KR102057597B1 - Photosensitive resin composition, black pixel defining layer using the same and display device - Google Patents

Abstract

(A) binder resin; (B) a black colorant comprising graphene oxide; (C) photopolymerizable monomer; (D) photoinitiator; And (E) a photosensitive resin composition comprising a solvent, a display device including a black pixel barrier layer and a black pixel barrier layer manufactured using the same.

Description

Photosensitive resin composition, black pixel partition layer and display device using the same {PHOTOSENSITIVE RESIN COMPOSITION, BLACK PIXEL DEFINING LAYER USING THE SAME AND DISPLAY DEVICE}

The present disclosure relates to a photosensitive resin composition, a black pixel partition layer and a display device using the same.

The photosensitive resin composition is a material essential for the production of display elements such as color filters, liquid crystal display materials, display devices such as organic light emitting elements, and display device panel materials. For example, in a color filter such as a color liquid crystal display, in order to increase the display contrast and the color development effect, photosensitivity such as a black pixel partition wall layer is formed at a boundary between colored layers such as red, green, and blue. A resin film is required, and this photosensitive resin film is mainly formed from the photosensitive resin composition.

In particular, a photosensitive resin film such as a pixel partition layer used as a material of a display device panel should have a low taper angle in order to have processability and device reliability. In addition, a colorant such as a pigment or a dye that absorbs light in the visible region for light shielding properties should be used.

Conventionally, a mixed black pigment, an organic black pigment, carbon black, or a mixture thereof is used as a light blocking material, that is, a black colorant used on a thin film transistor (TFT). However, in this case, there is a problem that the optical density per film thickness is low or the dielectric constant is high.

Therefore, the research to develop the photosensitive resin composition for black pixel partition layer manufacture which can solve the said problem is continued.

One embodiment is to provide a photosensitive resin composition having excellent sensitivity, high optical density, low dielectric constant, and easy adjustment of the taper angle.

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

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

One embodiment includes (A) a binder resin; (B) a black colorant comprising graphene oxide; (C) photopolymerizable monomer; (D) photoinitiator; And (E) provides a photosensitive resin composition comprising a solvent.

The black colorant may further include carbon black, organic black pigment or mixed black pigment.

The carbon black may be included in an amount of 20 to 70 parts by weight based on 100 parts by weight of the graphene oxide.

The organic black pigment or mixed black pigment may be included 110 to 160 parts by weight based on 100 parts by weight of the graphene oxide.

The binder resin may include at least one selected from the group consisting of a polyamic acid polymer, a polyamic acid ester polymer, a polyhydroxyamide polymer, a polyimide polymer, a polybenzoxazole polymer, and copolymers thereof.

The binder resin may be a polyamic acid-polyimide copolymer.

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 included in a molar ratio of 5: 5 to 9: 1.

The polyamic acid-polyimide copolymer may have a weight average molecular weight of 3,000 g / mol to 20,000 g / mol.

The photosensitive resin composition may further include a cardo-based binder resin.

The photopolymerizable monomer may include a compound including at least two or more functional groups represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

The compound including at least two or more functional groups represented by Formula 1 may be a compound represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

p, q, r and s are each independently an integer of 1 to 10.

The said photosensitive resin composition is 1 weight%-20 weight% of said (A) binder resin with respect to the total amount of photosensitive resin composition; 1% to 20% by weight of the black colorant (B); 0.5 wt% to 10 wt% of the (C) photopolymerizable monomer; 0.1% to 5% by weight of the photopolymerization initiator (D); And (E) may include the remaining amount of the solvent.

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

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

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

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

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

The photosensitive resin composition according to the exemplary embodiment may maintain a low dielectric constant while minimizing a decrease in optical density with excellent sensitivity by using a black colorant including graphene oxide. Therefore, it is very useful for manufacturing black pixel partition layer.

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

Unless stated otherwise in the specification, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, and "cycloalkenyl group" means a C3 to C20 cycloalkenyl group , "Heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C6 to C20 arylalkyl group, "alkylene group" Is a C1 to C20 alkylene group, and "arylene group" refers to a C6 to C20 arylene group, and "alkylarylene group" refers to a C6 to C20 alkylarylene group, and a "heteroarylene group" to C3 to C20 hetero It means an arylene group and a "alkoxy group" means a C1-C20 alkoxylene group.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom is halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group, Azido, amidino, hydrazino, hydrazono, carbonyl, carbamyl, thiol, ester, ether, carboxyl or salts thereof, sulfonic acid or salts thereof, phosphoric acid or salts thereof, C1 To C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C20 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 To C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a combination thereof.

In addition, unless otherwise specified in the present specification, "hetero" means that at least one hetero atom of N, O, S, and P is included in a chemical formula.

Also, unless stated otherwise in the present specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". "Both mean it's possible.

Unless otherwise defined herein, “combination” means mixed or copolymerized. In addition, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means block copolymer to random copolymerization.

Unless stated otherwise in the present specification, unsaturated bonds include not only multiple bonds between carbon and carbon atoms, but also include other molecules such as carbonyl bonds, azo bonds, and the like.

Unless otherwise defined in the chemical formulas herein, when a chemical bond is not drawn at the position where the chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.

In the present specification, the cardo-based resin refers to a resin in which at least one functional group selected from the group consisting of Formulas 11-1 to 11-11 is included in a backbone in the resin.

Unless otherwise defined herein, "*" means the part connected with the same or different atoms or formulas.

Photosensitive resin composition according to one embodiment is (A) binder resin; (B) a black colorant comprising graphene oxide; (C) photopolymerizable monomer; (D) photoinitiator; And (E) a solvent. Conventionally, inorganic black pigments, such as carbon black, were used alone as a black colorant, but in this case, the optical density could be increased, but there was a problem that the dielectric constant was too high and the sensitivity was also inferior. However, according to one embodiment, by allowing the black colorant to include graphene oxide, while the required properties of the light-shielding material satisfy both low dielectric constant and high optical density simultaneously, sensitivity may also be improved.

Each component is demonstrated concretely below.

(B) black colorant

The black colorant includes graphene oxide. When graphite is oxidized, a graphite oxide having a multilayer structure can be obtained, and only one layer of the multilayer structure of the graphite oxide is extracted (peeled) from graphene oxide. Thus, graphene oxide is structurally different from graphite oxide, and its effect is also different.

The black colorant may further include carbon black, organic black pigment or mixed black pigment together with the graphene oxide. The mixed black pigment refers to a pigment that realizes black by mixing a red pigment, an orange pigment, a blue pigment, a violet pigment, a green pigment, and a yellow pigment. For example, the mixed black pigment may be a pigment in which three or more selected from the group consisting of a pigment, an orange pigment, a blue pigment, and a violet pigment are mixed. For example, the mixed black pigment may be a pigment in which a red pigment, a blue pigment, and a violet pigment are mixed. For example, the mixed black pigment may be a pigment in which an orange pigment, a blue pigment and a violet pigment are mixed.

The red pigment is CI red pigment 179, CI red pigment 254, CI red pigment 255, CI red pigment 264, CI red pigment 270, CI red pigment 272, CI red pigment 177, CI red pigment within the Color Index. 89 and the like, and these may be used alone or in combination of two or more, but is not necessarily limited thereto.

The blue pigment has a color index of C.I. Blue pigment 15: 6, C.I. Blue pigment 15: 0, C.I. Blue pigment 15: 1, C.I. Blue pigment 15: 2, C.I. Blue pigment 15: 3, C.I. Blue pigment 15: 4, C.I. Blue pigment 15: 5, C.I blue pigment 15: 6, C.I. Blue pigment 16 and the like can be used, these may be used alone or in combination of two or more, but is not necessarily limited thereto.

The violet pigment has a C.I. Violet pigment 29, dioxazine violet, first violet B, methyl violet lake, indanthrene brilliant violet and the like can be used, these may be used alone or in combination of two or more, but is not necessarily limited thereto.

When the black colorant further includes carbon black together with the graphene oxide, the graphene oxide may be included in more content than the carbon black. For example, the carbon black may be included in 70 parts by weight or less (for example, 20 parts by weight to 70 parts by weight) with respect to 100 parts by weight of the graphene oxide. For example, the carbon black may be included in an amount of 50 parts by weight or less (eg, 20 parts by weight to 50 parts by weight) with respect to 100 parts by weight of the graphene oxide. When graphene oxide and carbon black are included in the content range, low dielectric constant and excellent sensitivity can be obtained with high optical density.

When the black colorant further includes an organic black pigment or a mixed black pigment together with the graphene oxide, the graphene oxide may be included in a smaller amount than the organic black pigment or the mixed black pigment. For example, the organic black pigment or mixed black pigment may be included in an amount of 110 parts by weight or more (eg, 110 parts by weight to 160 parts by weight) with respect to 100 parts by weight of the graphene oxide. When graphene oxide and organic black pigment or mixed black pigment are included in the content range, it is possible to obtain a low dielectric constant and excellent sensitivity while minimizing a decrease in optical density.

When the graphene oxide or the graphene oxide and the pigment is used as the black colorant, a dispersant may be used together to disperse it. Specifically, the graphene oxide and the pigment may be used by surface treatment as a dispersant in advance, or when the composition is prepared, a dispersant may be added together with the graphene oxide and the pigment.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like may be used. Specific examples of the dispersant include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, and carboxylates. , Alkyl amide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more thereof.

Examples of commercially available products of the above dispersants include BYPER's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, 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, EFKA-450, etc. of EFKA Chemical Co., Ltd .; Zenspera Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, and the like; Or PB711, PB821 from Ajinomoto.

The dispersant may be included in an amount of 0.1 wt% to 15 wt% based on the total amount of the photosensitive resin composition. When the dispersant is included in the above range, according to the dispersibility of the composition is excellent in stability, developability and patternability when manufacturing the black pixel partition layer.

The pigment may be used after pretreatment using a water-soluble inorganic salt and a humectant. When the pigment is used after the pretreatment, the average particle diameter of the pigment can be refined.

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

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

Examples of the water-soluble inorganic salts include sodium chloride and potassium chloride, but are not limited thereto. The wetting agent serves as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed so that the pigment can be easily pulverized. Examples thereof include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like. Alkylene glycol monoalkyl ethers; Alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol, and the like, and the like, and these may be used alone or in combination of two or more thereof.

The pigment passed through the kneading step may have an average particle diameter of 5 nm to 200 nm, such as 5 nm to 150 nm. When the average particle diameter of a pigment is in the said range, stability in a pigment dispersion liquid is excellent and there is no fear of the resolution fall of a pixel.

Specifically, the graphene oxide and the pigment may be used in the form of a dispersion containing the dispersant and the solvent described below, the dispersion may include a graphene oxide (or pigment), a dispersant and a solvent of a solid content. The solid graphene oxide (or pigment) may be included in an amount of 5 wt% to 20 wt%, such as 8 wt% to 20 wt%, based on the total amount of the dispersion.

The black colorant may be included in an amount of 1 wt% to 20 wt%, such as 2 wt% to 15 wt%, based on solids, based on the total amount of the photosensitive resin composition. For example, the black colorant may be included in an amount of 15 wt% to 50 wt%, such as 20 wt% to 45 wt%, based on the pigment dispersion based on the total amount of the photosensitive resin composition. When the black colorant is included in the above range, the coloring effect and development performance is excellent.

(A) binder resin

Photosensitive resin composition according to one embodiment comprises a binder resin, the binder resin is a polyamic acid polymer, polyamic acid ester polymer, polyhydroxyamide polymer, polyimide polymer, polybenzoxazole polymer and copolymers thereof It may include at least one selected from the group consisting of.

For example, the binder resin may be a polyamic acid-polyimide copolymer. By using a polyamic acid-polyimide copolymer as said binder resin, a low taper angle can be maintained.

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 the embodiment has a polyimide unit having solubility in an organic solvent and a polyamic acid unit having a polyimide precursor structure at the same time, thereby making it difficult to implement a high heat resistant black pixel partition layer. It can be provided, and is also advantageous to implement the step.

In order to prevent overdissolution of the polyamic acid as a polyimide precursor to the aqueous alkali solution, the solubility is controlled by copolymerizing polyimide, which is the main structure of the polymer, so that an appropriate solubility difference can be obtained between the exposed part and the non-exposed part during the pattern process. Through this, the black pixel barrier layer having excellent heat resistance and pattern formation property can be realized.

For example, the polyamic acid-polyimide copolymer includes a polyamic acid repeat unit and a polyimide repeat unit, wherein the polyamic acid repeat unit and the polyimide repeat unit have a molar ratio of 5: 5 to 9: 1, such as 5 Molar ratios of 5: 5 to 8: 2, such as 5: 5 to 7: 3, such as 5: 5 to 6: 4. When the polyamic acid repeating unit and the polyimide repeating unit are included in the molar ratio in the above range, it is easier to implement a step of 1 μm, and the crosslinking properties of the copolymer resin are excellent. In other words, when the polyimide repeating unit and the polyamic acid repeating unit in the copolymer resin are out of the molar ratio, that is, when the polyimide repeating unit is included in excess of the polyamic acid repeating unit, the developability of the composition is increased. Will fall.

That is, the copolymer can easily adjust the solubility of the photosensitive resin itself in the aqueous alkali solution by adjusting the molar ratio of the polyimide unit having a structure imidized in advance on the solution. Thus, by adjusting the copolymerization ratio of the alkali-soluble imide structure and the polyamic acid structure which is a polyimide precursor, it has moderate solubility in aqueous alkali solution, and introduces a crosslinkable functional group into the terminal (and / or chain) of the copolymer resin, The exposure area is cross-linked when irradiating the light source of the area band, so that the unexposed area is formed with a fine pattern through a developing process, and thermally cured at a high temperature of 250 ° C. or higher to provide excellent heat resistance.

For example, the polyamic acid-polyimide copolymer may have a weight average molecular weight of 3,000 g / mol to 20,000 g / mol, such as 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 formability, the prepared thin film may have excellent mechanical and thermal properties.

The copolymer may have unsaturated double bonds at at least one end, such as at both ends. The unsaturated double bond may be present in the middle of the chain of the copolymer resin in addition to the terminal of the copolymer. The unsaturated double bond at the end (and / or the middle of the chain) may act as a crosslinkable functional group to improve the crosslinking properties of the copolymer. That is, the photosensitive resin composition which has more excellent contrast by introduce | transducing the monomer which can be bridge | crosslinked by the photoinitiator mentioned above in the terminal group (and / or intermediate chain) of a main structure in order to give the crosslinking characteristic by exposure of the said copolymer itself. It may be implemented, the monomer capable of crosslinking by the photopolymerization initiator may be any one selected from the group consisting of the following formula (4) to (7).

For example, the unsaturated double bond may be derived from any one compound selected from the group consisting of Chemical Formulas 4 to 7, but is not limited thereto.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 7 to 10,

R ²⁰ to R ²⁴ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ⁰ and L ² 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 Chemical Formula 8, but is not limited thereto.

[Formula 8]

In Chemical Formula 8,

X ¹ and X ² are each independently a substituted or unsubstituted tetravalent alicyclic organic group or a substituted or unsubstituted tetravalent 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 ²⁵ 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 (9).

[Formula 9]

The C6 to C20 arylene group may include a linking group represented by Formula 10 below.

[Formula 10]

In Chemical Formula 10,

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

When the binder resin according to one embodiment includes only the polyamic acid-polyimide copolymer alone, the melting property may be reduced, so that the binder resin may be, in addition to the polyamic acid-polyimide copolymer, It may further include an acrylic binder resin and / or cardo binder resin.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin including one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof may 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 wt% to 50 wt%, such as 10 wt% to 40 wt%, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether, etc .; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; Vinyl cyanide compounds such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These etc. can be mentioned, These can be used individually or in mixture of 2 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-hydroxyethyl methacrylate. Methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in combination of two or more thereof. have.

The weight average molecular weight of the acrylic binder resin may be 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 physical and chemical properties of the photosensitive resin composition are excellent, the viscosity is appropriate, and the adhesion to the substrate is excellent when the color filter is manufactured.

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 cardo-based binder resin may be represented by the following formula (11).

[Formula 11]

In Chemical Formula 11,

R ⁵¹ and R ⁵² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxy alkyl 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, or Any one of a linking group represented by Formula 11-1 to Formula 11-11,

[Formula 11-1]

[Formula 11-2]

[Formula 11-3]

[Formula 11-4]

[Formula 11-5]

(In Chemical Formula 11-5,

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 11-6]

[Formula 11-7]

[Formula 11-8]

[Formula 11-9]

[Formula 11-10]

[Formula 11-11]

Z ² is an acid dianhydride residue,

n1 and n2 are each independently an integer of 0-4.

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

The cardo-based binder resin may include a functional group represented by Formula 12 at at least one of both terminals.

[Formula 12]

In Chemical Formula 12,

Z ³ may be represented by the following Formula 12-1 to Formula 12-7.

[Formula 12-1]

(In Formula 12-1, 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 12-2]

[Formula 12-3]

[Formula 12-4]

[Formula 12-5]

(In Formula 12-5, R ^d is O, S, NH, substituted or unsubstituted C1 to C20 alkylene group, C1 to C20 alkylamine group or C2 to C20 allylamine group.)

[Formula 12-6]

[Formula 12-7]

The cardo-based binder resin may be, for example, a fluorene-containing compound such as 9,9-bis (4-oxyranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetra carboxylic dianhydride, benzophenone tetra carboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetra carboxylic dianhydride, phen Anhydride compounds such as relenetetracarboxylic acid dianhydride, tetrahydrofurantetracarboxylic 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; Solvent compounds such as propylene glycol methylethyl acetate and N-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; And amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, and the like.

When the binder resin according to one embodiment includes only the cardo-based binder resin alone, the development may be so fast that the taper property may be greatly reduced (T-top profile is observed). Can be used with polyimide copolymers.

The content of the acrylic binder resin or the cardo-based 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 cardo-based binder resin is the same as the polyamic acid-polyimide copolymer content, it may have excellent developability and sensitivity.

The binder resin may be included in an amount of 1 wt% to 20 wt%, such as 1 wt% to 10 wt%, such as 3 wt% to 8 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included in the above range, excellent sensitivity, developability, resolution and linearity of the pattern can be obtained.

(C) Photopolymerizable  Monomer

The photopolymerizable monomer in the photosensitive resin composition according to one embodiment may be a single compound or a mixture of two different compounds.

When the photopolymerizable monomer is a mixture of two different compounds, any one of the two compounds may be a compound including at least two functional groups represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

For example, the compound including at least two or more functional groups represented by Formula 1 may include 2 to 6 functional groups represented by Formula 1. In this case, a sufficient polymerization can be caused during exposure in the pattern forming step to form a pattern excellent in heat resistance, light resistance and chemical resistance.

For example, the compound including at least two or more functional groups represented by Formula 1 may be a compound represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

p, q, r and s are each independently an integer of 1 to 10.

When the photopolymerizable monomer is a mixture of two different compounds, the other one of the two compounds may be a monofunctional or polyfunctional ester compound of (meth) acrylic acid having at least one ethylenically unsaturated double bond. have.

The monofunctional or polyfunctional ester compound of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be, for example, 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, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipenta Erythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylic Y, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylic Rate or a combination thereof.

Examples of commercially available products of the monofunctional or polyfunctional ester compound of (meth) acrylic acid having at least one ethylenically unsaturated double bond are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, doah Gosei cultivating the T (weeks)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®, and the like; Nihon Kayaku Co., Ltd. KAYARAD TC-110S ^® , TC-120S ^®, etc .; The V-158 ^® and V-2311 ^{® of} Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the difunctional ester of the (meth) acrylic acid include, but are not limited to, Aronix M-210 ^® , M-240 ^® , M-6200 ^®, etc. manufactured by Toagosei Chemical Industries, Ltd .; Nippon Kayaku Co., Ltd. KAYARAD HDDA ^® , HX-220 ^® , R-604 ^®, etc .; The V-260 ^® , V-312 ^® , V-335 HP ^® etc. of Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei the cultivating T (weeks)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , M-8030 ^® , M-8060 ^®, etc .; Nippon Kayaku Co., Ltd. KAYARAD TMPTA ^® , DPCA-20 ^® , East-30 ^® , East-60 ^® , East-120 ^®, etc .; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. The above products can be used alone or in combination of two or more.

The photopolymerizable monomer may be used by treating with an acid anhydride in order to impart better developability.

The photopolymerizable monomer may be included in an amount of 0.5 wt% to 10 wt%, such as 1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included in the above range, curing occurs sufficiently during exposure in the pattern forming process, thereby providing excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, and excellent resolution and adhesion.

(D) Photopolymerization Initiator

The photosensitive resin composition according to one embodiment includes a photopolymerization initiator. The photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or the like.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt -Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone-based compound include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diiso Propyl thioxanthone, etc. are mentioned.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine and 2- (3 ', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-bis (trichloro Romethyl) -6-piperonyl-s-triazine, 2-4-bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like.

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

In addition to the compound, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or the like.

The photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, such as 0.5 wt% to 3 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the above range, the photopolymerization occurs sufficiently during exposure in the pattern forming process for manufacturing the color filter, so that the sensitivity is excellent and the transmittance is improved.

(E) solvent

The solvent may be a material that has compatibility with the black colorant (or a dispersion including the same), the binder resin, the photopolymerizable monomer, and the photopolymerization initiator but does not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy acetate; 3-oxypropionate alkyl esters, such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxy propionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionate alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; Alkyl alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionate esters, such as 2-oxy-2-methyl propionate and 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate and 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of alkyl alkoxy-2-methylpropionates such as methyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate and the like, and N-methylformamide, N, N-dimethylformamide, N-methylformanilade, N-methylacetamide, and N, N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid High boiling point solvents, such as ethyl, diethyl oxalate, diethyl maleate, (gamma) -butyrolactone, ethylene carbonate, a propylene carbonate, and phenyl cellosolve acetate, are mentioned.

Among them, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc. in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included in a balance, such as 30% by weight to 70% by weight, such as 30% by weight to 60% by weight, based on the total amount of the photosensitive resin composition. When the solvent is included in the above range, as the photosensitive resin composition has an appropriate viscosity, processability in manufacturing the black pixel partition layer is excellent.

(F) other additives

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

The silane coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, or the like to improve adhesion to a substrate.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycol. Cidoxypropyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

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, it is excellent in adhesion, storage property and the like.

In addition, the photosensitive resin composition may further include a surfactant, a surfactant, for example, a fluorine-based surfactant and / or a silicone-based surfactant, in order to improve coating properties and prevent defects.

Examples of the fluorine-based surfactants include BM-1000 ^® , BM-1100 ^® , and the like from BM Chemie Co .; Mechapack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^®, etc. from Dai Nippon Inki Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Co., Ltd .; Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^{® from} Asahi Glass Co., Ltd .; May be selected from commercially available under the name, such as Toray Silicone ^® (Note)社SH-28PA, the copper ^® -190, copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

As the silicone surfactant, BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, Commercially available products such as BYK-325 can be used.

The surfactant 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 surfactant is included in the above range, coating uniformity is secured, staining does not occur, and wetting of the IZO substrate or the glass substrate is excellent.

In addition, the photosensitive resin composition may be added a certain amount of other additives such as antioxidants, stabilizers, etc. within a range that does not impair the physical properties.

The photosensitive resin composition according to the exemplary embodiment may be positive or negative, but in order to more completely remove residues in the region where the pattern is exposed after exposure and development of the light-shielding composition, it is more negative. desirable.

Another embodiment provides a black pixel partition layer manufactured by exposing, developing, and curing the photosensitive resin composition described above.

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

(1) application and coating film forming step

After apply | coating the said photosensitive resin composition to a desired thickness on the board | substrate, such as a glass substrate or an ITO board | substrate which gave predetermined | prescribed pretreatment, using a method, such as a spin or a slit coat method, a roll coat method, the screen printing method, an applicator method, 70 The photosensitive resin film is formed by heating at 1 to 10 minutes for 1 to 10 minutes to remove the solvent.

(2) exposure step

After the mask is formed to form a pattern necessary for the obtained photosensitive resin film, active rays of 200 nm to 500 nm are irradiated. As a light source used for 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, etc. can be used, and X-rays, an electron beam, etc. can also be used in some cases.

The exposure amount varies depending on the kind of each component of the composition, the compounding amount and the dry film thickness, but when using a high pressure mercury lamp, the exposure amount is 500 mJ / cm ² or less (by a 365 nm sensor).

(3) developing stage

In the developing method, following the exposure step, an alkaline aqueous solution is used as a developing solution to dissolve and remove unnecessary portions, thereby remaining only the exposed portions to form a pattern.

(4) post-processing steps

There is a post-heating step 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, it may be heated for 1 hour in a convection oven at 250 ℃ after development.

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

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

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

( Example )

(Binder resin synthesis)

Synthesis Example  One

86.6 g of N-methyl-2-pyrrolidone (NMP) was added while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector, and a cooler, and 4,4 '-(hexaple 12.3 g of oroisopropylidene) diphthalic hydride (6-FDA) was added to dissolve it. When the solid was completely dissolved, 3.25 g of 3-aminophenyl sulfone (3-DAS) was added thereto, followed by stirring at room temperature for 2 hours. After the temperature was raised to 90 ° C., pyridine 5.6 g and acetic anhydride (A ₂ CO) 2.05 g were added thereto, followed by stirring for 3 hours. After cooling the temperature in the reactor to room temperature, 1.6 g of 2-hydroethyl methacrylate (HEMA) was added and stirred for 6 hours. Then, 3.25 g of 3-aminophenyl sulfone (3-DAS) was added thereto, followed by reaction for 6 hours to terminate the reaction. The reaction mixture was poured into water to form a precipitate, and the precipitate was filtered off and sufficiently washed with water, and then dried under vacuum at a temperature of 50 ° C. for at least 24 hours to prepare a polyamic acid-polyimide copolymer. The weight average molecular weight calculated | required by the GPC (Gel Permeation Chromatography) standard polystyrene conversion of the copolymer was 7,500 g / mol, and dispersion degree was 1.75. (Molar ratio of polyimide unit and polyamic acid unit = 50: 50)

(Photosensitive resin composition production)

Example  1 to Example  13 and Comparative example  1 to Comparative example  6

To the composition shown in Table 1 to Table 3, after dissolving the photopolymerization initiator in a solvent, it was stirred at room temperature for 2 hours. Binder resin and a photopolymerizable monomer were added here, and it stirred at room temperature for 1 hour. After adding a fluorine-based surfactant (other additive) and a black colorant thereto, the mixture was stirred at room temperature for 1 hour, and then the whole solution was stirred for 2 hours. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

(Unit: g) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 (A) binder resin (A-1) 3.141 3.157 3.166 3.174 3.068 3.031 (A-2) 3.141 3.157 3.166 3.174 3.068 3.031 (B) black colorant (B-1) 40.9 27.3 20.5 13.6 27.3 20.5 (B-2) - 7.560 11.341 15.121 - - (B-3) - - - - 10.0 15.0 (B-4) - - - - - - (B-5) - - - - - - (B-6) - - - - - - (C) photopolymerizable monomer (C-1) 0.938 0.943 0.946 0.948 0.916 0.905 (C-2) 0.938 0.943 0.946 0.948 0.916 0.905 (D) photoinitiator 1.060 1.066 1.069 1.072 1.036 1.024 (E) solvent (E-1) 26.018 32.045 35.058 38.072 29.868 31.794 (E-2) 23.800 23.800 23.800 23.800 23.800 23.800 (F) other additives 0.055 0.055 0.055 0.055 0.055 0.055

(Unit: g) Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 (A) binder resin (A-1) 2.995 3.076 3.043 3.011 3.110 3.094 (A-2) 2.995 3.076 3.043 3.011 3.110 3.094 (B) black colorant (B-1) 13.6 27.3 20.5 13.6 27.3 20.5 (B-2) - - - - - - (B-3) 20.0 - - - - - (B-4) - 10.0 15.0 20.0 - - (B-5) - - - - 10.0 15.0 (B-6) - - - - - - (C) photopolymerizable monomer (C-1) 0.895 0.919 0.909 0.899 0.929 0.924 (C-2) 0.895 0.919 0.909 0.899 0.929 0.924 (D) photoinitiator 1.011 1.039 1.028 1.017 1.050 1.045 (E) solvent (E-1) 33.719 29.845 31.759 33.673 29.745 31.609 (E-2) 23.800 23.800 23.800 23.800 23.800 23.800 (F) other additives 0.055 0.055 0.055 0.055 0.055 0.055

(Unit: g) Example 13 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 (A) binder resin (A-1) 3.079 3.191 3.141 3.157 2.995 3.011 3.079 (A-2) 3.079 3.191 3.141 3.157 2.995 3.011 3.079 (B) black colorant (B-1) 13.6 - - - - - - (B-2) - 22.681 - 7.560 - - - (B-3) - - - - 20.0 - - (B-4) - - - - - 20.0 - (B-5) 20.0 - - - - - 20.0 (B-6) - - 40.9 27.3 13.6 13.6 13.6 (C) photopolymerizable monomer (C-1) 0.920 0.953 0.938 0.943 0.895 0.899 0.920 (C-2) 0.920 0.953 0..938 0.943 0.895 0.899 0.920 (D) photoinitiator 1.040 1.077 1.060 1.066 1.011 1.017 1.040 (E) solvent (E-1) 33.473 44.098 26.018 32.045 33.719 33.673 33.473 (E-2) 23.800 23.800 23.800 23.800 23.800 23.800 23.800 (F) other additives 0.055 0.055 0.055 0.055 0.055 0.055 0.055

(A) binder resin

(A-1) Polyamic acid-polyimide copolymer of Synthesis Example 1

(A-2) Cardo Binder Resin (KBR-101, Kyungin Corporation)

(B) black colorant

(B-1) Graphene oxide dispersion (DGO-15D, Daeju Electronic Materials Co., Ltd.)

(B-2) Carbon black mill base (BK-6925) dispersion (TOKUSHIKI Co., Ltd.)

(B-3) Organic black pigment (CIM-126) dispersion (SAKATA company)

(B-4) Millbase Dispersion with Y139, B15: 6, V29 (SAKATA)

(B-5) Millbase dispersion with O64, B15: 6, V29 (SAKATA)

(B-6) Graphite Oxide Dispersion (ACS METERIAL)

(C) Photopolymerizable  Monomer

(C-1) dipentaerythritol hexa (meth) acrylate (DPHA, Nippon Kayaku Co., Ltd.)

(C-2) A compound represented by the following formula (A) (LTM II, BASF Corporation)

[Formula A]

(In Formula A, r and s are each independently an integer of 2)

(D) Photopolymerization Initiator

Oxime initiator (NCI-831, ADEKA Corporation)

(E) solvent

(E-1) Propylene Glycol Monomethyl Ether Acetate (PGMEA), BP 146 ° C (Sigma-Aldrich)

(E-2) 3-methoxybutanol acetate (3-MBA), BP 172 ° C (Sigma-Aldrich)

(F) other additives

Surfactant (BYK-307, BYK Chem)

Evaluation 1: Sensitivity

The photosensitive resin compositions according to Examples 1 to 13 and Comparative Examples 1 to 6 were applied to 10 cm * 10 cm ITO glass (resistance 30Ω), heated to a proxy type for 1 minute on a hot plate at 100 ° C, The film was heated for 1 minute to form a photosensitive resin film having a thickness of 1 μm. The photosensitive resin film-coated substrate was exposed using a mask engraved with a pattern of various sizes with an exposure unit (Ushio's UX-1200SM-AKS02) with a change in exposure dose, and then developed with a 2.38% TMAH solution at room temperature. After dissolving and removing an exposure part, it wash | cleaned with pure water for 50 second and formed the pattern. Sensitivity was evaluated by the method of confirming the energy to implement a 20 ㎛ pattern based on the pattern size measured using the Olympus MX51T-N633MU, the results are shown in Table 4 below.

Evaluation 2: optical density

The photosensitive resin compositions according to Examples 1 to 13 and Comparative Examples 1 to 6 were applied to 10 cm * 10 cm ITO glass (resistance 30Ω), heated in a hot plate at 100 ° C. for 1 minute, and then heated to 2.2. A photosensitive resin film having a thickness was formed. After curing the photosensitive resin film at 250 ° C. for 1 hour, the optical density was measured using an X-rite Exact densimeter, and the results are shown in Table 4 below.

Evaluation 3: permittivity

The photosensitive resin compositions according to Examples 1 to 13 and Comparative Examples 1 to 6 were applied onto a Cr substrate, and heated to a contact type for 1 minute on a 100 ° C. hot plate to form a 2.2 μm thick photosensitive resin film. It was. One side was wiped off with acetone about 0.5 cm before hardening the said photosensitive resin film. And cured for 1 hour at 250 ℃, Al Electrode deposition, Capacitance (C) was measured, the dielectric loss (dielectric constant) was measured using a Precision Impedance Analyzer (Model: 4294A, HP) equipment, the results are shown in the table below 4 is shown.

Sensitivity (mJ / cm ² ) Optical Density (/ ㎛) permittivity Example 1 70 2.8 3.9 Example 2 70 2.8 4.0 Example 3 75 2.9 4.1 Example 4 75 2.9 4.2 Example 5 60 2.5 3.9 Example 6 55 2.0 3.8 Example 7 50 1.8 3.7 Example 8 50 2.2 3.9 Example 9 50 1.8 3.8 Example 10 50 1.6 3.8 Example 11 55 2.2 3.9 Example 12 55 1.9 3.7 Example 13 55 1.7 3.7 Comparative Example 1 80 2.0 5.8 Comparative Example 2 90 3.0 5.8 Comparative Example 3 80 2.6 5.6 Comparative Example 4 60 1.5 5.7 Comparative Example 5 70 1.3 5.8 Comparative Example 6 70 1.5 5.9

Through Table 4, the photosensitive resin composition according to the embodiment is superior to the photosensitive resin composition using a black colorant containing no graphene oxide by using a black colorant containing graphene oxide, optical density It can be seen that the decrease in the dielectric constant and the dielectric constant can be reduced at the same time.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (16)

(A) binder resin;
(B) a black colorant comprising graphene oxide and a mixed black pigment;
(C) photopolymerizable monomer;
(D) photoinitiator; And
(E) solvent
Including,
The mixed black pigment is 110 to 160 parts by weight based on 100 parts by weight of the graphene oxide photosensitive resin composition.
The method of claim 1,
The black colorant is a photosensitive resin composition further comprising a carbon black or an organic black pigment.
The method of claim 2,
The carbon black is a photosensitive resin composition containing 20 to 70 parts by weight based on 100 parts by weight of the graphene oxide.
The method of claim 2,
The organic black pigment is 110 to 160 parts by weight based on 100 parts by weight of the graphene oxide photosensitive resin composition.
The method of claim 1,
The binder resin is a photosensitive resin composition comprising at least one selected from the group consisting of polyamic acid polymer, polyamic acid ester polymer, polyhydroxyamide polymer, polyimide polymer, polybenzoxazole polymer and copolymers thereof.
The method of claim 1,
The binder resin is a photosensitive resin composition which is a polyamic acid-polyimide copolymer.
The method of claim 6,
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 are included in a molar ratio of 5: 5 to 9: 1. Composition.
The method of claim 7, wherein
The polyamic acid-polyimide copolymer has a weight average molecular weight of 3,000 g / mol to 20,000 g / mol.
The method of claim 6,
The photosensitive resin composition further comprises a cardo-based binder resin.
The method of claim 1,
The photopolymerizable monomer is a photosensitive resin composition comprising a compound containing at least two or more functional groups represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
The method of claim 10,
A compound comprising at least two or more functional groups represented by Formula 1 is a compound represented by the following formula (2) or formula (3):
[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,
p, q, r and s are each independently an integer of 1 to 10.
The method of claim 1,
The said photosensitive resin composition is with respect to the photosensitive resin composition total amount.
1% to 20% by weight of the (A) binder resin;
1% to 20% by weight of the black colorant (B);
0.5 wt% to 10 wt% of the (C) photopolymerizable monomer;
0.1% to 5% by weight of the photopolymerization initiator (D); And
30 to 70 wt% of the solvent (E)
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition further comprises an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.
Black pixel defining layer manufactured using the photosensitive resin composition of any one of Claims 1-13.
A display device comprising the black pixel partition layer of claim 14.
The method of claim 15,
The display device is an organic light emitting device (OLED).