KR20140083693A - Photosensitive resin composition for insulating film of display device, insulating film using the same, and display device using the same - Google Patents

Abstract

The present invention relates to a positive-type photosensitive resin composition comprising (A) alkali-soluble resin, (B) a photosensitive diazoquinone compound, (C) siloxane-containing particles having a specific surface area of 100-400 m^2/g, and (D) a solvent; and to an insulation film and a display device using the photosensitive resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for a display device insulating film, and a display device using the same. [0001] The present invention relates to a photosensitive resin composition for a display device,

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

BACKGROUND ART Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, and mechanical characteristics has been used for a surface protective film and an interlayer insulating film of a semiconductor device. Such a polyimide resin has recently been used in the form of a photosensitive polyimide precursor composition and is easy to apply. After coating the polyimide precursor composition on a semiconductor device, the polyimide resin is subjected to ultraviolet ray patterning, development, thermal imidization, and the like A surface protective film, an interlayer insulating film and the like can be easily formed. Therefore, it has a feature that a process can be significantly shortened compared with the conventional non-photosensitive polyimide precursor composition.

The photosensitive polyimide precursor composition has a positive type in which the exposed portion is dissolved by development and a negative type in which the exposed portion is cured, and in the case of the positive type, a non-toxic alkaline aqueous solution can be used as a developer. The positive photosensitive polyimide precursor composition includes polyamic acid which is a polyimide precursor, diazonaphthoquinone which is a photosensitive material, and the like. However, the positive photosensitive polyimide precursor composition has a problem that a desired pattern can not be obtained because the solubility of the carboxylic acid of the polyamic acid used in the alkali is too high. To solve this problem, there has been proposed a material in which a phenolic hydroxyl group is introduced in place of carboxylic acid such as the content of reacting an alcohol compound having at least one hydroxyl group with an ester bond to a polyamic acid (see JP-A-10-307393) This material has insufficient developability and has a problem that the film is peeled off or the resin peels off from the substrate.

Another method in which a diazonaphthoquinone compound is mixed with a polybenzoxazole precursor (Japanese Patent Publication No. 63-96162) has recently attracted attention, but when a polybenzoxazole precursor composition is actually used, It is difficult to obtain a desired pattern after development because the amount of decrease in the film thickness of the unexposed portion is large. If the molecular weight of the polybenzoxazole precursor is increased, the amount of decrease in the film thickness of the unexposed portion is reduced. However, a phenomenon (scum) is generated in the exposed portion during development, resulting in poor resolution and a longer developing time of the exposed portion there was. To solve such a problem, it has been reported that the addition of a specific phenol compound to the polybenzoxazole precursor composition suppresses the amount of reduction of the film in the unexposed area at the time of development (JP-A-9-302221 and 2000 -292913). However, with this method, there is insufficient effect of suppressing the amount of reduction of the unexposed portion, research for increasing the film reduction suppression effect without generating a developing residue (scum) has been continuously required. In addition, since the phenol used for controlling the solubility causes problems such as decomposition at a high temperature at the time of thermosetting or side reaction, resulting in a serious damage to the mechanical properties of the resultant cured film, a dissolution control agent Research is also required.

In the field of display devices, the positive photosensitive resin composition containing the polybenzoxazole precursor can be applied as an organic insulating film or a barrier rib material. The liquid crystal display device, which is one of the display devices, has advantages such as lightness, thinness, low cost, low power consumption driving and bonding with an excellent integrated circuit, and its use range is expanding for notebook computers, monitors and TV images. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and ITO pixel electrodes are formed, and an upper substrate on which an active circuit portion composed of a liquid crystal layer, a thin film transistor, and a capacitor layer and an ITO pixel electrode are formed. The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate so as to shield the boundary between pixels and a plurality of colors (typically red (R), green (G), blue ) Are arrayed in a predetermined order, and the pixel portions are stacked in this order.

In addition, in the case of an organic light emitting diode (OLED) which has been actively developed recently, each organic EL element may be arranged as a matrix-shaped pixel in order to constitute a fluorescent device, (R), green (G), and blue (B) colors so as to emit various colors.

An embodiment of the present invention is to provide a positive photosensitive resin composition for a display device having a high residual film ratio, a high sensitivity and a high dielectric constant, and a low residual rate of the exposed portion.

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

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

One embodiment of the present invention relates to a photosensitive composition comprising (A) an alkali-soluble resin, (B) a photosensitive diazoquinone compound, (C) a siloxane-containing particle having a specific surface area of 100 to 400 m ² / g, and (D) Type photosensitive resin composition.

The siloxane-containing particles (C) may have a specific surface area of 100 to 300 m ² / g.

The alkali-soluble resin (A) may be a polybenzoxazole precursor, a polyamic acid, a polyimide, or a combination thereof.

The siloxane-containing particles may be represented by the following formula (1).

[Chemical Formula 1]

R _{m is} Si (OR ¹ ) _4-m

In Formula 1, R is a hydrogen atom, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and R < ^{1 >} Represents a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C3 to C30 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and m is an integer of 1 to 3 One can.

Wherein the positive photosensitive resin composition comprises 5 to 100 parts by weight of the photosensitive diazoquinone compound (B), 1 to 10 parts by weight of the siloxane-containing particles (C), and (B) (D) 100 to 400 parts by weight of a solvent.

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

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

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

The photosensitive resin composition for an insulating film according to an embodiment of the present invention, the insulating film using the same, and the display device including the same have excellent residual film ratios, sensitivity, and dielectric constant, and have a low residue rate in the exposed portion.

1 is a schematic (cross-sectional) view showing a display device according to one embodiment.
2 is a schematic view showing an insulating film pattern after exposure / development of the photosensitive resin composition according to one embodiment.

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

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

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

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

(A) an alkali-soluble resin, (B) a photosensitive diazoquinone compound, (C) a siloxane-containing particle having a specific surface area of 100 to 400 m ² / g, and D) solvent.

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

(A) an alkali-soluble resin

The alkali-soluble resin (A) is not limited as long as it is an alkali-soluble resin generally used in the technical field of the present invention. Specifically, the alkali-soluble resin includes a polybenzoxazole precursor containing a repeating unit represented by the following formula (2), a polyamic acid containing a repeating unit represented by the following formula (3), and a repeating unit represented by the following formula At least one selected from polyimide can be used.

Polybenzoxazole  Precursor

(2)

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

In Formula 2, X ¹ may be a residue derived from an aromatic diamine as an aromatic organic group.

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

In the above formula (2), Y ¹ is an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent alicyclic group, and may be a residue of a dicarboxylic acid or a residue of a dicarboxylic acid derivative. Specifically, Y ¹ may be an aromatic organic group, or a divalent to hexavalent alicyclic organic group.

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

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

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

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

Polyamic acid  And polyimide

(3)

[Chemical Formula 4]

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

Specifically, in the above formulas (3) and (4), X ² and X ³ may each independently be a residue derived from an aromatic diamine, an alicyclic diamine, or a silicone diamine. At this time, the aromatic diamine, alicyclic diamine and silicon diamine may be used singly or in combination of one or more thereof.

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

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

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

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

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

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

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

The alkali-soluble resin may have a weight average molecular weight (Mw) of 3,000 to 300,000 g / mol, and more specifically, a weight average molecular weight (Mw) of 5,000 to 30,000 g / mol. When the weight average molecular weight (Mw) is within the above range, a sufficient residual film ratio can be obtained in an unexposed area at the time of development with an aqueous alkali solution, and patterning can be efficiently performed.

(B) Photosensitive Diazoquinone  compound

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

The photosensitive diazoquinone compound may be at least one selected from compounds represented by the following general formulas (5) and (7) to (9), but is not limited thereto.

[Chemical Formula 5]

In the general formula (5), R ⁶⁰ to R ⁶² each independently represent a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, and specifically may be a methyl group.

In Formula 5, R ⁶³ to R ⁶⁵ may each independently be OQ, and Q may be a hydrogen atom, a functional group represented by the following Formula 6a or a functional group represented by the following Formula 6b, There is no.

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

[Chemical Formula 6a]

[Formula 6b]

(7)

In Formula 7, R ⁶⁶ may be a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, and R ⁶⁷ to R ⁶⁹ may each independently be OQ, and Q is the same as defined in Formula 5 , n ²³  To n ²⁵ each may be an integer of 0 to 5.

[Chemical Formula 8]

In Formula 8, A ³ may be CO or CR ⁷⁴ R ⁷⁵ , and R ⁷⁴  And R ⁷⁵ may each independently be a substituted or unsubstituted C1 to C30 alkyl group.

In formula (8), R ⁷⁰ to R ⁷³ each independently represent a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, OQ or NHQ, and Q is the same as defined in the above formula (5).

In Formula 8, n ²⁶ to n ²⁹ may each be an integer of 0 to 4, and n ²⁶ + n ²⁷ and n ²⁸ + n ²⁹ may each be an integer of 5 or less.

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

[Chemical Formula 9]

In the above formula (9)

R ⁷⁴ to R ⁸¹ may be a C1 to C30 alkyl groups each independently represent a hydrogen atom or a substituted or unsubstituted, n ³⁰ and n ³¹ may be an integer from 1 to 5, respectively, Q is as defined in the general formula (5) same.

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

(C) Siloxane  Containing particle

The siloxane-containing particles can be produced by surface-modifying a siloxane-containing compound by a spray drying method. The siloxane-containing particles thus formed can be of a size smaller than nanometers, crystalline or amorphous, transparent because of higher purity than ordinary silica, and have a low refractive index of light and a small loss of light propagation.

The specific surface area of the siloxane-containing particles according to one embodiment may be 100 to 400 m ² / g, specifically 100 to 300 m ² / g. When the specific surface area of the siloxane-containing particles is within the above range, the function of heat resistance and insulation can be enhanced while maintaining a high sensitivity of the positive photosensitive barrier rib pixel layer.

The siloxane-containing particles may be specifically represented by the following formula (1).

[Chemical Formula 1]

R _{m is} Si (OR ¹ ) _4-m

In Formula 1, R is a hydrogen atom, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and R < ^{1 >} Represents a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C3 to C30 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and m is an integer of 1 to 3 One can.

The siloxane-containing particles may be contained in an amount of 1 to 10 parts by weight, specifically 1 to 7 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When it is contained in the above range, it is possible to obtain a photosensitive pixel barrier layer composition which can be uniformly applied to a substrate by preventing the aggregation of silica particles and has high heat resistance and insulation without light loss.

(D) Solvent

The photosensitive resin composition for a display device insulating film may include a solvent capable of easily dissolving each component.

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

The solvent may be included in the positive photosensitive resin composition in an amount of 100 to 400 parts by weight based on 100 parts by weight of the alkali-soluble resin. When it is contained within the above range, it is possible to coat a film of sufficient thickness and have good solubility and coating properties.

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

(E) phenol compound

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

Examples of the phenol compound include compounds represented by the following formulas (10) to (16), but are not limited thereto.

[Chemical formula 10]

In Formula 10,

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

(11)

In Formula 11,

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

[Chemical Formula 12]

In Formula 12,

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

[Chemical Formula 13]

In Formula 13,

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

[Chemical Formula 14]

In Formula 14,

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

[Chemical Formula 15]

In Formula 15,

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

[Chemical Formula 16]

In Formula 16,

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

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

The amount of the phenol compound may be 1 to 40 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the phenol compound is within the above range, a good pattern can be obtained by appropriately increasing the dissolution rate of the unexposed portion without inducing a decrease in sensitivity during development. Further, since the precipitation does not occur during freezing storage, have.

(F) Other additives

The photosensitive resin composition for a display device insulating film according to an embodiment may further include other additives.

The photosensitive resin composition for a display device insulating film may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid to prevent spots, anti-spotting, leveling, 3-amino-1,2-propanediol; A silane-based coupling agent having a vinyl group or (meth) acryloxy group; And the like. The amount of these additives to be used can be easily controlled depending on the desired physical properties. The silane coupling agent can improve adhesion between the photosensitive resin composition for a display device insulating film and the substrate. Examples of the silane coupling agent include compounds represented by the following general formulas (17) to (19); Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (? -Methoxyethoxy) silane; 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- - methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; And carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy [3- (phenylamino) propyl] silane, but are not limited thereto.

[Chemical Formula 17]

In the general formula (17), R ²⁰ is a vinyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, specifically, 3- (meth) acryloxypropyl, ) ≪ / RTI > profile.

In Formula 17, R < ²¹ >  To R ²³ are each independently a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, or a halogen, where R ²¹  To R ²³  At least one of them is an alkoxy group or halogen, specifically, the alkoxy group may be a C1 to C8 alkoxy group, and the alkyl group may be a C1 to C20 alkyl group.

[Chemical Formula 18]

In Formula 18, R ²⁴ is -NH ₂ or -CH ₃ CONH, and R ²⁵ to R ²⁷ are each independently a substituted or unsubstituted C 1 to C 20 alkoxy group. Specifically, the alkoxy group is OCH ₃ or OCH ₂ CH ₃ , and n ₃₄ may be an integer of 1 to 5.

[Chemical Formula 19]

In Formula 19, R < ²⁸ >  To R ³¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 unsubstituted alkoxy groups, specifically, CH ₃ or OCH ₃ Lt; / RTI >

In the above formula (19), R ³² and R ³³ may each independently be a substituted or unsubstituted amino group, and specifically may be NH ₂ or CH ₃ CONH. And n ₃₅ and n ₃₆ may be an integer of 1 to 5, respectively.

The silane-based coupling agent may be used in an amount of 0.1 to 30 parts by weight, preferably 1 to 7 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When it is used within the above range, the adhesion to the upper and lower film layers is excellent, and the remaining film is not left after development, and the mechanical properties such as tensile strength, elongation and the like as well as optical characteristics such as transmittance can be improved.

In addition, the photosensitive resin composition for a display device insulating film may further contain an epoxy compound as an additive for improving adhesion and the like. Examples of the epoxy compound include epoxy novolac acrylate carboxylate resin, orthocresol novolak epoxy resin, phenol novolak epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, or a combination thereof .

When the epoxy compound is further included, it may further include a radical polymerization initiator such as a peroxide initiator or an azobis-based initiator.

The epoxy compound may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition for a display device insulating film. When the epoxy compound is contained within the above range, the adhesion and other properties can be improved in terms of storage stability and economy.

The method for producing the photosensitive resin composition for a display device insulating film is not particularly limited. Specifically, the above-mentioned dye, acrylic binder resin, photopolymerization initiator, photopolymerizable monomer, solvent and optional additives are mixed to form a photosensitive resin A composition can be prepared.

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

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

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

According to another embodiment, there is provided a display device insulation film manufactured using the photosensitive resin composition for a display device insulation film.

The display device insulating film can be manufactured by the following method. The photosensitive resin composition thus prepared is applied to the surface of a substrate by a spraying method, a roll-coating method, a spin coating method, or the like, and then the solvent is removed by pre-bake to form a coating film. The prebaking is preferably carried out at 70 to 150 DEG C for 1 to 5 minutes. Thereafter, a predetermined pattern is formed by irradiating a visible ray, ultraviolet ray, far ultraviolet ray, electron ray, far ultraviolet ray, electron ray, X-ray or the like to the coating film formed according to a previously prepared pattern and developing it with a developer to remove unnecessary portions. At this time, as the developing solution to be used, an aqueous alkali solution may be used, and specific examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; And a mixture thereof can be used. The concentration of the alkaline compound in the developer is preferably 0.1 to 10%. In addition, a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be used together with the solvent. In addition, after developing with the developer as described above, it is cleaned with ultrapure water for 30 to 140 seconds to remove unnecessary portions and dried to form a pattern. After irradiating the formed pattern with light such as ultraviolet rays, And then heated at 110 to 300 DEG C for 30 to 120 minutes by a heating device to obtain a final pattern.

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

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.

( Polybenzoxazole  Precursor preparation)

Synthetic example  One : Polybenzoxazole  Precursor ( PBO -1)

In a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injector and a condenser, 2,2-bis (3- (amino-4-hydroxyphenyl) -1,1,1,3,3 Hexafluoropropane were dissolved in 125 g of N-methyl-2-pyrrolidone (NMP) to dissolve it. When the solid was completely dissolved, 4.2 g of pyridine was added to the solution, and the temperature was adjusted to 0 to 5 ° C Methyldipyrrolidone (NMP) dissolved in 9 g of 4,4'-oxydibenzoyl chloride was slowly added dropwise over 30 minutes while maintaining the temperature at 0 to 5 ° C. for 1 hour after the dropwise addition The reaction was carried out, the temperature was raised to room temperature, and the reaction was terminated by stirring for 1 hour.

To this was added 1.1 g of 5-norbornene-2,3-dicarboxyanhydride and the mixture was stirred at 70 ° C for 24 hours to complete the reaction. The reaction mixture is poured into water to form a precipitate, and the precipitate is filtered and sufficiently washed with water. The polybenzoxazole precursor (PBO-1) was prepared by drying at 80 DEG C under vacuum for 24 hours or more.

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-dicarboxyanhydride.

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

(A) an alkali-soluble resin

(A-1) The polybenzoxazole precursor prepared in Synthesis Example 1 was used.

(A-2) The polybenzoxazole precursor prepared in Synthesis Example 2 was used.

(B) Photosensitive Diazoquinone  compound

A photosensitive diazoquinone represented by the following formula (20) was used.

[Chemical Formula 20]

In formula (20), two of Q are substituted by the following formula (21), and the other is hydrogen.

[Chemical Formula 21]

(C) Siloxane  Containing particle

(C-1) Siloxane-containing particles (R805, Aerosil) having a specific surface area of 150 25 m ² / g were used.

(C-2) Siloxane-containing particles (R812, Aerosil) having a specific surface area of 260 ± 30 m ² / g were used.

(C-3) Siloxane-containing particles (R816, Aerosil) having a specific surface area of 190 ± 20 m ² / g were used.

(C-4) Siloxane-containing particles (R200, manufactured by Aerosil) having a specific surface area of 200 ± 25 m ² / g were used.

(C-5) Siloxane-containing particles (OX50, Aerosil) having a specific surface area of 50 ± 15 m ² / g were used.

(D) Solvent

? -butyrolactone was used.

(E) phenol compound

A phenol compound represented by the following formula (22) was used.

[Chemical Formula 22]

Example  1 to 5 and Comparative Example  1 and Comparative Example  2

Each component was mixed with the composition shown in Table 1 below to prepare a positive photosensitive resin composition. Specifically, the alkali-soluble resin (A) was dissolved in the solvent (D), and the photosensitive diazoquinone compound (B) and the phenol compound (E) were added and dissolved. Thereafter, the siloxane-containing particles were charged into the mixture, stabilized by stirring at room temperature for 1 hour, and then filtered through a 0.45 占 퐉 fluorine resin filter to prepare a positive photosensitive resin composition.

(Parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example
One Comparative Example 2  (A) an alkali-soluble resin (A-1) 100 100 100 100 - 100 100 (A-2) - - - - 100 - -  (B) Photosensitive diazoquinone compound 30 30 30 30 30 30 30  (C) Siloxane-containing particles (C-1) 5 - - - 5 - - (C-2) - 5 - - - - - (C-3) - - 5 - - - - (C-4) - - - 5 - - - (C-5) - - - - - - 5  (D) Solvent 350 350 350 350 350 350 350  (E) phenol compound 20 20 20 20 20 20 20

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

Pattern membrane  Produce

The positive photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were applied to ITO glass using a spin coater and then heated on a hot plate at 120 DEG C for 100 seconds to form a photosensitive polyimide precursor coating film Respectively. The polyimide precursor coating film was exposed to light using an exposure apparatus (I-line stepper, Nikon Corporation, NSR i10C) using a pattern mask in which patterns of various sizes were engraved, and then a 23% aqueous solution of tetramethylammonium hydroxide Lt; 0 > C for 60 seconds. Subsequently, the obtained pattern was cured at 250 DEG C for 40 minutes at an oxygen concentration of 1000 ppm or less by using an electric furnace to obtain a patterned film.

Evaluation example

The residual film ratio, sensitivity, heat resistance, residue, dielectric constant, coating property and transparency of the prepared pattern film were evaluated by the following methods. The results are shown in Table 2 below.

(One) Residual film ratio  Measure

The prefired film was developed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C for 60 seconds, washed with ultrapure water for 60 seconds, dried and measured for film thickness change using AlphaStep (Tencor) And was calculated by the following equation (1).

[Equation 1]

Remaining film ratio = (film thickness after development / initial film thickness before development) x 100

(?: Excellent at a residual film ratio of 90% or more,?: Normal to 80 to 90%, X: 80% or less,

(2) Sensitivity measurement

An exposure time in which a 10 mu m L / S pattern was formed with a line width of 1: 1 after exposure and development was obtained, and this was regarded as an optimum exposure time. The resolution was measured with the minimum pattern size in the optimum exposure time as the resolution.

(?: Excellent sensitivity at 100 mJ / cm 2 or less,?: Normal sensitivity at 100 to 200 mJ / cm 2, and sensitivity at X: 200 mJ / cm 2 or more)

(3) Residue  evaluation

Residual levels of the pattern formed using the photosensitive resin composition prepared above were confirmed by optical microscope and CD-SEM.

(○: clean level of residue, △: slight residual level, X: level of residue)

(4-1) Evaluation of heat resistance: Glass transition temperature ( Tg ) Measure

The wafer coated with the photosensitive resin film formed using the photosensitive resin composition prepared above was immersed in a 2% hydrofluoric acid (HF) aqueous solution to separate the resin film without damaging it. The glass transition temperature was measured by TMA (thermo-mechanical analyzer) analysis of each separated resin film.

(O: excellent heat resistance at a Tg of 280 deg. C or higher, B: heat resistance at a temperature of 230 deg. C to 280 deg. C, and X:

(4-2) Evaluation of heat resistance: 5% weight reduction temperature ( Td ) Measure

The wafer coated with the photosensitive resin film formed using the photosensitive resin composition prepared above was immersed in a 2% hydrofluoric acid (HF) aqueous solution to separate the resin film without damaging it. The thermogravimetric analyzer (TGA) analysis of each of the separated resin films was used to measure the 5% weight loss temperature.

?: Td: Excellent heat resistance at 380 占 폚 or higher,?: Fair heat resistance at Td 330 to 380 占 폚, and X: Low heat resistance at Td 330 占 폚 or less)

(5) Measurement of dielectric constant

The prepared positive photosensitive resin composition was coated on a chromium substrate and treated on a hot plate at 120 ° C for 100 seconds to form a coating film having a final thickness of 3.0 μm. The resulting coating film was cured in an electric furnace at 250 ° C for 40 minutes and dielectric constant was confirmed through a DEA (dielectric analyzer) device.

(?: Dielectric constant 3.0 or less, X: dielectric constant 3.0 or more)

(6) Coating property  evaluation

The prepared positive photosensitive resin composition was coated on ITO glass using a spin coater and treated on a hot plate at 120 ° C for 100 seconds to confirm the uniformity and defects of the coated film by using an optical microscope and SP1 equipment.

(?: Excellent coating property,?: Good coating property / some defects present, X: poor coating property)

(7) Evaluation of transparency: Haze meter  Measure

The coated positive photosensitive resin composition was coated on a quartz substrate using a spin coater and then treated on a hot plate at 120 ° C for 100 seconds. The coated film was cured in an electric furnace at 250 ° C for 40 minutes, and then the haze meter (NDH-2000 , DENSHOKU) equipment to confirm transparency.

?: Excellent in transmittance of 90% or more,?: Transparency in a transmittance of 80 to 90%, and X: transmittance of 80% or less,

division Residual film ratio Sensitivity Residue Heat resistance (1) Heat resistance (2) permittivity Coating property Transparency Example 1 ○ ○ ○ ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ ○ ○ ○ Example 5 ○ ○ ○ ○ ○ ○ ○ ○ Comparative Example 1 ○ ○ ○ X X X ○ ○ Comparative Example 2 ○ △ X ○ ○ ○ △ △

Through the above evaluation examples, it can be confirmed that the positive photosensitive resin composition of the present invention can realize the sensitivity (EOP) at the time when the residual film is not left by appropriately adjusting the development speed of the exposed portion, It was confirmed that no residue was generated in the region.

As shown in Table 2, in Comparative Example 1, the glass transition temperature and the 5% weight reduction temperature were low, so that the heat resistance was low. In Examples 1 to 5, the residual film ratio and sensitivity, dielectric constant, and heat resistance of the non- The residual film of the exposed portion was cleanly removed while maintaining a good level. In the case of Comparative Example 2, it was somewhat superior in terms of heat resistance and dielectric constant. However, due to the small specific surface area of the siloxane-containing particles, coating and transparency deteriorated and the sensitivity was adversely affected.

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

Claims (8)

(A) an alkali-soluble resin;
(B) a photosensitive diazoquinone compound;
(C) siloxane-containing particles having a specific surface area of 100 to 400 m ² / g; And
(D) Solvent
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition. The method of claim 1,
The siloxane-containing particles (C) have a specific surface area of 100 to 300 m ² / g. The method of claim 1,
The alkali-soluble resin (A) is a polybenzoxazole precursor, a polyamic acid, a polyimide or a combination thereof. The method of claim 1,
Wherein the siloxane-containing particles are represented by the following formula (1).
[Chemical Formula 1]
R _{m is} Si (OR ¹ ) _4-m
(Wherein R represents a hydrogen atom, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted A substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group,
R ¹ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, A substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
and m is an integer of 1 to 3.) The method of claim 1,
The positive photosensitive resin composition
With respect to 100 parts by weight of the alkali-soluble resin (A)
5 to 100 parts by weight of the photosensitive diazoquinone compound (B);
1 to 10 parts by weight of the siloxane-containing particles (C); And
100 to 400 parts by weight of the solvent (D)
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition. The method of claim 1,
Wherein the positive photosensitive resin composition further comprises a phenol compound. An insulating film produced by using the positive photosensitive resin composition of any one of claims 1 to 6. A display device comprising an insulating film according to claim 7.

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