Formula 50 and Formula 51, X ₃ is an aromatic organic group or a divalent to hexavalent alicyclic organic group, and Y ₃ and Y ₄ are the same or different from each other, and each independently an aromatic organic group, or tetravalent to hexavalent alicyclic an organic group, X ₄ is an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a group represented by the formula 3, R ₁₀₀ to R ₁₀₃ are the same as or different from each other, and are each independently , Hydrogen, or a substituted or unsubstituted C1 to C20 alkyl group.

The thermal acid generator may be at least one of compounds represented by the following Chemical Formulas 22 to 24.

[Chemical Formula 22]

(23)

≪ EMI ID =

In Chemical Formulas 22 to 24,

R ₄₃ to R ₄₉ is a C1 to C30 alkyl group substituted or unsubstituted with a halogen atom, an alkyl group, an alcohol group or an alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, or a R ₅₀ to R ₅₃ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, or a combination thereof In combination, n may be 1 to 5.

In addition, the thermal acid generator may be a compound represented by the following Chemical Formula 22a or 22b.

[Formula 22a]

In Formula 22a, m1 and m2 are each independently an integer of 0 to 10, preferably 0 to 6, and Z ₁ and Z ₂ are each independently a C1 to C10 alkoxy group or a hydrogen atom, or a halogen atom , A C1 to C10 alkyl group substituted or unsubstituted with an alkyl group, an alcohol group or an alkoxy group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkynyl group, or a combination thereof,

[Formula 22b]

In Formula 22b, R ₅₄ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a combination thereof, and R ₅₅ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or It may be an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, or a combination thereof.

In addition, the thermal acid generator may be a compound represented by any one of the following Formula 25 to 35.

(25)

(26)

(27)

(28)

*

[Formula 29]

(30)

(31)

(32)

(33)

[Formula 34]

(35)

The positive photosensitive resin composition comprises (B) 5 to 100 parts by weight of (B) photosensitive diazoquinone compound, (C) 1 to 15 parts by weight of thermal acid generator, and (D) 100 to 400 solvents based on 100 parts by weight of alkali-soluble resin. It may include parts by weight.

Another embodiment of the present invention provides a display element comprising an insulating layer formed using the positive photosensitive resin composition.

Another embodiment of the present invention provides an organic light emitting device using the display device.

The present invention provides a positive photosensitive resin composition having an excellent ring-closure rate even by a low temperature curing reaction, and lowers the curing temperature and curing time in the curing reaction, thereby realizing an insulating film and a display device including the same having improved mechanical properties and insulation properties. .

1 shows a cross-sectional view of an OLED substrate.
2 shows the transverse direction (X-X ') and the longitudinal direction (Y-Y') of the opening of the insulating layer.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

In addition, "alkyl group" means a C1 to C30 alkyl group, preferably C1 to C16 alkyl group, unless otherwise specified herein, "alkylene group" means a C1 to C30 alkylene group, preferably a C1 to C16 alkylene group "Alkenyl group" means a C2 to C30 alkenyl group, preferably C2 to C16 alkenyl group, "alkynyl group" means a C2 to C30 alkynyl group, preferably C2 to C16 alkynyl group, " Cycloalkyl group "means a C3 to C30 cycloalkyl group," alkoxy group "means a C1 to C30 alkoxy group, preferably C1 to C16 alkoxy group," alcohol group "means a C1 to C30 alcohol group, preferably C1 To C16 alkoxy group, “aryl group” means C6 to C30 aryl group, preferably C6 to C18 aryl group, “arylene group” means C6 to C30 arylene group, preferably C6 to C18 arylene group "Heteroaryl group" means C2 to C30 He Teraryl groups, preferably C1 to C16 heteroaryl groups, and "heterocyclic groups" mean C2 to C30 heterocyclic groups, preferably C2 to C18 heterocyclic groups.

In addition, the term "aliphatic organic group" herein refers to C1 to C30 alkyl, C2 to C30 alkenyl, or C2 to C30 alkynyl, "alicyclic organic group" and "alicyclic group" means C3 to C30 cycloalkyl, C3 To C30 cycloalkenyl, or C3 to C30 cycloalkynyl, and “aromatic organic group” means C6 to C30 aryl group or C2 to C30 heteroaryl group.

In the present specification, "substituted" means, unless otherwise defined, at least one hydrogen atom of the functional group of the present invention is halogen atom (F, Cl, Br, or I), hydroxy group, nitro group, cyano group, imino group ( = NH, = NR, R is a C1 to C10 alkyl group, amino group (-NH2, -NH (R '), -N (R ") (R"'), R 'to R "' are each independently C1 To C10 alkyl group), amidino group, hydrazine, hydrazone group, carboxyl group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted Or an unsubstituted C3 to C30 heteroaryl group and a substituted or unsubstituted C2 to C30 heterocycloalkyl group.

In addition, in the present specification, "hetero" means one to three hetero atoms selected from the group consisting of N, O, S, and P in one ring, and the remainder is carbon unless otherwise defined. .

In addition, in this specification, "*" means the part connected with the same or different atom or formula.

In addition, "combination thereof" in the present specification means that two or more substituents are bonded to a single bond or a linking group, or two or more substituents are condensed to each other unless otherwise defined.

One embodiment of the present invention is an alkali-soluble resin selected from (A) polybenzoxazole precursor, polyimide precursor or a combination thereof, (B) photosensitive diazoquianone compound, (C) decomposition temperature of 150 ℃ to 200 ℃ Provided is a positive photosensitive resin composition comprising a thermal acid generator having a (D) silane compound and a solvent (E). Hereinafter, a specific embodiment of each component will be described.

(A) an alkali-soluble resin

The alkali-soluble resin is selected from polybenzoxazole precursors, polyimide precursors, or a combination thereof.

The polybenzoxazole precursor may include a repeating unit represented by the following Formula 1 or may include a repeating unit of the following Formulas 1 and 2. And at least one terminal portion has a thermopolymerizable functional group.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, X ₁ is an aromatic organic group or a 4-6 valent aliphatic organic group, Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group or a 2-6 valent aliphatic organic group , X ₂ is an aromatic organic group, a 2-6 valent aliphatic organic group, a 2-6 valent alicyclic organic group, or an organic group having a structure represented by the following formula (3).

(3)

In Formula 3, R ₂₃ to R ₂₆ are the same or different from each other, and each independently, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxy group, R ₂₇ and R ₂₈ are the same or different, and each independently, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, k is an integer from 1 to 50.

The form of the polybenzoxazole precursor is not particularly limited, and may be any random, block, or alternating copolymer.

In addition, when the polybenzoxazole precursor includes both the repeating unit of Formula 1 and the repeating unit of Formula 2, the repeating unit of Formula 1 may be included in an amount of 60 mol% or more and less than 100 mol%.

X ₁ is typically 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino 4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone , 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl ) -1,1,1,3,3,3-hexafluoropropane, 2,2'-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2 '-Bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2'-bis (3-amino-4-hydroxy-2-triflumethylphenyl) hexafluoro Propane, 2,2'-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2'-bis (4-amino-3-hydroxy-6-trifluoro Chloromethylphenyl) hexafluoropropane, 2 , 2'-bis (4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2'-bis (3-amino-4-hydroxy-5-pentafluoroethylphenyl Hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2 '-(3-amino-4-hydroxy-5-pentafluoroethylphenyl) hexafluoro Propane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2 '-(3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2- ( 3-amino-4-hydroxy-5-trifluoromethylphenyl) -2 '-(3-hydroxy-4-amino-6-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4 -Hydroxy-5-trifluoromethylphenyl) -2 '-(3-hydroxy-4-amino-2-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-2 -Trifluoromethylphenyl) -2 '-(3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino Residues derived from 4-hydroxy-6-trifluoromethylphenyl) -2 '-(3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, and combinations thereof It is not limited to this.

In addition, X ₁ is preferably a compound represented by the following formula (4) and (5).

[Formula 4]

[Chemical Formula 5]

(In Chemical Formulas 4 and 5,

A ₁ may be selected from the group consisting of O, CO, CR ₈ R ₉ , SO ₂ , S, and a single bond,

R ₈ And R ₉ are the same or different from each other, and each independently hydrogen and a substituted or unsubstituted alkyl group may be selected, preferably R ₈ And R ₉ is a fluoroalkyl group,

R ₅ to R ₇ are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, 　 It may be selected from the group consisting of a hydroxyl group, a carboxylic acid group, and a thiol group,

n ₁ may be an integer from 1 to 2,

n ₂ and n ₃ are the same or different from each other, and each independently may be an integer of 1 to 3.)

X ₂ may also be derived from aromatic diamines, silicone diamines, and cycloaliphatic diamines.

Specific examples of the aromatic diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6- Naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether , 1,4-bis (4-aminophenoxy) benzene, and the like, but is not limited thereto. In addition, these aromatic diamine monomers can be used individually or in mixture.

Specific examples of the silicone diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetra Methyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, 1,3-bis (amino Propyl) tetramethyldisiloxane 　 And the like, but is not limited thereto.

Specific examples of the alicyclic diamine include, but are not limited to, cyclohexyldiamine, methylenebiscyclohexylamine, and the like.

In addition, the said aromatic diamine monomer can be used individually or in mixture, and can use suitably the aromatic diamine monomer, a silicone diamine monomer, or an alicyclic diamine.

In addition, Y ₁ and Y ₂ may be representative of a residue of a dicarboxylic acid or a dicarboxylic acid derivative.

Specific examples of the dicarboxylic acid may be Y (COOH) ₂ (where Y is Y ₁ And Y ₂ ).

Specific examples of the dicarboxylic acid derivatives include carbonyl halide derivatives or  And active compounds which are active ester derivatives obtained by reacting Y (COOH) ₂ with 1-hydroxy-1,2,3-benzotriazole and the like. Examples thereof include 4,4'-oxydibenzoyl chloride, diphenyloxydicarboxylic acid chloride, bis (phenylcarboxylic acid chloride) sulfone, bis (phenylcarboxylic acid chloride) ether and bis (phenylcarboxylic acid Chloride) phenone, phthalic carboxylic acid dichloride, terephthalic acid dichloride, isophthalic carboxylic acid dichloride, carboxylic acid dichloride, diphenyloxydicarboxylate benzotriazole and combinations thereof Can be mentioned

In addition, it is preferable that Y ₁ and Y ₂ are compounds represented by the following Chemical Formulas 6 to 8.

[Formula 6]

[Formula 7]

[Formula 8]

(In Chemical Formulas 6 to 8,

R ₁₀ to R ₁₃ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₆ , n ₈ , and n ₉ are the same or different and each independently can be an integer from 1 to 4, n ₇ can be an integer from 1 to 3,

A ₂ may be O, CR ₁₄ R ₁₅ , CO, CONH, S, or SO ₂ , wherein R ₁₄ And R ₁₅ are the same or different and are each independently hydrogen, a substituted or unsubstituted alkyl group, or a fluoroalkyl group.)

In addition, the polybenzoxazole precursor may have a thermopolymerizable functional group derived from a reactive endblocking monomer at either or both of the branched chain ends.

The reactive terminal block monomer may be monoamines having a double bond, monoanhydrides having a double bond, or a combination thereof.

Monoamines having the double bond may be used toluidine, dimethylaniline, ethylaniline, aminophenol, aminobenzyl alcohol, amino indan (aminoindan), amino acetophenone, or a combination thereof, but is not limited thereto.

Mono-hydrides having the double bond are 5-norbornene-2,3-dicarboxylic hydride of formula 9, 3,6-epoxy-1,2,3,6-tetra hydride of formula 10 Loftalic anhydride, isobutenylsuccinic anhydride of formula 11, maleic anhydride, aconitic anhydride, 4,5,6-tetrahydrophthalic anhydride (3 , 4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, itaconic anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) itaconic anhydride (IA), citraconicanhydride (CA), 2,3-dimethylmaleic anhydride (DMMA) or a combination thereof 　 Or the like may be used, but the present invention is not limited thereto.

* [Formula 9]

[Formula 10]

[Formula 11]

In addition, the following Chemical Formulas 12 to 16 are representative examples of the thermopolymerizable functional group positioned at the terminal of the polybenzoxazole precursor, and the thermopolymerizable functional group may be crosslinked in the heating process. 　

[Chemical Formula 12]

(In Chemical Formula 12, R ₁₆ is H, CH ₂ COOH, or CH ₂ CHCHCH _3. )

[Chemical Formula 13]

(In Formula 13, R ₁₇ and R ₁₈ are the same or different from each other, and each independently H or CH _3. )

[Formula 14]

[Formula 15]

(In Formula 15, R ₁₉ is H or CH ₃ , R ₂₀ is CH ₂ or oxygen atom.)

[Chemical Formula 16]

(In Formula 16, R ₂₁ and R ₂₂ are the same or different from each other, and each independently, H, CH ₃ or OCOCH _3. )

The polybenzoxazole precursor may have a weight average molecular weight (Mw) of 3,000 to 300,000. When the weight average molecular weight is in the above range, sufficient physical properties can be obtained, and it is easy to handle because of excellent solubility in organic solvents.

The polyimide precursor may include a repeating unit represented by Formula 50 and Formula 51. By including a repeating unit represented by the following formula (50) can be quickly cured resin at high temperature curing, by including a repeating unit represented by the formula (51) can improve the thermal properties at high temperature curing. 　

(50)

(51)

In Chemical Formulas 50 to 51, X ₃ is an aromatic organic group or a divalent to hexavalent alicyclic organic group, Y ₃ and Y ₄ are the same or different from each other, and each independently an aromatic organic group, or tetravalent to 6 It is a valent alicyclic organic group, X ₄ is an aromatic organic group, a divalent to hexavalent alicyclic organic group, or a functional group represented by the formula (3), R ₁₀₀ to R ₁₀₃ are the same or different from each other, each independently, Hydrogen or a substituted or unsubstituted C1 to C20 alkyl group.

In the positive photosensitive resin composition, when the sum of the repeating unit represented by Formula 50 and the repeating unit represented by Formula 51 is 100 mol%, the repeating unit represented by Formula 50 is 5 mol% to 50 mol. %, The repeating unit represented by Formula 51 may be included in 50 mol% to 95 mol%.

The polyimide precursor may have a weight average molecular weight (Mw) of 3,000 to 300,000.

(B) Photosensitive Diazoquinone  compound

As the photosensitive diazoquinone compound, a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure can be preferably used. It is a material known by US Pat. Nos. 2,772,975, 2,797,213, or 3,669,658, the contents of which are incorporated herein by reference.

Representative examples of the photosensitive diazoquinone compound include compounds represented by the following Chemical Formula 17 and Chemical Formulas 19 to 21, but are not limited thereto.

[Chemical Formula 17]

In Formula 17,

R ₃₁ to R ₃₃ may be the same or different from each other and may each independently be hydrogen or a substituted or unsubstituted alkyl group, preferably CH ₃ ,

D ₁ to D ₃ may be the same or different from each other, and each independently, may be OQ, and Q may be hydrogen, or Chemical Formula 18a or 18b, wherein Q may not be hydrogen at the same time,

n ₃₁ to n ₃₃ are the same or different from each other, and each independently an integer of 1 to 3.

[Formula 18a]

[Formula 18b]

[Chemical Formula 19]

In the above formula (19)

R ₃₄ is hydrogen or a substituted or unsubstituted alkyl group,

D ₄ to D ₆ may be OQ, wherein Q is the same as defined in Formula 17,

n ₃₄ to n ₃₆ are the same or different and are each independently an integer of 1 to 3.

[Chemical Formula 20]

In the above formula (20)

A ₃ may be CO or CRR ', and R and R' may be the same or different from each other, and each independently, a substituted or unsubstituted alkyl group,

D ₇ to D ₁₀ are the same or different from each other, and each independently, may be hydrogen, a substituted or unsubstituted alkyl group, OQ, or NHQ, wherein Q is the same as defined in Formula 17,

n ₃₇ , n ₃₈ , n ₃₉ and n ₄₀ are the same or different from each other, and each independently an integer of 1 to 4,

n ₃₇ + n ₃₈ and n ₃₉ + n ₄₀ may be each independently an integer of 5 or less,

Provided that at least one of the D ₇ to D ₈ is OQ, one aromatic ring has an OQ can contain 1 to 3, there is OQ can contain one to four and one of the aromatic ring.

[Chemical Formula 21]

In Formula 21,

R ₃₅ to R ₄₂ may be the same or different from each other, and may each independently be hydrogen or a substituted or unsubstituted alkyl group,

n ₄₁ and n ₄₂ may be the same or different from each other and may each independently be an integer of 1 to 5, more preferably an integer of 2 to 4,

Q is the same as defined in Formula 17 above.

The photosensitive diazoquinone compound is preferably included in an amount of 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 by exposure, and a good pattern can be obtained without developing a film thickness loss during development.

(C) Thermal acid generator

The thermal acid generator used in the present invention is a compound which promotes a curing reaction by generating an acid while being decomposed by heat. In addition, the decomposition temperature of the thermal acid generator is 150 to 250 ℃, by generating an acid at a temperature of 250 ℃ or less, unlike the curing reaction requiring a curing temperature of 250 ℃ or more of the photosensitive resin composition even at a relatively low temperature Promotes the imidization reaction.

The thermal acid generator may be represented by any one of the following Chemical Formulas 22 to 24.

[Chemical Formula 22]

(23)

≪ EMI ID =

In Chemical Formulas 22 to 24,

R ₄₃ to R ₄₉ is a C1 to C30 alkyl group substituted or unsubstituted with a halogen atom, an alkyl group, an alcohol group or an alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, or a And a combination, for example, -CF ₃ , -CH ₃ , -CH ₂ CH ₂ OCH ₃ , toluene group, a cyclohexyl group substituted with an alcohol group, a cyclopentyl group or a phenyl group, and the like, wherein R ₅₀ to R ₅₃ are each Independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, or a combination thereof, n is 1 to 5;

Formula 22 may be a compound represented by the following Formula 22a.

[Formula 22a]

In Formula 22a, m1 and m2 are each independently an integer of 0 to 10, preferably 0 to 6, and Z ₁ and Z ₂ are each independently a C1 to C10 alkoxy group or a hydrogen atom, or a halogen atom , A C1 to C10 alkyl group substituted or unsubstituted with an alkyl group, an alcohol group or an alkoxy group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkynyl group, or a combination thereof.

Formula 22a may specifically be a compound represented by any one of the following Formulas 25 to 27.

(25)

(26)

(27)

In addition, Chemical Formula 22 may specifically be a compound represented by Chemical Formula 22b. .

[Formula 22b]

In Formula 22b, R ₅₄ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a combination thereof, for example, 2-hydroxycyclohexyl group, 2-hydroxy Cyclohexyl group, 3-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, 4-hydroxycyclohexyl group, 2-methylbenzene group, 3-methylbenzene group, 2-hydroxybenzene group, 3-hydroxy Hydroxybenzene group, R ₅₅ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, or a combination thereof, for example -CF ₃ ,  -CH ₃ , toluene group, -CH ₂ CH ₂ OCH ₃ ,  -C ₅ H ₃ OH and the like.

Formula 22b may specifically be a compound represented by any one of the following Formulas 28 to 31.

(28)

[Formula 29]

(30)

(31)

Formula 23 may specifically be a compound represented by the following Formula 32 or 33.

(32)

(33)

In addition, Chemical Formula 24 may specifically be a compound represented by Chemical Formula 34 or 35.

[Formula 34]

(35)

The thermal acid generator thermally decomposes at a temperature of 150 to 250 ° C., so that the polybenzoxazole precursor or polyimide precursor is dehydrated into a structure of polybenzoxazole or polyimide to promote cyclization, and thus, the lower curing temperature is lowered. The degree of cyclization may be lowered. Therefore, since the photosensitive resin composition having an excellent cyclization rate can be produced even through a curing process having a relatively low curing temperature and a short curing time, even at a temperature lower than that of the conventional curing reaction, it is more advantageous in terms of manufacturing process cost and time. Has an advantage. In addition, at the low curing temperature, the gas generation rate during the curing reaction is reduced, and there is no fear that the formed insulating film is exposed to a high temperature environment for a long time, so that the mechanical properties and insulating properties of the insulating film can be inevitably lowered.

The thermal acid generator may be included in an amount of 1 to 15 parts by weight, preferably 3 to 10 parts by weight, based on 100 parts by weight of the alkali water-soluble resin. When the content of the thermal acid generator is too small, sufficient closing ring of the insulating film may not occur, resulting in degradation of thermal and mechanical properties as the insulating film, which may cause a defect of the display device. When the content is too high, the storage stability of the composition for forming the insulating film is reduced. In addition, there is a possibility that the sensitivity may be impaired in the exposure step. After the curing, residues of the thermal acid generator remain in the insulating film to increase the gas generation rate, thereby increasing the generation rate of the defective display element.

The thermal acid generator may be selectively used according to the curing temperature conditions, it may be used by mixing one or more kinds.

The positive photosensitive resin composition may be used together with the thermal acid generator such as allyl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, perfluoroalkyl sulfonic acid such as trifluoromethane sulfonic acid, fluorobutane sulfonic acid, methane sulfonic acid, ethane sulfonic acid, butane sulfonic acid and the like. Alkyl sulfonic acids may be included.

*

(D) Solvent

The solvent used in the present invention is N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, di Ethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3- Butylene glycol-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 thereof.

The amount of the solvent used in the photosensitive resin composition of the present invention is preferably 100 to 400 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the amount of the solvent used is included in this range, a film of sufficient thickness can be coated, and it is preferable because of excellent solubility and coating property.

(E) Silane  compound

The photosensitive resin composition may further include a silane compound in order to improve adhesion to the substrate.

As the silane compound, a compound represented by the following Formula 36 may be used.

(36)

In Chemical Formula 36,

R ₆₁ may be a vinyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, preferably 3- (methacryloxy) propyl, p-styryl, or 3- (phenylamino) propylyl Can be.

R ₆₂ to R ₆₄ are the same or different from each other, and each independently a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, or halogen, wherein at least one of R ₆₂ to R ₆₄ is an alkoxy group or halogen Preferably, the alkoxy group is a C1 to C8 alkoxy group, the alkyl group may be a C1 to C20 alkyl group.

Representative examples of the silane compound include compounds represented by the following Chemical Formulas 37 and 38; Silane compounds having an aryl group such as trimethoxy [3- (phenylamino) propyl] silane; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl trichlorosilane, vinyltris (β-methoxyethoxy) silane; Or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldi Silane compounds containing carbon-carbon unsaturated bonds, such as ethoxysilane, are mentioned, Most preferably, vinyl trimethoxysilane or vinyl triethoxysilane is mentioned.

[Formula 37]

In Chemical Formula 37,

R ₆₅ is NH ₂ or CH ₃ CONH,

R ₆₆ to R ₆₈ are the same or different from each other, and each independently, a substituted or unsubstituted alkoxy group, preferably the alkoxy group may be OCH ₃ or OCH ₂ CH ₃ ,

n ₆₁ may be an integer from 1 to 5.

(38)

In Formula 38,

R ₆₉ to R ₇₂ are the same or different from each other, and each independently, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, preferably CH ₃ Or OCH ₃ , R ₇₃ and R ₇₄ are the same or different from each other, each independently represent a substituted or unsubstituted amino group, preferably NH ₂ or CH ₃ CONH, and n ₆₂ and n ₆₃ are the same Or different from each other, and each independently may be an integer of 1 to 5.

The silane compound may be used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the silane compound is in the above range, the adhesion with the upper and lower film layers is excellent, and no residual film is left after development, and optical characteristics It is preferable because the mechanical properties of the film such as (transmittance) and tensile strength, elongation, and Young's modulus can be improved.

(F) Other additives

The photosensitive resin composition of this invention may further contain the thermal latent acid generator as an additive. The heat latent acid generator may preferably be an alkyl sulfonic acid such as allyl sulfonic acid such as p-toluene sulfonic acid, benzene sulfonic acid, perfluoroalkyl sulfonic acid such as trifluoromethane sulfonic acid, fluorobutane sulfonic acid, methane sulfonic acid, ethane sulfonic acid, butane sulfonic acid, and the like. Can be. The heat latent acid generator may prevent a phenomenon in which the structure of the polyphenol oxazole precursor-containing polyamide has a dehydration reaction and the degree of cyclization is lowered even when the curing temperature is lowered as a cyclization catalyst.

Further, the photosensitive resin composition of the present invention may further contain a suitable surfactant or a levifying agent as an additive in order to prevent unevenness in film thickness or to improve developability.

The process of forming a pattern using the positive photosensitive resin composition of this invention is a process of apply | coating a positive photosensitive resin composition on a support substrate; Drying the applied composition to form a photosensitive polybenzoxazole precursor film; Exposing the polybenzoxazole precursor film; Developing the exposed polybenzoxazole precursor film with an aqueous alkali solution to produce a photosensitive resin film; And a step of heat-treating the photosensitive resin film. Process conditions for forming the pattern, etc. are well known in the art, so detailed description thereof will be omitted.

Another embodiment of the present invention provides an insulating layer formed using the positive photosensitive resin composition and a display device including the same.

Another embodiment of the present invention provides an organic light emitting device using the display device. That is, the positive photosensitive resin composition of the present invention can be usefully used as a surface protective film and an interlayer insulating film of a semiconductor device.

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

[ Synthetic example  One] Polybenzoxazole  Precursor ( PBO -1) Synthesis of

2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3 while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device, and a cooler 12.4 g of, 3-hexafluoropropane and 125 g of N-methyl-2-pyrrolidone (NMP) were added and dissolved.

When the solid was completely dissolved, 4.2 g of pyridine was added as a catalyst and 9.4 g of 4,4'-oxydibenzoyl chloride was added to NMP 100 g while maintaining the temperature at 0 to 5 ° C. in a four-necked flask equipped with a solution for 30 minutes. It was dripped slowly. After the dropping was completed, the reaction was carried out at 0 to 5 ° C. for 1 hour, and the reaction was carried out for 1 hour by raising the temperature to room temperature.

1.1 g of 5-norbornene-2,3-dicarboxylic hydride was added thereto, stirred at 70 ° C. for 24 hours, and then the reaction was completed. The reaction mixture was added to a solution of water / methanol = 10/1 (volume ratio) to form a precipitate. The precipitate was filtered and washed sufficiently with water, and dried under vacuum at 80 ° C. for at least 24 hours to obtain a polybenzoxazole precursor ( PBO-1) was prepared.

[ Synthetic example  2] Polybenzoxazole  Precursor ( PBO -2)

A polybenzoxazole precursor (PBO-2) was prepared in the same manner as in Synthesis Example 1 except that maleic anhydride was used instead of 5-norbornene-2,3-dicarboxylic hydride.

(Synthesis of Positive Photosensitive Resin Composition)

[ Synthetic example  3]

15 g of the polybenooxazole precursor (PBO-1) prepared in Synthesis Example 1 was dissolved in 35.0 g of gamma-butyrolactone (GBL), followed by melting of 0.75 g of the thermal acid generator compound represented by the following Chemical Formula 25, and the structure of Chemical Formula # 39. 3 g of photosensitive diazoquinone and 0.75 g of trimethoxy [3- (phenylamino) propyl] silane represented by the following Chemical Formula 40 were dissolved as a photoacid generator, and then filtered through a 0.45 μm fluorine resin filter to obtain a positive photosensitive resin composition. .

(25)

[Chemical Formula 39]

이며, 나머지는 수소이다.) (In Chemical Formula 39, Q ₁ , Q ₂ And Q ₃ , two

And the rest is hydrogen.)

[Formula 40]

[ Synthetic example  4]

A positive photosensitive resin composition was obtained in the same manner as in Synthesis Example 3, except that 0.75 g of the thermal acid generator of Formula 25 was changed to 0.75 g of the compound of Formula 27, in Synthesis Example 3.

(27)

[ Synthetic example  5]

A positive photosensitive resin composition was obtained in the same manner as in Synthesis Example 3, except that 0.75 g of the thermal acid generator of Formula 25 was changed to 0.75 g of the compound of Formula 28, in Synthesis Example 3.

(28)

[ Synthetic example  6]

A positive photosensitive resin composition was obtained in the same manner as in Synthesis Example 3, except that 0.75 g of the thermal acid generator of Formula 25 was changed to 0.75 g of the compound of Formula 30, in Synthesis Example 3.

(30)

[ Synthetic example  7]

A positive photosensitive resin composition was obtained in the same manner as in Synthesis Example 3, except that 0.75 g of the thermal acid generator of Formula 25 was changed to 0.75 g of the compound of Formula 32 in Synthesis Example 3.

(32)

[ Synthetic example  8]

Synthesis Example 3 A positive photosensitive resin composition was obtained in the same manner as in Synthesis Example 3, except that 0.75 g of the thermal acid generator of Chemical Formula 25 was changed to 0.75 g of the compound of Chemical Formula 33.

(33)

　

* [Synthesis Example 9]

Synthesis Example 3 A positive photosensitive resin composition was obtained in the same manner as in Synthesis Example 4, except that 0.75 g of the thermal acid generator represented by Chemical Formula 25 was changed to 0.75 g of the compound represented by the following Chemical Formula 34.

[Formula 34]

[ Synthetic example  10]

Positive photosensitive performance was performed in the same manner as in Synthesis Example 3, except that the polybenzoxazole precursor (PBO-2) prepared in Synthesis Example 2 was used instead of the polybenooxazole precursor (PBO-1) prepared in Synthesis Example 1. The resin composition was obtained.

[ Synthetic example  11]

Positive type photosensitive resin in the same manner as in Synthesis Example 4 except that the polybenzoxazole precursor (PBO-2) prepared in Synthesis Example 2 was used instead of the polybenooxazole precursor (PBO-1) prepared in Synthesis Example 1 A composition was obtained.

[ Synthetic example  12]

Positive type photosensitive resin in the same manner as in Synthesis Example 5 except that the polybenzoxazole precursor (PBO-2) prepared in Synthesis Example 2 was used instead of the polybenooxazole precursor (PBO-1) prepared in Synthesis Example 1 A composition was obtained.

[ Synthetic example  13]

Positive type photosensitive resin in the same manner as in Synthesis Example 6 except that the polybenzoxazole precursor (PBO-2) prepared in Synthesis Example 2 was used instead of the polybenooxazole precursor (PBO-1) prepared in Synthesis Example 1 A composition was obtained.

[ Synthetic example  14]

Positive type photosensitive resin was prepared in the same manner as in Synthesis Example 7 except that the polybenzoxazole precursor (PBO-2) prepared in Synthesis Example 2 was used instead of the polybenoxazole precursor (PBO-1) prepared in Synthesis Example 1 A composition was obtained.

[ Synthetic example  15]

Positive photosensitive resin was prepared in the same manner as in Synthesis Example 8 except that the polybenzoxazole precursor (PBO-2) prepared in Synthesis Example 2 was used instead of the polybenooxazole precursor (PBO-1) prepared in Synthesis Example 1. A composition was obtained.

[ Synthetic example  16]

Positive type photosensitive resin in the same manner as in Synthesis Example 9, except that the polybenzoxazole precursor (PBO-2) prepared in Synthesis Example 2 was used instead of the polybenoxazole precursor (PBO-1) prepared in Synthesis Example 1 A composition was obtained.

[synthesis Comparative example  One]

A positive photosensitive resin composition was obtained in the same manner as in Synthesis example 3 except that the thermal acid generator of Chemical Formula 25 was not used.

[synthesis Comparative example  2]

A positive photosensitive resin composition was obtained in the same manner as in Synthesis example 10 except that the thermal acid generator of Chemical Formula 25 was not used.

The polybenzoxazole precursor and the thermal acid generator used in the positive photosensitive resin compositions according to Synthesis Examples 3 to 16 and Synthesis Comparative Examples 1 and 2 are shown in Table 1 below.

Synthesis of Photosensitive Resin Composition Polybenzoxazole precursors Thermal acid generator Resin type Encapsulant Type Siloxane diamine Synthesis Example 3 PBO-1

Yes

Synthesis Example 4

Synthesis Example 5

Synthesis Example 6

Synthesis Example 7 　

Synthesis Example 8

Synthesis Example 9

Synthesis Example 10 PBO-2

Yes

Synthesis Example 11

Synthesis Example 12

Synthesis Example 13 　

Synthesis Example 14

Synthesis Example 15

Synthesis Example 16

Comparative Synthesis Example 1 PBO-1

Yes No Comparative Synthesis Example 2 PBO-2

Yes No

(Photosensitive Resinous  Produce)

( Example  One)

The glass substrate in which the ITO transparent electrode film of thickness 100nm was formed on the alkali free glass surface of thickness 0.5um by the sputtering deposition method was cut | disconnected to the magnitude | size of 100 mm X 100 mm. The photoresist was apply | coated on the ITO board | substrate, and it patterned by exposure and image development by a normal photolithographic method. After the unnecessary portion of ITO was removed by etching, the ITO film was patterned into a stripe shape having a length of 80 mm and a width of 20 um by removing the photoresist. The stripe-type first electrodes are arranged 500 at a pitch of 100 um.

Subsequently, the positive photosensitive resin composition according to Synthesis Example 3 was applied onto the substrate on which the first electrode was formed by spin coating and soft-baked at 120 ° C. for 2 minutes on a hot plate. The film was subjected to UV exposure through a photomask, and then developed by dissolving only the exposed portion with a 2.38% aqueous TMAH solution, followed by washing with distilled water. The glass substrate on which the pattern was formed was heated and cured in an oven for high temperature. At this time, the organic substrate to which the positive photosensitive resin composition according to Synthesis Example 3 was applied was cured at 200 ° C. for 30 minutes to form a photosensitive resin film.

( Example  2 to 14)

Instead of using the positive photosensitive resin composition according to Synthesis Example 3, except for using the positive photosensitive resin composition prepared according to Synthesis Examples 4 to 16 Examples 2 to 14 by the same method as in Example 1 To form a photosensitive resin film.

( Comparative example  One)

Instead of using the positive photosensitive resin composition according to Synthesis Example 3, a photosensitive resin film was formed in the same manner as in Example 1 except for using the positive photosensitive resin composition prepared according to Comparative Synthesis Example 1.

( Comparative example  2)

Instead of using the positive photosensitive resin composition according to Synthesis Example 3, a photosensitive resin film was formed in the same manner as in Example 1 except for using the positive photosensitive resin composition prepared according to Comparative Synthesis Example 2.

( Comparative example  3)

Instead of using the positive photosensitive resin composition according to Synthesis Example 3, the same method as in Example 1 except for using a positive photosensitive resin composition prepared according to Comparative Synthesis Example 1, the curing temperature is 320 ℃ The photosensitive resin film was formed by this.

( Comparative example  4)

Instead of using the positive photosensitive resin composition according to Synthesis Example 3, using the positive photosensitive resin composition prepared according to Comparative Synthesis Example 2, the same method as in Example 1 except that the curing temperature is 320 ℃ The photosensitive resin film was formed by this.

( Insulating layer  And manufacturing a display device comprising the same)

Using the photosensitive resin film produced by the method according to Examples 1 to 14 and Comparative Examples 1 to 4, an OLED insulating layer substrate having an opening having a width of 10 μm and a length of 50 μm was obtained. Each opening was formed by an insulating layer comprising a polyimide film in a shape that exposes the central portion of the first electrode and covers the edge portion of the first electrode as shown in FIG. As shown in FIG. 2, the thickness of the insulating layer is 1.5 µm in the X-X 'portion (the transverse insulation layer thickness between the openings) and 3.1 µm in the Y-Y' portion (the longitudinal insulation layer thickness between the openings). It was.

Subsequently, an organic electroluminescent device was manufactured using the substrate on which the insulating layer was formed. The thin film layer including the light emitting layer was formed by a vacuum deposition method by a resistance wire heating method. In addition, the vacuum degree at the time of vapor deposition is 5 X 10 <^-4> Pa or less, and during vapor deposition, the substrate was rotated with respect to the vapor deposition source. First, 15 nm of copper phthalocyanine and 60 nm of bis (N-ethylcarbazole) were deposited on the entire surface of the substrate effective region to form a hole transport layer. 8-hydroxyquinoline doped with 0.3% weight of 1,3,5,7,8-pentamethyl-4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene in this state -21 nm of aluminum complex (Alq3) was deposited and the green light emitting layer was patterned.

(Property evaluation)

(One) Lung exchange rate  Measure

By scraping the photosensitive resin film formed according to Examples 1 to 14 and Comparative Examples 1 to 4 in the same manner as above, and measuring an infrared spectrometer (IR), the degree of disappearance of the 1710 cm ^-1 peak was confirmed. poly benzo waste rates for oxazole precursor (full cure extinction of 1710 cm ^-1 peak in the immediately preceding 150 ℃ for the 1710 cm ^-1 peak before curing) was calculated.

(2) permittivity measurement

In order to evaluate the insulation of the insulating layer formed after curing, the dielectric constant of each of the photosensitive resin films formed according to Examples 1 to 14 and Comparative Examples 1 to 4 was measured using a DEA (dielectric analyzer) equipment. Confirmed.

(3) 5% weight loss temperature

Wafers coated with a photosensitive resin film formed using the positive photosensitive resin composition formed according to Examples 1 to 14 and Comparative Examples 1 to 4 were immersed in a 2% aqueous hydrofluoric acid (HF) solution to separate the resin film without damage. . 5% weight loss temperature of each separated resin film was measured by thermogravimetric analyzer (TGA) analysis.

(4) glass transition temperature ( Tg ) Measure

The wafers coated with the photosensitive resin film formed using the positive photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4 were immersed in a 2% hydrofluoric acid (HF) aqueous solution to separate the resin film without damage. The glass transition temperature was measured by TMA (thermo-mechanical analyzer) analysis of each resin film separated.

(5) Taper  Angle measurement

Moreover, in the insulating layer containing the polyimide film of the shape which coat | covers the edge part of a 1st electrode, the taper angle of the cross section of the insulating film located in the edge part of an opening part was confirmed using vertical SEM.

The experimental results obtained from the physical property evaluation of the above (1) to (5) are shown in Table 2 below.

Polybenzoxazole precursors Curing condition Lung exchange rate
(%) permittivity 5% weight loss temperature
(℃) Tg
(℃) Taper
Angle
(°) Curing temperature
(℃) Curing time
(minute) Example 1 PBO-1 200 30 80 3.3 350 250 32 Example 2 200 30 89 2.9 360 270 29 Example 3 200 30 87 3.2 350 250 32 Example 4 200 30 84 3.0 330 240 34 Example 5 200 30 85 3.0 400 300 30 Example 6 200 30 88 3.2 330 240 31 Example 7 200 30 90 3.0 370 270 32 Example 8 PBO-2 200 30 82 3.3 330 250 30 Example 9 200 30 82 3.1 400 300 32 Example 10 200 30 85 3.0 350 250 35 Example 11 200 30 88 3.3 360 280 30 Example 12 200 30 86 3.2 360 270 34 Example 13 200 30 79 3.2 370 270 32 Example 14 200 30 77 3.0 340 250 29 Comparative Example 1 PBO-1 200 30 35 4.1 230 160 34 Comparative Example 2 PBO-2 200 30 41 3.9 250 180 35 Comparative Example 3 PBO-1 320 30 81 3.2 470 290 32 Comparative Example 4 PBO-2 320 30 84 3.0 500 300 32

(* The ring closure rate is measured by Example and Comparative Example assuming 100% ring closure of the product cured at 380 ° C. for 1 hour at full curing conditions.)

As shown in Table 2, the positive photosensitive resin composition according to Examples 1 to 14 including the thermal acid generator according to the present invention was confirmed to have a high closing rate and excellent mechanical properties and insulation.

In particular, when compared with Comparative Examples 1 and 2, which were subjected to a curing reaction under the same conditions except that the thermal acid generator was included, Examples 1 to 14 had better ring closure rates and insulation properties, and a 5% weight reduction temperature and Higher values also resulted in excellent heat resistance properties at glass transition temperatures.

On the other hand, Comparative Examples 3 and 4, although the imidization reaction was carried out at a curing temperature (320 ℃) higher than Examples 1 to 14, it had a lower or similar closing rate than Examples 1 to 14. In addition, Examples 1 to 14 were found to implement a taper angle similar to Comparative Examples 3 to 4 cured at higher temperatures.

From the above experimental results, when the thermal acid generator of the present invention is included, the imidation reaction of the polybenzoxazole precursor occurs sufficiently even at a low temperature, and it can be seen that an insulating layer excellent in insulation can be produced even at a low temperature.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

1: first electrode opening
2: second electrode opening
3: cathode
4: organic light emitting layer
5: insulation layer
6: anode
7: TFT electrode layer
8: glass

Claims (10)

(A) alkali-soluble resin selected from polybenzoxazole precursor, polyimide precursor, or a combination thereof;
(B) photosensitive diazoquianone compound;
(C) a thermal acid generator having a decomposition temperature of 150 ℃ to 200 ℃; And
(D) solvent
Positive photosensitive resin composition comprising a. The method of claim 1,
The polybenzoxazole precursor includes a repeating unit represented by the following formula (1) or a positive photosensitive resin having a thermopolymerizable functional group in at least one terminal portion including both repeating units of the following formulas (1) and (2). Composition:
[Formula 1]

(2)

In the above Formulas 1 and 2,
X ₁ is an aromatic organic group or a 4-6 valent aliphatic organic group,
Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group or a 2 to 6-valent aliphatic organic group,
X ₂ is an aromatic organic group, a 2-6 valent aliphatic organic group, a 2-6 valent alicyclic organic group, or an organic group having a structure represented by the following general formula (3),
(3)

In Formula 3,
R ₂₃ to R ₂₆ are the same or different from each other, and each independently, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxy group,
R ₂₇ and R ₂₈ are the same or different, and each independently, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, k is an integer of 1 to 50. The method of claim 1,
The positive photosensitive resin composition wherein the polyimide precursor comprises a repeating unit represented by the following Chemical Formula 50 and Chemical Formula 51:
(50)

(51)

In Chemical Formula 50 and Chemical Formula 51,
X ₃ is an aromatic organic group or a divalent to hexavalent alicyclic organic group,
Y ₃ and Y ₄ are the same or different from each other, and each independently an aromatic organic group or a tetravalent to hexavalent alicyclic organic group,
X ₄ is an aromatic organic group, a divalent to hexavalent alicyclic organic group, or a functional group represented by Formula 3,
R ₁₀₀ to R ₁₀₃ are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C20 alkyl group. The method of claim 1,
A positive photosensitive resin composition wherein the thermal acid generator is at least one of compounds represented by the following Chemical Formulas 22 to 24:
[Chemical Formula 22]

(23)

[Formula 24]

In Chemical Formulas 22 to 24,
R ₄₃ to R ₄₉ are C1 to C30 alkyl groups substituted or unsubstituted with a halogen atom, alkyl group, alcohol group or alkoxy group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 cycloalkyl group or their Combination,
R ₅₀ to R ₅₃ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, or a combination thereof,
N is 1 to 5; The method of claim 1,
Positive photosensitive resin composition wherein the thermal acid generator is a compound represented by the following formula 22a or 22b:
[Formula 22a]

In Chemical Formula 22a,
m1 and m2 are each independently an integer of 0 to 10, preferably 0 to 6 integer,
Z ₁ and Z ₂ are each independently a C1 to C10 alkoxy group or a hydrogen atom, a C1 to C10 alkyl group unsubstituted or substituted with a halogen atom, an alkyl group, an alcohol group or an alkoxy group, a substituted or unsubstituted C2 to C10 alkenyl group, A substituted or unsubstituted C1 to C10 alkynyl group or a combination thereof,
[Formula 22b]

In Chemical Formula 22b,
R ₅₄ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a combination thereof,
R ₅₅ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, or a combination thereof. The method of claim 1,
Positive photosensitive resin composition wherein the thermal acid generator is a compound represented by any one of the following formulas (25) to (35):
(25)

(26)

(27)

(28)

[Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

The method of claim 1,
Positive type photosensitive resin composition containing a silane compound further. The method of claim 1,
The resin composition
(A) 100 parts by weight of alkali-soluble resin
(B) 5 to 100 parts by weight of the photosensitive diazoquinone compound;
(C) 1 to 15 parts by weight of the thermal acid generator; And
(D) 100 to 400 parts by weight of solvent
Positive photosensitive resin composition comprising a. A display element comprising an insulating layer formed using the positive photosensitive resin composition of any one of claims 1 to 8. An organic light emitting device using the display device according to claim 9.

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