KR101991697B1 - Photosensitive resin composition, black pixel defining layer using the same and display device - Google Patents

Abstract

(A) a binder resin comprising a polyamic acid-polyimide copolymer; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a black colorant; And (E) a solvent, wherein the solvent comprises a first solvent having a boiling point of not less than 140 ° C. and not more than 150 ° C. and a second solvent having a boiling point of not less than 150 ° C. and not more than 200 ° C., There is provided a display device including a black pixel barrier wall layer and a black pixel barrier wall layer manufactured using the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, a black pixel partition wall layer using the same, and a display device using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a photosensitive resin composition, a black pixel barrier wall layer and a display device using the same.

Conventionally, in the case of a color filter such as a color liquid crystal display, a black photosensitive resin composition is used as a barrier rib material at the boundary between color coloring layers to enhance contrast and coloring effect. On the other hand, the organic light emitting diode (OLED) is composed of a TFT, an organic light emitting element, and an electrode for supplying power. The TFT and the electrode use a metal having high electrical conductivity, and thus the reflectance of light is very high. In addition, the barrier rib material and the planarizing layer of the organic light emitting diode use an organic material having a transparency or a transmittance close to that of the transparent organic light emitting diode, there is a problem that real black is difficult to implement, the contrast ratio is reduced, and outdoor visibility is lowered.

Therefore, various attempts have been made to improve the external light reflection as described above. For example, there has been proposed a method of raising a light absorbing material on the electrode surface, that is, applying a black electrode. However, Therefore, it is not preferable. In addition, a method of using a circularly polarizing plate to improve the outdoor visibility by reducing the degree of reflection of external light has been developed and commercialized. However, even if the light emitted from the organic light emitting diode (OLED) is transmitted through the polarizing plate, There is a need to supply a higher current in order to maintain the luminance, which may adversely affect the lifetime of the organic light emitting diode (OLED). In addition, various attempts have been made to improve the contrast by reducing the reflection of external light by applying an antireflection layer. However, there still remains a problem with the reflection of external light, and in the case of a large-area display, such a problem is more serious. Do.

Furthermore, in the case of organic light emitting diodes, efforts are being made to develop photosensitive resin compositions having high heat resistance and low outgassing characteristics to solve such a problem, have.

One embodiment includes a binder resin comprising a polyamide acid-polyimide copolymer having high heat resistance and low outgassing characteristics, and has a solvent system that sufficiently dissolves the binder resin, and has excellent coating properties, To provide a photosensitive resin composition.

Another embodiment is to provide a black pixel partition wall layer made using the above photosensitive resin composition.

Another embodiment is to provide a display device including the black pixel partition wall layer.

One embodiment includes (A) a binder resin comprising a polyamic acid-polyimide copolymer; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a black colorant; And (E) a solvent, wherein the solvent comprises a first solvent having a boiling point of 140 ° C or more and 150 ° C or less and a second solvent having a boiling point of 150 ° C or more and 200 ° C or less.

The second solvent may have a boiling point of more than 150 ° C but not more than 180 ° C.

The first solvent may be included in an amount of 25 wt% to 80 wt% based on the total amount of the solvent, and the second solvent may be included in an amount of 20 wt% to 75 wt% based on the total amount of the solvent.

The first solvent may be contained in an amount of 50 wt% to 80 wt% based on the total amount of the solvent, and the second solvent may be included in an amount of 20 wt% to 50 wt% based on the total amount of the solvent.

The polyamic acid-polyimide copolymer includes a polyamic acid repeating unit and a polyimide repeating unit, and the polyamic acid repeating unit and the polyimide repeating unit may be contained in a molar ratio of 5: 5 to 9: 1.

The polyamic acid-polyimide copolymer may have a weight average molecular weight of 5,000 g / mol to 20,000 g / mol.

The binder resin may further include a cadmium-based binder resin, an acrylic-based binder resin, or a combination thereof.

The binder resin may include a polyamic acid-polyimide copolymer and a carcass binder resin in a weight ratio of 50:50.

The black colorant may include at least one of an organic black pigment and an inorganic black pigment.

The black colorant may have an optical density of 1 to 3 per 1 mu m.

The photopolymerization initiator may include an O-acyloxime compound having a maximum absorbance at 360 to 410 nm.

Wherein the photosensitive resin composition comprises (A) 1 to 10% by weight of a binder resin, (B) 1 to 15% by weight of a photopolymerizable monomer; (C) 0.1 to 5% by weight of a photopolymerization initiator; (D) 1% to 10% by weight of a black colorant; And (E) solvent balance.

The photosensitive resin composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine surfactant, a radical polymerization initiator, or a combination thereof.

Another embodiment provides a manufactured Black Pixel Defining Layer manufactured using the photosensitive resin composition.

Another embodiment provides a display device including the black pixel barrier layer.

The display device may be an organic light emitting diode (OLED).

Other aspects of the present invention are included in the following detailed description.

The photosensitive resin composition according to one embodiment includes a polyamic acid-polyimide copolymer to improve external light reflection, has low outgas characteristics, and has a solvent system capable of sufficiently dissolving the copolymer, , Storage stability and residual film ratio, and vapor pressure can be controlled appropriately, so that the stain occurring in the dried film during the Vccum chamber dry process can be controlled.

1 is a graph showing the absorbance of NCI-831 as a photopolymerization initiator according to the wavelength.

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

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, "an aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the "alkoxysilylene group" means a C1 to C20 alkoxysilylene group.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, An ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1-C10 alkyl group, a C1- A C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkyl group, To C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, C3 to C20 heteroaryl groups, or combinations thereof.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.

&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.

"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.

Unless otherwise specified herein, an unsaturated bond includes not only multiple bonds between carbon-carbon atoms but also other molecules such as carbonyl bonds, azo bonds, and the like.

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

In the present specification, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following formulas (8-1) to (8-11) is contained in the main backbone of the resin.

Unless otherwise stated, the boiling point means the boiling point at atmospheric pressure.

Also, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.

The photosensitive resin composition according to one embodiment comprises (A) a binder resin comprising a polyamic acid-polyimide copolymer; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a black colorant; And (E) a solvent, wherein the solvent comprises a first solvent having a boiling point of 140 ° C or more and 150 ° C or less and a second solvent having a boiling point of 150 ° C or more and 200 ° C or less.

Generally, when a coating film is formed using a photosensitive resin composition, a solvent is volatilized and a thin coating film is formed through a vacuum drying (VCD) process and a soft-baking process. In general, a soft- Lt; 0 > C. If the boiling point of the solvent is similar to or the same as the temperature during the soft-bake process, the solvent is rapidly volatilized and the coating film becomes uneven and the coating property is deteriorated. Therefore, it is preferable to select a solvent having a boiling point higher by 20 ° C than the temperature during the soft-baking, and the residual solvent content, developing property and residual film ratio may vary depending on the content of the solvent having a high boiling point. It is important.

In particular, since the photosensitive resin composition according to one embodiment includes the polyamide acid-polyimide copolymer in the binder resin, unless the ratio of the solvent capable of sufficiently dissolving the binder resin is secured, the photosensitive resin composition A uniform solution can not be produced in the mixing step of the composition or the storage stability is lowered.

The photosensitive resin composition according to an embodiment uses a polyamide acid-polyimide copolymer having high heat resistance and low outgassing characteristics as a binder resin and sufficiently dissolves the resin to improve coatability, VCD characteristics, and processability Solvent system, the coating property, the residual film ratio, and the outgas characteristics are excellent, and the occurrence of VCD stain can be suppressed. In the present invention, a VCD (Vaccum Chamber Dry) process is performed in order to rapidly evaporate the solvent after coating the composition in a lithography process using a photosensitive resin composition of the present invention. At this time, the solvent is not uniformly evaporated And unevenness unevenness that occurs on the surface of the coating film.

Each component will be described in detail below.

(E) Solvent

The solvent may be a solvent having compatibility with a black colorant, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, which will be described later. However, the solvent may be a first solvent having a boiling point of 140 ° C or more and 150 ° C or less, Lt; RTI ID = 0.0 > 200 C < / RTI >

At least one of the first solvent and the second solvent can dissolve the binder resin including the polyamic acid-polyimide copolymer, so that it is possible to produce a uniform solution having storage stability.

For example, the second solvent may have a boiling point of more than 150 ° C but not more than 180 ° C.

The first solvent may be included in an amount of 25 wt% to 80 wt% based on the total amount of the solvent, and the second solvent may be included in an amount of 20 wt% to 75 wt% based on the total amount of the solvent. For example, the first solvent may be contained in an amount of 50 wt% to 80 wt% with respect to the total amount of the solvent, and the second solvent may be included in an amount of 20 wt% to 50 wt% with respect to the total amount of the solvent.

When the content of the first solvent and the second solvent is within the above ranges, it is possible to sufficiently dissolve the binder resin containing the polyamic acid-polyimide copolymer, to have compatibility with the black colorant, And no VCD smear is generated, and a photosensitive resin composition having excellent pattern formability in a TMAH 2.38% developer can be obtained.

Particularly, when the photosensitive resin composition according to one embodiment contains only a solvent having a boiling point of less than 140 캜, the coating property is significantly lowered and VCD stain is also generated. In addition, when the photosensitive resin composition according to one embodiment contains only a solvent having a boiling point of higher than 200 ° C., the residual film ratio characteristic is significantly lowered and the solvent is not completely volatilized even after the soft-baking step and the vacuum drying step, There is a problem that residual solvent remains. Further, the coating property is poor, and VCD stain is also generated.

In addition, when the photosensitive resin composition according to one embodiment contains only the first solvent, the coating property is lowered, and when the second solvent alone is included, the coating property and the residual film ratio are lowered.

Therefore, if the photosensitive resin composition according to one embodiment contains the first solvent and the second solvent in the above-mentioned content range, it is possible to suppress the occurrence of VCD unevenness in addition to excellent coating properties, residual film ratio, and outgas characteristics.

Examples of the first solvent include acetates such as propylene glycol monomethyl ether acetate (PGMEA, boiling point at 145 캜), methyl-3-methoxypropionate (MMP, boiling point at 144 캜) , Ethers such as propionates such as 2-methoxyethyl acetate (boiling point at 145 占 폚), butyl ether (boiling point at 142 占 폚), dibutyl ether (boiling point at 142.4 占 폚) 144.4 占 폚), and the like, but the present invention is not limited thereto.

The second solvent includes, for example, 1-ethoxy-2- (2-methoxyethoxy) ethane, EDM, boiling point of 176 ° C, ethylene glycol monobutyl Ethers such as ethylene glycol monobutyl ether (boiling point at 171 占 폚), isoamyl ether (boiling point at 173 占 폚), ethyl lactate (ethyl lactate, EL, boiling point at 153 占 폚) Alcohols such as butyl lactate (boiling point at 170 캜), amides such as dimethylformamide (DMF, boiling point at 153 캜), ketones such as cyclohexanone (boiling point at 156 캜) 3-alkoxypropionic acid alkyl esters such as ethyl 3-ethoxypropionate (boiling point at 166 deg. C), and the like, but are not limited thereto.

The solvent may be contained in an amount of from 40% by weight to 90% by weight, for example, from 50% by weight to 90% by weight, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity and therefore, the processability in the production of the black pixel barrier wall layer is excellent.

(A) Binder resin

The photosensitive resin composition according to one embodiment includes a binder resin comprising a polyamic acid-polyimide copolymer.

For example, the polyamic acid-polyimide copolymer may be an alkali-soluble polyamic acid-polyimide copolymer.

The binder resin constituting the photosensitive resin composition according to one embodiment has a polyimide unit soluble in an organic solvent and a polyamide acid unit a polyimide precursor structure at the same time to form a high heat resistant black pixel barrier rib layer And it is also advantageous to realize the step difference.

In order to prevent overcharging of the polyamic acid, which is a polyimide precursor, in alkaline aqueous solution, the polyimide, which is the main structure of the polymer, is copolymerized to control the solubility so that a proper difference in solubility between the exposed portion and the non- , Whereby a black pixel barrier wall layer having excellent heat resistance and pattern forming properties can be realized.

For example, the polyamic acid-polyimide copolymer comprises a polyamic acid repeating unit and a polyimide repeating unit, wherein the polyamic acid repeating unit and the polyimide repeating unit have a molar ratio of 5: 5 to 9: 1, such as 5 : 5 to 8: 2, such as a molar ratio of 5: 5 to 7: 3, such as a molar ratio of 5: 5 to 6: 4. When the polyamic acid repeating unit and the polyimide repeating unit are contained in the molar ratio within the above range, the step difference of 1 占 퐉 level becomes easier and the crosslinking property of the copolymer resin becomes excellent. In other words, when the polyimide repeating unit and the polyamic acid repeating unit in the copolymer resin are out of the above-mentioned molar ratio range, that is, when the polyimide repeating unit is contained in an excess amount over the polyamide acid repeating unit, Fall off.

That is, the copolymer can easily control the solubility of the photosensitive resin per se in the alkali aqueous solution by controlling the molar ratio of the polyimide unit having the structure imidized in advance in the solution phase. By adjusting the copolymerization ratio of the alkali soluble imide structure and the polyamic acid structure as the polyimide precursor, the crosslinkable functional group is introduced into the terminal (and / or the chain) of the copolymer resin with appropriate solubility in an alkali aqueous solution, When the light source of the area is irradiated, the exposure area is crosslinked, and the unexposed area forms a fine pattern through the development process. The unexposed area can be thermally cured at a high temperature of 250 캜 or more to have excellent heat resistance.

For example, the polyamic acid-polyimide copolymer may have a weight average molecular weight of 5,000 g / mol to 20,000 g / mol, for example, a weight average molecular weight of 6,000 g / mol to 10,000 g / mol. When the weight average molecular weight of the copolymer is in the above range, it has excellent pattern forming properties, and the produced thin film can have excellent mechanical and thermal properties.

The copolymer may have at least one terminal, for example, an unsaturated double bond at both terminals. The unsaturated double bond may be present in the chain of the copolymer resin besides the terminal of the copolymer. The unsaturated double bond at the terminal (and / or in the middle of the chain) acts as a crosslinkable functional group and can improve the crosslinking property of the copolymer. That is, in order to give the crosslinking property of the copolymer itself by exposure, a monomer capable of crosslinking by a photopolymerization initiator described later is introduced into the terminal group (and / or the middle of the chain) of the main structure to give a photosensitive resin composition And the monomer capable of crosslinking by the photopolymerization initiator may be any one selected from the group consisting of the following formulas (1) to (4).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 1 to 3,

R ¹ to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ to L ⁵ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

For example, the copolymer may be represented by the following general formula (5), but is not limited thereto.

[Chemical Formula 5]

In Formula 5,

X ¹ and X ² are each independently a substituted or unsubstituted quadrivalent alicyclic organic group or a substituted or unsubstituted quadrivalent aromatic organic group,

L ⁶ and L ⁷ are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C10 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group,

R ²⁰ is a substituted or unsubstituted acrylic group, a substituted or unsubstituted methacryl group or a substituted or unsubstituted norbornene group,

m and n are each independently an integer of 1 to 100,000.

For example, the tetravalent aromatic organic group may be represented by the following formula (6).

[Chemical Formula 6]

The C6 to C20 arylene group may include a linking group represented by the following general formula (7).

(7)

In Formula 7,

L ⁸ is a substituted or unsubstituted C1 to C8 alkylene group.

The polyamic acid-polyimide copolymer may be included in an amount of 1 wt% to 10 wt%, for example, 1 wt% to 5 wt% with respect to the total amount of the photosensitive resin composition. When the polyamic acid-polyimide copolymer is contained in the above range, excellent sensitivity, developability, resolution, and straightness of pattern can be obtained.

When the binder resin according to one embodiment contains only the polyamic acid-polyimide copolymer alone, the melting property may be lowered. Therefore, in addition to the polyamic acid-polyimide copolymer, An acrylic binder resin, a carotene binder resin, a novolak resin, a bisphenol A resin, a bisphenol F resin, a silanol group-containing resin, a silsesquioxane-containing resin, or a combination thereof.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and is a resin containing at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.

Specific examples of the acrylic binder resin include (meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate / 2- Acrylate copolymer, a (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but not limited thereto, and they may be used alone or in combination have.

The weight average molecular weight of the acrylic binder resin may be from 5,000 g / mol to 15,000 g / mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion to a substrate during the production of a color filter.

The acid value of the acrylic binder resin may be 80 mgKOH / g to 130 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The cadmium-based binder resin may be represented by the following general formula (8).

[Chemical Formula 8]

In Formula 8,

R ⁵¹ and R ⁵² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ⁵³ and R ⁵⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ⁵⁵ R ⁵⁶ , SiR ⁵⁷ R ⁵⁸ (wherein R ⁵⁵ to R ⁵⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) Is a linking group represented by the following formulas (8-1) to (8-11)

[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

[Formula 8-4]

[Formula 8-5]

(In the formula 8-5,

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH = CH ₂ or a phenyl group.

[Formula 8-6]

[Formula 8-7]

[Formula 8-8]

[Formula 8-9]

[Chemical Formula 8-10]

[Formula 8-11]

Z ² is an acid anhydride residue,

n1 and n2 are each independently an integer of 0 to 4;

The weight average molecular weight of the cationic binder resin may be from 500 g / mol to 50,000 g / mol, such as from 1,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cadmium binder resin is within the above range, the pattern formation is good without residue in the production of the light-shielding layer, and there is no loss of film thickness during development, and a good pattern can be obtained.

The cadmium-based binder resin may include a functional group represented by the following formula (9) in at least one of the two terminals.

[Chemical Formula 9]

In the above formula (9)

Z ³ may be represented by the following formulas (9-1) to (9-7).

[Formula 9-1]

(In the above formula (9-1), R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group.)

[Formula 9-2]

[Formula 9-3]

[Formula 9-4]

[Formula 9-5]

Wherein R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group or a C2 to C20 allylamine group.

[Formula 9-6]

[Formula 9-7]

Examples of the cationic binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, Anhydride compounds such as lyrenetetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic acid dianhydride, and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Propylene glycol methyl ethyl acetate, and N-methyl pyrrolidone; Phosphorus compounds such as triphenylphosphine; And an amine or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, or the like.

When the binder resin according to one embodiment contains only the cation binder binder, the development becomes too fast and the taper characteristics may be greatly reduced (T-top profile observed). To prevent this, the polyamide acid - < / RTI > polyimide copolymer.

The content of the acrylic binder resin or the cation binder resin in the binder resin may be the same as the content of the polyamic acid-polyimide copolymer. When the content of the acrylic binder resin or the cadmium binder resin is equal to the content of the polyamic acid-polyimide copolymer, the melt flow and sensitivity of the composition are excellent and the outgas improvement effect have.

The binder resin may be contained in an amount of 1% by weight to 10% by weight based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

(B) Photopolymerization  Monomer

The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.

By having the ethylenically unsaturated double bond, the photopolymerizable monomer can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethacrylate (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate and the like.

Examples of commercially available products of photopolymerizable monomers are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties.

The photopolymerizable monomer may be contained in an amount of 1 wt% to 15 wt%, for example, 5 wt% to 10 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern forming step, and therefore, the photopolymerizable monomer is excellent in reliability and developability in an alkaline developer.

(C) Light curing Initiator

The photosensitive resin composition according to one embodiment includes a photopolymerization initiator. When the above photopolymerization initiator is used together with a black colorant to be described later in the production of a photosensitive resin composition, internal curing can be efficiently performed while exhibiting black color, thereby maximizing the process margin.

As the photopolymerization initiator, a benzophenone compound, a thioxanone compound, a benzoin compound, a triazine compound, an oxime compound, an acetophenone compound or a combination thereof may be used.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) (Trichloromethyl) -6- (4-methoxystyryl) -s-triazine, 2- [4 (trifluoromethyl) - (4-ethylphenyl) -phenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine.

Examples of the oxime compounds include O-acyloxime compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-a-oxyamino-1-phenylpropan- Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione -1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butan-1-one oxime- O-acetate and the like can be used.

For example, the photosensitive resin composition according to one embodiment may include an O-acyloxime compound having a maximum absorbance at 360 to 410 nm as a photopolymerization initiator. For example, the O-acyloxime compound may have a maximum absorbance at 360 to 390 nm.

For example, the O-acyloxime compound having the maximum absorbance at 360 to 410 nm may be represented by the following general formula (10).

[Chemical formula 10]

In Formula 10,

R ⁶ is a nitro group,

R ⁷ and R ⁸ are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C1 to C10 alkoxy group,

R ⁹ is a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁰ is a substituted or unsubstituted C1 to C10 alkoxy group,

q1 to q3 each independently represent an integer of 0 to 5, provided that 1? q2 + q3? 5.

Examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and the like can be mentioned .

For example, the photopolymerization initiator may further include a compound having a maximum absorption wavelength different from that of the O-acyloxime compound having the maximum absorbance at 360 to 410 nm described above. At this time, the O-acyloxime compound having the maximum absorbance at 360 to 410 nm and the compound having the maximum absorption wavelength may be used at a weight ratio of 1: 9 to 9: 1, such as 4: 6 to 6: 4 have. When the O-acyloxime compound having the maximum absorbance at 360 nm to 410 nm, which is a comparatively long wavelength, is mixed with a compound having a maximum absorption wavelength, the absorption of light occurs in a broader wavelength range, thereby increasing the efficiency of the photopolymerization initiator . In particular, in the case of a photosensitive resin composition containing a black colorant, light may be absorbed / blocked by a photosensitive material, which may lead to a decrease in the efficiency of the photopolymerization initiator. Therefore, a photopolymerization initiator capable of absorbing light at various wavelengths may be mixed in an appropriate ratio, Can be prevented.

For example, the compound having the maximum absorption wavelength different from that of the O-acyloxime compound having the maximum absorbance at 360 to 410 nm may be represented by the following general formula (11) or (12), but is not limited thereto.

(11)

In Formula 11,

R ¹³ to R ¹⁶ are each independently a substituted or unsubstituted C1 to C10 alkyl group,

[Chemical Formula 12]

In Formula 12,

R ¹⁷ to R ¹⁹ are each independently a substituted or unsubstituted C1 to C10 alkyl group.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .

The photopolymerization initiator may be contained in an amount of 0.1 wt% to 5 wt%, for example, 0.1 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, it is possible to obtain sufficient reliability due to sufficient curing during exposure in the pattern formation step, to have excellent heat resistance, light resistance and chemical resistance, excellent resolution and adhesion, It is possible to prevent the transmittance from being lowered.

(D) a black colorant

The photosensitive resin composition according to one embodiment includes a black colorant.

The black colorant may include at least one of an organic black pigment and an inorganic black pigment. The organic black pigment may be, for example, lactam-based organic black, RGB black, RVB black, or the like. The inorganic black pigment may include, for example, aniline black, perylene black, titanium black, cyanine black, lignin black, carbon black or a combination thereof. The black colorant may also include a black dye.

The RGB black or RVB black means a pigment in which at least two or more kinds of colored pigments such as a red pigment, a green pigment, a blue pigment, a violet pigment, a yellow pigment and a purple pigment are mixed to form a black color.

When the black colorant contains only an inorganic black pigment such as carbon black, the inorganic black pigment such as carbon black may have a high optical density because of excellent light shielding property. However, since the UV transmittance of the inorganic black pigment is low, Only the surface hardening is performed and internal hardening may not be performed. If the developing process is performed in this state, the process margin may be lowered. Accordingly, the photosensitive resin composition according to one embodiment is a black coloring agent, which is an organic black pigment capable of ensuring light transmittance in the visible light region and ensuring transmittance in the near infrared region so that photocuring can be sufficiently performed, Can be used with pigments.

The black colorant may have an optical density of 1 to 3, such as 1 to 2, per 1 mu m.

On the other hand, color compensators such as anthraquinone pigments, perylene pigments, phthalocyanine pigments, and azo pigments may be further used together with the black colorant.

A dispersing agent may be used together to disperse the black colorant and the color correcting agent. Specifically, a black coloring agent such as the above-mentioned pigments and a color correcting agent may be surface-treated in advance with a dispersing agent, or a dispersant may be added together with a black coloring agent such as a pigment or a color correcting agent in the production of the photosensitive resin composition.

As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent and the like can be used. Specific examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, Alkylamido alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more thereof.

DISPERBYK-161, DISPERBYK-160, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160, DISPERBYK-130, DISPERBYK- -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.

The dispersant may be contained in an amount of 0.1 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersing agent is contained within the above range, the dispersibility of the photosensitive resin composition is excellent, and thus the stability, developability and patterning property of the black pixel partition wall layer are excellent.

The black colorant such as the pigment may be pretreated by using a water-soluble inorganic salt and a wetting agent. When the black colorant such as a pigment is pre-treated and used, the average particle diameter of the pigment can be made fine.

The pretreatment may be performed by kneading the black colorant such as the pigment with the water-soluble inorganic salt and the wetting agent, and filtering and washing the black colorant such as the pigment obtained in the kneading step.

The kneading may be carried out at a temperature of 40 to 100 DEG C, and the filtration and washing may be performed by washing the inorganic salt with water, etc., followed by filtration.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent acts as a medium through which the black coloring agent such as the pigment and the water-soluble inorganic salt are uniformly mixed to easily pulverize the black coloring agent such as pigment. Examples thereof include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, Alkylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and the like; And alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol and the like. These may be used singly or in combination of two or more thereof.

Specifically, the black coloring agent such as the pigment can be used in the form of a pigment dispersion including the dispersing agent and a solvent described later, and the pigment dispersion may include a solid pigment (black coloring agent), a dispersing agent and a solvent.

The black colorant may be included in an amount of 1 wt% to 10 wt%, for example, 3 wt% to 10 wt% with respect to the total amount of the photosensitive resin composition. When the black colorant is contained within the above range, the brightness, the color recall, the pattern curability, the heat resistance and the adhesion are excellent.

(F) Other additives

Meanwhile, the photosensitive resin composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine surfactant, a radical polymerization initiator, or a combination thereof.

The silane-based coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group in order to improve adhesion with a substrate.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanate propyltriethoxysilane,? -Glycine (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These may be used singly or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included in the above range, the adhesion and storage stability are excellent.

In addition, the photosensitive resin composition may further include a fluorine-based surfactant or a leveling agent for improving coatability and preventing defect formation, if necessary.

The fluorine-containing surfactant or a leveling agent, a ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Mecha Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® , Copper F 554 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray silicone (Note)社SH-28PA ^®, copper -190 ^®, may be used copper -193 ^®, a fluorine-based surfactant or a leveling agent commercially available under the name, such as ^{SZ-6032 ®, SF-8428} ®.

The fluorine-based surfactant or leveling agent may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the fluorine-based surfactant or leveling agent is contained within the above range, coating uniformity is ensured, no unevenness occurs, and wettability to an IZO substrate or a glass substrate is excellent.

The photosensitive resin composition may contain a certain amount of other additives such as an antioxidant and a stabilizer within a range that does not impair the physical properties.

Another embodiment provides a black pixel partition wall layer prepared by exposing, developing and curing the above-mentioned photosensitive resin composition.

The method of manufacturing the black pixel barrier rib layer is as follows.

(1) Coating and Film Formation Step

The photosensitive resin composition is coated on a substrate such as a glass substrate or an IZO substrate subjected to a predetermined pretreatment to a desired thickness by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method or the like, Deg.] C to 110 [deg.] C for 1 minute to 10 minutes to remove the solvent to form a photosensitive resin film.

(2) Exposure step

After the mask is interposed for forming the pattern necessary for the obtained photosensitive resin film, active lines of 200 nm to 500 nm are irradiated. As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used.

The exposure dose differs depending on the kind of each component of the composition, the blending amount, and the dried film thickness, but is 500 mJ / cm ² (according to the 365 nm sensor) or less when high pressure mercury lamp is used.

(3) Development step

As a developing method, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution following the above-described exposure step, so that only the exposed portion is left to form a pattern.

(4) Post-treatment step

There is a post-heating process for obtaining an image pattern obtained by development in the above process, in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability. For example, after development, it may be heated in a convection oven at 250 ° C for 1 hour.

Another embodiment provides a display device including the black pixel barrier layer.

The display device may be an organic light emitting diode (OLED).

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

( Example )

( Polyamidic acid -Polyimide Copolymer Synthesis)

Synthetic example  One: Polyamidic acid Synthesis of Polyimide Copolymer 1

86.6 g of N-methyl-2-pyrrolidone (NMP) was put into a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injector and a condenser while nitrogen was passed through the flask. O-isopropylidene) diphthalic anhydride (6-FDA) were added and dissolved. When the solid was completely dissolved, 3.25 g of 3-aminophenylsulfone (3-DAS) was added and stirred at room temperature for 2 hours. After the temperature was raised to 90 ° C, 5.6 g of pyridine and 2.05 g of acetone hydride (A ₂ CO) were added and stirred for 3 hours. After the temperature in the reactor was cooled to room temperature, 1.6 g of 2-hydroethyl methacrylate (HEMA) was added and stirred for 6 hours. Then, 3.25 g of 3-aminophenylsulfone (3-DAS) was added and reacted for 6 hours to complete the reaction. The reaction mixture was poured into water to form a precipitate, and the precipitate was filtered and sufficiently washed with water, followed by drying at a temperature of 50 DEG C under a vacuum condition for 24 hours or more to prepare a polyamic acid-polyimide copolymer Amide acid-polyimide copolymer 1). The copolymer had a weight average molecular weight of 7,500 g / mol determined by GPC (Gel Permeation Chromatography) standard polystyrene conversion and a degree of dispersion of 1.75. (Molar ratio of polyimide unit and polyamic acid unit = 50: 50)

Synthetic example  2: Polyamidic acid Synthesis of Polyimide Copolymer 2

86.6 g of N-methyl-2-pyrrolidone (NMP) was put into a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injector and a condenser while nitrogen was passed through the flask. O-isopropylidene) diphthalic anhydride (6-FDA) were added and dissolved. When the solid was completely dissolved, 3.25 g of 3-aminophenylsulfone (3-DAS) was added and stirred at room temperature for 2 hours. After the temperature was raised to 90 ° C, 5.6 g of pyridine and 2.05 g of acetone hydride (A ₂ CO) were added and stirred for 3 hours. The temperature in the reactor was cooled to room temperature, and 1.6 g of 2-hydroethyl methacrylate (HEMA) was added thereto, followed by stirring for 6 hours. Then, 3.2 g of 4,4'-oxydianiline (ODA) was added and the reaction was completed for 6 hours. The reaction mixture was poured into water to produce a precipitate. The precipitate was filtered and sufficiently washed with water, and then dried at a temperature of 50 DEG C under a vacuum condition for 24 hours or more to prepare a polyamic acid-polyimide copolymer Acid-polyimide copolymer 2). The copolymer had a weight average molecular weight of 6,800 g / mol as determined by GPC standard polystyrene conversion and a degree of dispersion of 1.82. (Molar ratio of polyimide unit and polyamic acid unit = 50: 50)

Synthetic example  3: Polyamidic acid Synthesis of Polyimide Copolymer 3

N-methyl-2-pyrrolidone (NMP) (86.6 g) was added to a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injector and a condenser, O-isopropylidene) diphthalic anhydride (6-FDA) were added and dissolved. When the solid was completely dissolved, 3.25 g of 4,4'-oxydianiline (ODA) was added and stirred at room temperature for 2 hours. After the temperature was raised to 90 ° C, 5.6 g of pyridine and 2.05 g of acetone hydride (A ₂ CO) were added and stirred for 3 hours. The temperature in the reactor was cooled to room temperature, and 1.6 g of 2-hydroethyl methacrylate (HEMA) was added thereto, followed by stirring for 6 hours. Then, 3.25 g of 3-aminophenylsulfone (3-DAS) was added and reacted for 6 hours to complete the reaction. The reaction mixture was poured into water to produce a precipitate. The precipitate was filtered and sufficiently washed with water, and then dried at a temperature of 50 DEG C under a vacuum condition for 24 hours or more to prepare a polyamic acid-polyimide copolymer Acid-polyimide copolymer 3). The copolymer had a weight average molecular weight of 7,200 g / mol as determined by GPC standard polystyrene conversion and a degree of dispersion of 1.80. (Molar ratio of polyimide unit and polyamic acid unit = 50: 50)

Synthetic example  4: Polyamidic acid Synthesis of Polyimide Copolymer 4

86.6 g of N-methyl-2-pyrrolidone (NMP) was put into a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injector and a condenser while nitrogen was passed through the flask. O-isopropylidene) diphthalic anhydride (6-FDA) were added and dissolved. When the solid was completely dissolved, 2.6 g of 3-aminophenylsulfone (3-DAS) was added thereto, and the mixture was stirred at room temperature for 2 hours. After the temperature was raised to 90 ° C, 5.6 g of pyridine and 2.05 g of acetone hydride (A ₂ CO) were added and stirred for 3 hours. The temperature in the reactor was cooled to room temperature, and 1.6 g of 2-hydroethyl methacrylate (HEMA) was added thereto, followed by stirring for 6 hours. Then, 3.9 g of 3-aminophenylsulfone (3-DAS) was added and reacted for 6 hours to complete the reaction. The reaction mixture was poured into water to produce a precipitate. The precipitate was filtered and sufficiently washed with water, and then dried at a temperature of 50 DEG C under a vacuum condition for 24 hours or more to prepare a polyamic acid-polyimide copolymer Acid-polyimide copolymer 4). The copolymer had a weight average molecular weight of 6,700 g / mol as determined by GPC standard polystyrene conversion and a degree of dispersion of 1.73. (Molar ratio of polyimide unit and polyamic acid unit = 40: 60)

(Preparation of photosensitive resin composition)

Example  1 to Example  9 and Comparative Example  1 to Comparative Example  5

The photosensitive resin compositions according to Examples 1 to 9 and Comparative Examples 1 to 5 were prepared with the compositions shown in Tables 1 and 2 below using the following components.

Specifically, the content of the photopolymerization initiator was precisely measured, the solvent was then added, and the mixture was sufficiently stirred (more than 30 minutes) until the photopolymerization initiator was sufficiently dissolved. The binder resin and the photopolymerizable monomer were sequentially added thereto, followed by stirring for about 1 hour. Then, a colorant (pigment dispersion) was added, and other additives were added thereto, and finally the entire composition was stirred for 2 hours or more to prepare a photosensitive resin composition.

The specifications of each component used in the production of the photosensitive resin composition are as follows.

(A) Binder resin

(A-1) The polyamic acid-polyimide copolymer prepared in Synthesis Example 1

(A-2) The polyamide acid-polyimide copolymer prepared in Synthesis Example 2

(A-3) The polyamic acid-polyimide copolymer prepared in Synthesis Example 3

(A-4) The polyamide acid-polyimide copolymer prepared in Synthesis Example 4

(A-5) Cadmium binder resin (KBR-101, Kyungin Co., Ltd.)

(B) Photopolymerization  Monomer

Dipentaerythritol hexa (meth) acrylate (DPHA, sartomer)

(C) Light curing Initiator

NCI-831, ADEKA

(D) a black colorant

(D-1) Organic black pigment (CIIM-126) dispersion (SAKATA)

(D-2) Carbon black mill base (BK-6925) dispersion (TOKUSIKI)

(E) Solvent

(E-1) Propylene glycol monomethyl ether acetate (PGMEA, Sigma-aldrich) (boiling point: 145 占 폚)

(E-2) 1-ethoxy-2- (2-methoxyethoxy) ethane (EDM, Sigma-aldrich)

(E-3) butyl acetate (BA, Sigma-aldrich) (boiling point: 126 ° C)

(E-4) Gamma butyrolactone (GBL, Sigma-aldrich) (boiling point: 204 ° C)

(F) Other additives

(F-1) leveling agent (F-554 (using 10% diluent), DIC)

(F-2) coupling agent (S-710, Chisso)

(Unit: g) Kinds Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 (A) Binder resin A-1 4.54 4.54 4.54 4.54 2.27 4.54 2.27 2.27 2.27 A-2 - - - - - - 2.27 - - A-3 - - - - - - - 2.27 - A-4 - - - - - - - - 2.27 A-5 - - - - 2.27 - - - - (B) a photopolymerizable monomer 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 (C) a photopolymerization initiator 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 (D) a black colorant D-1 3.7 3.7 3.7 3.7 3.7 1.85 3.7 3.7 3.7 D-2 - - - - - 1.85 - - - (E) Solvent E-1 25.0 42.0 59.0 67.0 42.0 42.0 42.0 42.0 42.0 E-2 59.0 42.0 25.0 17.0 42.0 42.0 42.0 42.0 42.0 E-3 - - - - - - - - - E-4 - - - - - - - - - (F) Other additives F-1 0.020 0.020 0.020 0.020 0.020 0.020 0.020 0.020 0.020 F-2 0.037 0.037 0.037 0.037 0.037 0.037 0.037 0.037 0.037

(Unit: g) Kinds Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (A) Binder resin A-1 4.54 4.54 4.54 4.54 4.54 A-2 - - - - - A-3 - - - - - A-4 - - - - - A-5 - - - - (B) a photopolymerizable monomer 6.7 6.7 6.7 6.7 6.7 (C) a photopolymerization initiator 1.0 1.0 1.0 1.0 1.0 (D) a black colorant D-1 3.7 3.7 3.7 3.7 3.7 D-2 - - - - - (E) Solvent E-1 - - 84.0 - 42.0 E-2 - - - 84.0 - E-3 84.0 - - - - E-4 - 84.0 - - 42.0 (F) Other additives F-1 0.020 0.020 0.020 0.020 0.020 F-2 0.037 0.037 0.037 0.037 0.037

(evaluation)

Coating property

The photosensitive resin compositions according to Examples 1 to 9 and Comparative Examples 1 to 5 were applied to a 10 cm x 10 cm ITO glass (resistance 30 Ω), soft baked on a hot plate at 100 ° C. for 2 minutes The surface characteristics of the formed thin film of 1.2 탆 in thickness were observed with an optical microscope. It is preferable that a uniform and flat thin film is formed. The coating properties are measured by the above-mentioned method, and the results are shown in Tables 3 and 4 below. The evaluation criteria for coating properties are as follows.

○: Surface uniformity, excellent planarization, no defect

?: Surface uniformity, excellent planarization, partial defect

X: Surface unevenness such as surface unevenness, flatness degradation, cracks and unevenness caused by gloss degradation and edge curl

Residual film ratio

The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 5 were applied to ITO glass (resistance 30 Ω) of 10 cm × 10 cm, heated in a proxy type at 100 ° C. for 2 minutes in a proxy type, And heated for 1 minute with a contact type to form a photosensitive resin film having a thickness of 1.2 탆. The substrate coated with the photosensitive resin film was exposed using a mask engraved with various sizes of patterns using UX-1200SM-AKS02 manufactured by Ushio Co., Ltd., and exposed to 2.38% TMAH solution at room temperature to dissolve the exposed portion And then washed with pure water for 50 seconds to form a pattern. The residual film ratios were calculated according to the following equation (1), and the results are shown in Tables 3 and 4 below.

[Equation 1]

Thickness after development / initial (before development) thickness X 100

VCD (Vaccum Chamber Dry) stain

After applying the photosensitive resin composition on a 10x10 cm ITO glass, the VCD process was carried out. The first stage was decompressed from 760 ℃ to 365 torr, and the second stage was decompressed to 760 ℃ and 0.2 torr to volatilize the solvent. The dry film (thickness 1.2 mu m) formed after the VCD process was observed through an optical microscope to see whether or not stains were formed. The results are shown in Tables 3 and 4 below. The evaluation criteria for VCD staining are as follows.

O: Spot observed

X: No staining observed

Residual solvent in outgas

Headspace-GC / MS was used to determine the presence of residual solvent in outgas. The results are shown in Tables 3 and 4 below. The evaluation criteria for the detection of residual solvents in outgas are as follows.

O: Residual solvent in outgas detected

X: No residual solvent in outgass detected

Kinds Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Coating property △ ○ ○ ○ ○ ○ ○ ○ ○ VCD stain X X X X X X X X X Remaining film ratio (%) 80 82 83 83 84 85 88 89 88 Out gas
Residual solvent X X X X X X X X X

Kinds Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Coating property X X X X X VCD stain O O X X O Remaining film ratio (%) 86 70 84 77 74 Out gas
Residual solvent X O X X O

From Table 3 and Table 4, it can be seen that when the soft-baking condition is set to 100 ° C / 2 minutes, when the solvent having a relatively low boiling point or a very high solvent is applied, the coating property of the coating film is uneven and bad overall. In particular, when a very high gamma butyrolactone (GBL) having a boiling point exceeding 200 ° C was applied, the solvent was not completely volatilized after the soft-baking process and the vacuum drying (VCD) process, leaving tacky and therefore difficult to handle. In addition, when propylene glycol monomethyl ether acetate (PGMEA) having a boiling point in the range of 140 to 150 ° C was used alone as in Comparative Example 3, the coating property was lowered, and 1-ethoxy-2- Even when 2-methoxyethoxy) ethane (EDM) was applied alone, the coating and surface properties were not so good due to the relatively high boiling point compared to the soft-baking process. However, as in Examples 1 to 9, the 1-ethoxy-2- (2-methoxyethoxy) ethane (EDM) solvent having a boiling point of 176 ° C was mixed with the propylene glycol monomethyl ether acetate (PGMEA) , The coating properties were excellent and no VCD stain remained.

When the solvent having a high boiling point was used, the residual film ratio decreased remarkably due to the influence of the residual solvent, and the final remainder ratio was also low. In the case of outgassing, residual solvent was detected when a solvent having a high boiling point was applied It is possible to confirm that it acts as a factor that hinders reliability.

An organic solvent having an organic solvent having a boiling point of 140 ° C or higher and 150 ° C or lower at atmospheric pressure in an amount of 25 to 80% by weight, preferably 50 to 80% by weight based on the total weight of the organic solvent, Is 20 wt.% To 75 wt.%, Preferably 20 wt.% To 50 wt.% Based on the total amount of the organic solvent.

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.

Claims (14)

Based on the total weight of the photosensitive resin composition,
(A) 1 to 10% by weight of a binder resin comprising a polyamic acid-polyimide copolymer;
(B) 1 to 15% by weight of a photopolymerizable monomer;
(C) 0.1 to 5% by weight of a photopolymerization initiator;
(D) 1% by weight or more and less than 10% by weight of a black colorant; And
(E) residual solvent
Lt; / RTI >
Wherein the polyamic acid-polyimide copolymer comprises a polyamic acid repeating unit and a polyimide repeating unit, the polyamic acid repeating unit and the polyimide repeating unit are contained in a molar ratio of 5: 5 to 6: 4,
The polyamic acid-polyimide copolymer has a weight average molecular weight of 6,000 g / mol to 10,000 g / mol,
The solvent includes 50 wt% to 80 wt% of a first solvent having a boiling point of 140 ° C or more and 150 ° C or less based on the total amount of the solvent and 20 wt% to 50 wt% of a second solvent having a boiling point of 150 ° C or more and 200 ° C or less By weight.
The method according to claim 1,
And the second solvent has a boiling point of more than 150 DEG C but not more than 180 DEG C.
delete delete delete delete The method according to claim 1,
Wherein the binder resin further comprises a cadmium-based binder resin, an acrylic-based binder resin, or a combination thereof.
The method according to claim 1,
Wherein the black colorant comprises at least one of an organic black pigment and an inorganic black pigment.
The method according to claim 1,
Wherein the black colorant has an optical density of 1 to 3 per 1 mu m.
The method according to claim 1,
Wherein the photopolymerization initiator comprises an O-acyloxime compound having a maximum absorbance at 360 to 410 nm.
delete A Black Pixel Defining Layer produced by using the photosensitive resin composition of any one of claims 1, 2, and 7 to 10.
A display device comprising the black pixel barrier layer of claim 12.
14. The method of claim 13,
Wherein the display device is an organic light emitting diode (OLED).

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