KR102054275B1 - Photosensitive resin composition, photosensitive resin layer using the same and display device - Google Patents

Abstract

(A) Binder resin containing polyimide polyamic-acid copolymer resin; (B) photopolymerizable monomers; (C) photoinitiator; (D) a black colorant; And (E) a solvent, wherein the photopolymerizable monomer comprises a first photopolymerizable monomer represented by Formula 1 and a second photopolymerizable monomer different from the first photopolymerizable monomer, prepared using the same. A display device including the photosensitive resin film and the photosensitive resin film is provided.

Description

Photosensitive resin composition, photosensitive resin film and display device using same {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAYER USING THE SAME AND DISPLAY DEVICE}

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film manufactured using the same, and a display device including the photosensitive resin film.

The photosensitive resin composition is a material essential for the production of light-shielding films and partition materials of display elements such as color filters, liquid crystal display materials, organic light emitting elements (EL), and display panel materials. For example, a color filter such as a color liquid crystal display requires a light shielding film or a partition material at a boundary between colored layers such as red, green, and blue in order to enhance display contrast and color development effects. Such a light shielding film and a partition material are mainly formed using the photosensitive resin composition containing a black coloring agent. Carbon black is most commonly used as the black colorant, and in addition, RGB mixed black, perylene-based compound, cobalt oxide, lactam-based organic black, and the like may be used. On the other hand, the pixel barrier layer used as a barrier material and a planarization film of an organic light emitting device such as OLED is a transparent material, and since light from outside is reflected by metal to generate high external light reflection, low outdoor visibility and reagent angle There is a problem such as, and there is a demand for improvement.

Specifically, in order to manufacture a photosensitive resin film, especially a black pixel partition wall layer, a positive photosensitive resin composition is required, and it is preferable to use a polyimide precursor and / or an aromatic polybenzoxazole precursor as a binder resin in the positive photosensitive resin composition. It was common. The polyimide precursor and / or the aromatic polybenzoxazole precursor are representative polymers based on a rigid aromatic main chain, and are excellent in high heat resistance, low outgas, chemical resistance, weather resistance, and shape stability.

However, as mentioned above, as problems such as external light reflection and outdoor visibility have recently emerged, there is a need for development of a black pixel barrier layer having excellent development margin while maintaining and improving the advantages of the conventional products such as high heat resistance and low outgas. Soaring.

As an example, there has been an attempt to increase the optical density by applying carbon black or organic black pigment to the positive photosensitive resin composition, but there is a limit. As another example, there has been an attempt to apply the carbon black or the organic black pigment to the non-positive negative photosensitive resin composition, but also has a limit in expressing high heat resistance and low outgas characteristics.

One embodiment is to provide a photosensitive resin composition excellent in development margin, heat resistance, outgas characteristics and taper properties.

Another embodiment is to provide a photosensitive resin film prepared using the black photosensitive resin composition.

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

One embodiment includes (A) a binder resin comprising a polyimide-polyamic acid copolymer resin; (B) photopolymerizable monomers; (C) photoinitiator; (D) a black colorant; And (E) a solvent, wherein the photopolymerizable monomer includes a first photopolymerizable monomer represented by Formula 1 and a second photopolymerizable monomer different from the first photopolymerizable monomer.

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁴ are each independently represented by the following formula (2),

o, p, q and r are each independently an integer of 0 or 1,

[Formula 2]

In Chemical Formula 2,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group,

s is an integer of 1-3.

O and p may each independently represent an integer of 1, and q and r may each independently represent an integer of 0.

The first photopolymerizable monomer may be represented by the following Chemical Formula 3.

[Formula 3]

In Chemical Formula 3,

R ⁵ and R ⁶ are each independently represented by the following formula (4),

[Formula 4]

In Chemical Formula 4,

t is an integer of 1 or 2.

The second photopolymerizable monomer may be represented by the following Chemical Formula 5 or Chemical Formula 6.

[Formula 5]

[Formula 6]

In Chemical Formulas 5 and 6,

L ² to L ⁷ are each independently a substituted or unsubstituted C1 to C10 alkylene group,

L ⁸ to L ¹² are each independently a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,

n1 and n2 are each independently an integer of 1 to 19, provided that 2 ≦ n1 + n2 ≦ 20.

L ⁸ may be a substituted or unsubstituted C1 to C10 alkylene group, and L ⁹ and L ¹⁰ may be each independently a substituted or unsubstituted C6 to C20 arylene group.

The first photopolymerizable monomer and the second photopolymerizable monomer may be included in a weight ratio of 1: 3 to 3: 1.

The copolymer resin may have an unsaturated double bond at at least one terminal.

The unsaturated double bond may be derived from any one compound selected from the group consisting of the following Chemical Formulas 7 to 10.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Chemical Formulas 7 to 9,

R ⁷ to R ¹¹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹³ to L ¹⁷ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

The copolymer resin may include polyimide and polyamic acid in a molar ratio of 40:60 to 60:40.

The polyimide in the copolymer resin may be represented by the following formula (11).

[Formula 11]

In Chemical Formula 11,

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 ¹⁸ and L ¹⁹ 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 ¹² is a substituted or unsubstituted acrylic group, a substituted or unsubstituted methacryl group, or a substituted or unsubstituted norbornene group,

n3 and n4 are each independently an integer of 1 to 100,000.

The copolymer resin may have a weight average molecular weight of 3,000 g / mol to 100,000 g / mol.

The binder resin may further include an acrylic binder resin, a cardo binder resin, or a combination thereof.

The black colorant may include aniline black pigment, perylene black pigment, titanium black pigment, cyanine black pigment, lignin black pigment, lactam organic black pigment, RGB black pigment, carbon black pigment, black dye, or a combination thereof. .

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

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 fluorine-based surfactant, or a combination thereof.

Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

Another embodiment provides a color filter including the photosensitive resin film.

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

Photosensitive resin composition according to one embodiment is excellent in the pattern development in the alkaline developer by using a binder resin containing a polyimide-polyamic acid copolymer resin and a photopolymerizable monomer comprising a compound having an acrylate substituent in the bisfluorene matrix In addition, the development margin is excellent, and heat resistance, outgas characteristics, and taper characteristics can be improved together.

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 otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" refers to 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" Means C1 to C20 alkylene group, "arylene group" means C6 to C20 arylene group, "alkyl arylene group" means C6 to C20 alkylarylene group, and "heteroarylene group" means 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 a 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 C20 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, 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 stated herein, "combination" means mixed or copolymerized.

Unless stated otherwise in the present specification, unsaturated bonds include not only multiple bonds between carbon-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 14-1 to 14-11 is included in the backbone of the resin.

Also, unless stated otherwise in the present specification, "*" means a part connected with the same or different atoms or formulas.

Black photosensitive resin composition according to one embodiment includes (A) a binder resin comprising a polyimide-polyamic acid copolymer resin; (B) a photopolymerizable monomer comprising a first photopolymerizable monomer represented by Formula 1 and a second photopolymerizable monomer different from the first photopolymerizable monomer; (C) photoinitiator; (D) a black colorant; And (E) a solvent.

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁴ are each independently represented by the following formula (2),

o, p, q and r are each independently an integer of 0 or 1,

[Formula 2]

In Chemical Formula 2,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group,

s is an integer of 1-3.

Conventionally, a cardo-based binder resin has been used alone as an alkali-soluble resin constituting the photosensitive resin composition to secure heat resistance, but it is difficult to satisfy a desired level of high heat resistance by using the cardo-based resin alone. When using a composition containing an alkali-soluble resin, such as polyimide, polybenzoxazole precursor for securing, there was a problem that the pattern after curing flows down, the taper angle is lowered.

However, the photosensitive resin composition according to the embodiment uses a polyimide-polyamic acid copolymer resin as the alkali-soluble resin, and further, the first photopolymerizable monomer represented by Formula 1 and the second light different from the first photopolymerizable monomer. By using a synthetic monomer together, the pixel does not peel even when processed into a pattern, showing the appropriate optical density at the time of forming a photosensitive resin film, and can maintain the outstanding heat resistance even at the high temperature of 250 degreeC or more. Therefore, the said photosensitive resin film can function as a protective film, a light shielding film, a black pixel partition layer, an insulating film, an anti-light leakage film, and a support spacer for cell gap in a display process. In addition, since it has a high heat resistance property, it can also be used for a substrate employed between the glass and the active layer or the gate electrode.

Hereinafter, each component which comprises the said photosensitive resin composition is explained in full detail.

(B) Photopolymerizable  Monomer

The photopolymerizable monomer includes a first photopolymerizable monomer represented by Chemical Formula 1, and further includes a second photopolymerizable monomer different from the first photopolymerizable monomer to control the remaining film and scum of the non-exposed part. In other words, it is possible to realize a pattern having an excellent development margin.

The first photopolymerizable monomer is represented by the general formula (1), it is easy to control the development. In addition, when curing at a temperature of 250 ℃ or more to improve the flow of the pattern with the binder to be described later, may have a taper angle of 25 ° to 53 °, for example 25 ° to 45 °, the content of the first photopolymerizable monomer By appropriately adjusting the desired taper angle can be formed within the above range. In addition to this, the residual film and scum are controlled by using the second photopolymerizable monomer, which is a highly cross-linkable multifunctional monomer, to realize a pattern having excellent morphological stability.

The proper development time with an excellent development margin should be 30 seconds to 150 seconds, for example, 50 seconds to 100 seconds. In this case, the pattern line width is preferably ± 2 μm based on 20 μm. For example, if a pattern is formed within a developing time of 30 seconds or less, even if the development time is slightly changed during the process of manufacturing the panel, the pattern line width (CD) and the taper angle may be different, so that the development margin is poor. In addition, when the pattern is formed at the development time of 150 seconds or more, the unit process time for manufacturing the panel is long, and the process margin is not good in terms of manufacturing.

In Formula 1, o and p may each independently represent an integer of 1, and q and r may each independently represent an integer of 0.

For example, the first photopolymerizable monomer may be represented by the following Chemical Formula 3.

[Formula 3]

In Chemical Formula 3,

R ⁵ and R ⁶ are each independently represented by the following formula (4),

[Formula 4]

In Chemical Formula 4,

t is an integer of 1 or 2.

For example, the second photopolymerizable monomer may be represented by the following Chemical Formula 5 or Chemical Formula 6.

[Formula 5]

[Formula 6]

In Chemical Formulas 5 and 6,

L ² to L ⁷ are each independently a substituted or unsubstituted C1 to C10 alkylene group,

L ⁸ to L ¹² are each independently a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,

n1 and n2 are each independently an integer of 1 to 19, provided that 2 ≦ n1 + n2 ≦ 20.

In Formula 6, L ⁸ may be a substituted or unsubstituted C1 to C10 alkylene group, and L ⁹ and L ¹⁰ may be each independently a substituted or unsubstituted C6 to C20 arylene group.

The first photopolymerizable monomer and the second photopolymerizable monomer may be included in a weight ratio of 1: 3 to 3: 1. When the first photopolymerizable monomer and the second photopolymerizable monomer are not included in the weight ratio in the above range, the development margin is poor and the shape stability is lowered.

For example, the second photopolymerizable monomer may be 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) acrylic Late, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol mono Butyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) but the like acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, is not limited thereto.

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 7 wt%, based on the total amount of the photosensitive resin composition. When a photopolymerizable monomer is contained in the said range, hardening arises at the time of exposure in a pattern formation process, and it is excellent in reliability, and is excellent in developability to alkaline developing solutions.

(A) Binder Resin

The photosensitive resin composition according to one embodiment includes a binder resin, such as an alkali soluble resin, and the alkali soluble resin includes a polyimide-polyamic acid copolymer resin.

Alkali-soluble resin constituting the photosensitive resin composition according to the embodiment has a polyimide unit having a solubility in the organic solvent and a polyamic acid unit having a polyimide precursor structure at the same time, it was a high heat-resistant photosensitive resin film that was difficult to implement conventionally, For example, a high heat resistant light shielding film can be provided.

In order to prevent overdissolution characteristics of the polyamic acid, which is a polyimide precursor, in the aqueous alkali solution, copolymerization of the polyimide, which is the main structure of the polymer, is performed to control the solubility, so that an appropriate difference in solubility between the exposed part and the non-exposed part can be obtained during the pattern process Through this, a photosensitive resin film such as a light shielding film having excellent heat resistance and pattern formation property can be realized.

The copolymer resin may have an unsaturated double bond 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 resin. The unsaturated double bond at the terminal (and / or the middle of the chain) may act as a crosslinkable functional group to improve the crosslinking properties of the copolymer resin. That is, a photosensitive resin composition having more excellent contrast can be implemented by introducing a monomer capable of crosslinking by a photoinitiator in the terminal group (and / or the middle of the chain) of the main structure in order to impart crosslinking characteristics by exposure of the copolymer resin itself. The monomer capable of crosslinking by the photoinitiator may be any one selected from the group consisting of the following Chemical Formulas 7 to 10.

For example, the unsaturated double bond may be derived from any one compound selected from the group consisting of Formulas 7 to 10, but is not limited thereto.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Chemical Formulas 7 to 9,

R ⁷ to R ¹¹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹³ to L ¹⁷ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

The copolymer resin may include polyimide and polyamic acid in a molar ratio of 1:99 to 95: 5, such as 40:60 to 60:40.

When the polyimide and the polyamic acid in the copolymer resin satisfy the above range, the crosslinking characteristics of the copolymer resin are excellent. In other words, when the polyimide and the polyamic acid in the copolymer resin is out of the range, that is, when the polyimide is contained in excess of the polyamic acid, the developability of the composition is lowered, and the polyamic acid is more than the polyimide. When included as, the developability is so excellent that the pattern formability is greatly reduced.

That is, the copolymer resin 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, introduces a crosslinkable functional group into the terminal (and / or chain) of copolymer resin, and irradiates with UV. The time exposure region is cross-linked, and the unexposed region is formed with a fine pattern through a developing process, which is thermally cured at 250 ° C. or higher to provide excellent heat resistance.

For example, the copolymerization may be represented by the following Chemical Formula 11, but is not limited thereto.

[Formula 11]

In Chemical Formula 11,

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 ¹⁸ and L ¹⁹ 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 ¹² is a substituted or unsubstituted acrylic group, a substituted or unsubstituted methacryl group, or a substituted or unsubstituted norbornene group,

n3 and n4 are each independently an integer of 1 to 100,000.

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

[Formula A]

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

[Formula B]

In Formula B,

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

The copolymer resin may have a weight average molecular weight of 3,000 g / mol to 100,000 g / mol. When the weight average molecular weight of the copolymer resin is in the above range, it has excellent pattern formability, and the manufactured thin film may have excellent mechanical and thermal properties.

When the binder resin according to one embodiment includes only the polyamic acid-polyimide copolymer resin alone, since the melting property may be reduced, the binder resin may be used in addition to the polyamic acid-polyimide copolymer resin. It may further comprise 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; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic 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 (14).

[Formula 14]

In Chemical Formula 14,

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 14-1 to Formula 14-11,

[Formula 14-1]

[Formula 14-2]

[Formula 14-3]

[Formula 14-4]

[Formula 14-5]

(In Chemical Formula 14-5,

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 14-6]

[Formula 14-7]

[Formula 14-8]

[Formula 14-9]

[Formula 14-10]

[Formula 14-11]

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 the following Formula 15 at at least one of both ends.

[Formula 15]

In Chemical Formula 15,

Z ³ may be represented by the following Formula 15-1 to Formula 15-7.

[Formula 15-1]

(In Formula 15-1, 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 15-2]

[Formula 15-3]

[Formula 15-4]

[Formula 15-5]

(In Formula 15-5, 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 15-6]

[Formula 15-7]

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 together with the polyimide copolymer resin.

The content of the acrylic binder resin or the cardo-based binder resin in the binder resin may be less than the content of the polyamic acid-polyimide copolymer resin. For example, the content of the polyamic acid-polyimide copolymer may be two to three times the content of the acrylic binder resin or cardo-based binder resin. When the content of the acrylic binder resin or cardo-based binder resin is less than the polyamic acid-polyimide copolymer content, heat resistance and outgas characteristics may be further improved along with excellent developability.

The binder resin may be included in an amount of 1 wt% to 20 wt%, such as 3 wt% to 15 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) Photopolymerization Initiator

As the photopolymerization initiator, an initiator generally used in the photosensitive resin composition, for example, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, an oxime compound or a combination thereof may be used.

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 compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoic acid, 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 compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone 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, 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- (naphtho-1-yl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4 -Bis (trichloromethyl) -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-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, and 1- (o-acetyloxime ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one Etc. 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-dione2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione2 -Oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) -butan-1-one oxime-O- Acetate, and the like, but is not limited thereto.

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 include a first photopolymerization initiator having a maximum absorbance in a wavelength region of 300 nm or less and a second photopolymerization initiator having a maximum absorbance in a wavelength region of more than 300 nm. The first photopolymerization initiator is a short wavelength initiator and can improve the surface curing rate, and the second photopolymerization initiator is a long wavelength initiator to enhance the internal curing speed rather than the surface to increase adhesion to the lower substrate and have a forward tape after development. can do.

For example, the first photopolymerization initiator may be represented by the following Chemical Formula 12, and the second photopolymerization initiator may be represented by the following Chemical Formula 13.

[Formula 12]

[Formula 13]

In Chemical Formula 12 and Chemical Formula 13,

R ¹³ to R ¹⁴ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁵ to R ¹⁶ are each independently a substituted or unsubstituted C1 to C10 alkyl group,

n5 and n6 are integers of 0-5.

The first photopolymerization initiator and the second photopolymerization initiator may be included in a weight ratio of 1: 1.

The photopolymerization initiator may be used together with a photosensitizer which causes a chemical reaction by absorbing light and transferring energy after being excited. That is, the black photosensitive resin composition may further include a photosensitizer.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, and the like. It may include, but is not limited thereto.

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, curing occurs during exposure in the pattern forming process to obtain excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and unreacted initiator. The fall of the transmittance | permeability can be prevented.

(D) black colorant

The photosensitive resin composition according to one embodiment may include a black colorant, and the black colorant may include, for example, a pigment, a dye, or a combination thereof.

The pigment is used in the form of a pigment dispersion, the pigment dispersion may include a pigment, a dispersant and a solvent of a solid content. At this time, the pigment of the solid content relative to the total amount of the pigment dispersion may be included in 8% by weight to 30% by weight, such as 8% by weight to 15% by weight, such as 8% by weight to 12% by weight. In this case, the pigment can be effectively dispersed, dispersion stability can be ensured, and color characteristics such as luminance can be improved.

The black pigment may be an inorganic black pigment, an organic black pigment, or a combination thereof, such as aniline black, perylene black, titanium black, cyanine black, lignin black, lactam organic black, RGB black, carbon black, or a combination thereof. It may include. Specifically, the organic black pigment may be a lactam organic black represented by the following Chemical Formula C.

[Formula C]

The RGB black refers to a pigment exhibiting black by mixing at least two or more colored pigments among colored pigments such as red pigments, green pigments, blue pigments, violet pigments, yellow pigments, and purple pigments.

When the black pigment contains carbon black, it is excellent in light shielding property, surface smoothness, dispersion stability, compatibility with binder resin, and the like. In addition, when using the said black pigment, it can also be used with color correction agents, such as an anthraquinone pigment, a perylene pigment, a phthalocyanine pigment, and an azo pigment.

The primary particle diameter of the black pigment may be 10 nm to 80 nm, such as 10 nm to 70 nm. When the primary particle size falls within the particle size range, the pigment is excellent in stability in the pigment dispersion and there is no fear of lowering the resolution of the pixel.

As the solvent in the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol monomethyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, or 3-methoxy-1-butanol 사용할 may be used. Among them, propylene glycol monomethyl ether acetate may be preferably used. At this time, the content of the solvent is preferably adjusted so that the solid content of the pigment dispersion is 5% by weight to 30% by weight, but is not necessarily limited thereto.

The solvent is based on 100% by weight of the pigment dispersion, such as 30% by weight to 90% by weight, such as 40% by weight to 90% by weight, such as 50% by weight to 90% by weight, such as 60% by weight to 90% by weight, such as 70 wt% to 90 wt%, such as 80 wt% to 90 wt%.

In addition, the pigment dispersion may further comprise a dispersant. As the dispersant, all nonionic, anionic or cationic dispersants may be used, for example, polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts. , Sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines and the like can be used. These dispersants can be used individually by 1 type or in combination of 2 or more types as appropriate.

For example, the black pigment is BK-6912, BK-6913, BK-6616 manufactured by Tokushiki; TCD-006H from Nippon Steel Corporation; Sakata's CI-M 390, CI-M 391, CI-M 395, CI-M 400, CI-M 402, CI-M408, or a combination thereof may be used, but is not limited thereto.

For example, the black colorant may include both an organic black pigment for increasing a transmittance in the infrared region to enable aline during the patterning process and a carbon black for improving light shielding properties in the visible ray region.

For example, the black dye may include acridine dyes, anthraquinone dyes, arylmethane dyes, diarylmethane dyes, and triarylmethane dyes. dyes, azo dyes, diazonium dyes, nitro dyes, nitroso dyes, phthalocyanine dyes, quinone-imine dyes Quinone-imine dyes, Azin dyes, Eurhodin dyes, Safranin dyes, Indamins dyes, Indophenol dyes, Oxazine Oxazin dyes, Oxazone dyes, Thiazin dyes, Thiazole dyes, Xanthene dyes, Fluorene dyes, Pyronin dyes (Pyronin dyes), Rhodamine dyes and the like can be used, but It is not limited.

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 10% by weight to 30% by weight based on the pigment dispersion based on the total amount of the photosensitive resin composition. When the black colorant is included in the range, it is excellent in brightness, color reproducibility, curability of the pattern, heat resistance and adhesion.

(E) solvent

The solvent may be a material having a compatibility with a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a black colorant but not reacting according to an embodiment. For example, the solvent may have a boiling point of 100 ° C or more and 250 ° C or less.

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 and ethylene glycol monoethyl 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 methylethyl 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; Oxy acetic acid alkyl esters such as methyl oxy acetate, oxy ethyl acetate and oxy butyl acetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxy propionic acid alkyl esters such as 3-oxy methyl propionate and 3-oxy ethyl propionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate and 3-ethoxy methyl propionate; 2-oxy propionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate and 2-oxy propionic acid propyl; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionic acid esters, such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate and 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl propionic acid alkyls such as methyl methyl propionate; Esters such as ethyl 2-hydroxy propionate, ethyl 2-hydroxy-2-methyl propionate, ethyl hydroxy acetate, and methyl 2-hydroxy-3-methyl butanoate; Ketone acid esters such as ethyl pyruvate and the like, and N-methylformamide, N, N-dimethylformamide, N-methylformanilade, N-methylacetamide, 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 And high boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and 3-methoxybutyl acetate.

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

The solvent may be included in a balance, such as 40 wt% to 80 wt%, 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, the processability is excellent in manufacturing a color filter.

(F) other additives

The photosensitive resin composition may be used to prevent stains or spots upon application, to improve leveling performance, and to prevent generation of residue by undeveloped, malonic acid, 3-amino-1,2-propanediol, vinyl group Or other additives such as a silane coupling agent containing a (meth) acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, and γ -Glycidoxy propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

As the surfactant, a fluorine-based surfactant may be used. Examples of the fluorine-based surfactants include BM-1000 ^® , BM-1100 ^® , and the like by BM Chemie; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^®, etc., by Dai Nippon Inki Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Corporation; Asahi Grass Co., Ltd. Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^®, etc .; Toray Silicone Co., Ltd.'s SH-28PA ^{®, ®} -190 copper, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The content of the additive can be easily adjusted according to the desired physical properties.

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

As an example of the said epoxy compound, a phenol novolak epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol-A epoxy compound, an alicyclic epoxy compound, or a combination thereof is mentioned.

The epoxy compound may be included in an amount of 0.01 parts by weight to 5 parts by weight, such as 0.1 parts by weight to 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included in the above range, it is excellent in adhesion, heat resistance and chemical resistance.

The black photosensitive resin composition may be a negative black photosensitive resin composition. The photosensitive resin composition has a positive type in which the exposed part is dissolved by development and a negative type in which the exposed part is cured. A photosensitive resin film, for example, a light shielding film, is prepared by using the photosensitive resin composition containing the black colorant. In this case, the positive type may be difficult to implement a fine pattern because the transmittance of ultraviolet light is reduced.

Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition described above.

The photosensitive resin film may be, for example, a light blocking film or a black pixel partition layer.

The manufacturing method of the said photosensitive resin film 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 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 as needed.

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 photosensitive resin film.

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

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 )

(Copolymer Resin Synthesis)

Synthesis Example  1: Synthesis of Copolymer Resin

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., 5.6 g of pyridine and 2.05 g of acetic anhydride (A ₂ CO) 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. After repeating the precipitation / washing / filter four times, it was dissolved in 3-methoxy butyl acetate, and the water was controlled to 1000 ppm or less by a distillation process at a temperature of 40 ° C. to prepare a polyamic acid-polyimide copolymer resin. . 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  6 and Comparative example  1 to Comparative example  5

The photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 were prepared with the compositions shown in Tables 1 and 2 below using the components mentioned below.

Specifically, after accurately measuring the content of the photopolymerization initiator, a solvent was added, and the mixture was sufficiently stirred until the photopolymerization initiator was dissolved (at least 30 minutes). The binder resin and the photopolymerizable monomer were sequentially added thereto, followed by stirring for about 1 hour. Subsequently, a coloring agent (pigment dispersion) was added, other additives were added, and finally the whole composition was stirred for 2 hours or more to prepare a photosensitive resin composition.

The specification of each component used for manufacture of the photosensitive resin composition is as follows.

(A) Binder Resin

(A-1) Polyamic acid-polyimide copolymer resin prepared in Synthesis Example 1

(A-2) Cardo Binder Resin (V259ME, NSSC Co., Ltd.)

(B) Photopolymerizable  Monomer

First Photopolymerizable  Monomer

(B-1) 9,9-bis [4- (2-acryloyloxyethyloxy) panyl] fluorene (PN6310, Polynetron Co., Ltd.)

2nd Photopolymerizable  Monomer

(B-2) dipentaerythritol hexa (meth) acrylate (DPHA, Nippon Kayaku Co., Ltd.)

(B-3) A compound represented by the following Chemical Formula X (ABPE, Shin-Nakamura Co., Ltd.)

[Formula X]

(In the formula (X), m 1 + m 2 = 20.)

(C) Photopolymerization Initiator

(C-1) First photopolymerization initiator (NCI-831, ADEKA Co., Ltd.)

(C-2) Second photopolymerization initiator (IRG-819, BASF Corporation)

(D) black colorant

(D-1) Organic black pigment (CIM-126) dispersion (SAKATA, solid content 15% by weight)

(D-2) Carbon black mill base (BK-6925) dispersion (TOKUSIKI, solid content 15% by weight)

(E) solvent

(E-1) Propylene Glycol Monomethyl Ether Acetate (PGMEA, Sigma-aldrich)

(E-2) 3-methoxy butyl acetate (3-MBA, Sigma-aldrich)

(F) other additives

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

(Unit: weight%) Kinds Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 (A) Binder Resin A-1 10 10 10 10 10 10 A-2 4 4 4 4 4 4 (B) photopolymerizable monomer B-1 2.5 2.5 3.5 1.5 4 One B-2 2.5 - 1.5 3.5 One 4 B-3 - 2.5 - - - - (C) photopolymerization initiator C-1 0.6 0.6 0.6 0.6 0.6 0.6 C-2 0.6 0.6 0.6 0.6 0.6 0.6 (D) colorant D-1 14 14 14 14 14 14 D-2 5.6 5.6 5.6 5.6 5.6 5.6 (E) solvent E-1 40 40 40 40 40 40 E-2 20 20 20 20 20 20 (F) other additives 0.2 0.2 0.2 0.2 0.2 0.2

(Unit: weight%) Kinds Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (A) Binder Resin A-1 - - 10 10 10 A-2 14 14 4 4 4 (B) photopolymerizable monomer B-1 - - 5 - - B-2 5 - - 5 - B-3 - 5 - - 5 (C) photopolymerization initiator C-1 0.6 0.6 0.6 0.6 0.6 C-2 0.6 0.6 0.6 0.6 0.6 (D) colorant D-1 14 14 14 14 14 D-2 5.6 5.6 5.6 5.6 5.6 (E) solvent E-1 40 40 40 40 40 E-2 20 20 20 20 20 (F) other additives 0.2 0.2 0.2 0.2 0.2

(evaluation)

Coating and pattern formation

The photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 were applied to 10 cm * 10 cm ITO glass (resistance 30 Ω), heated for 1 minute on a 100 ° C hotplate, and 1.2 µm. A thick coating film was formed. After exposing the coated film to the I-line stepper (NSR i10C, Nikon Co., Ltd.) using a mask engraved with a pattern of various sizes, the exposure amount was changed, and then exposed in a 2.38% TMAH aqueous solution at room temperature for 10 seconds to 120 seconds. After splitting into seconds, the non-exposed part was dissolved (removed) through a puddle process, and then washed with ultrapure water (DIW) for 30 seconds. Subsequently, the obtained pattern was cured at an oxygen concentration of 1000 ppm or less and 250 ° C. for 60 minutes using an oven to obtain a pattern.

Development margin (pattern Line width  Measure)

Sensitivity suitable for the photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 was investigated, and the developing time was advanced from 10 seconds to 120 seconds. Subsequently, the line width of the 20 μm hole pattern was measured by optical equipment among the patterns of various sizes obtained, and the results are shown in Table 3 below.

Development margin
Pattern Linewidth (μm) at TMAH (2.38%) 10 sec 20 seconds 30 seconds 40 seconds 50 seconds 60 seconds 70 seconds 80 sec 90 sec 100 sec 110 seconds 120 seconds Example 1 18.25 19.80 20.05 20.20 20.72 21.78 Example 2 18.65 20.04 20.79 21.45 Example 3 18.50 19.01 19.55 20.00 20.35 20.67 21.02 Example 4 18.55 19.88 20.22 20.45 21.04 21.97 Example 5 18.54 19.91 19.98 20.05 20.11 20.75 Example 6 20.25 20.71 21.10 21.87 Comparative Example 1 20.10 21.78 Comparative Example 2 18.90 Comparative Example 3 18.50 19.88 19.90 20.01 20.03 20.70 Comparative Example 4 18.08 20.03 20.55 21.90 Comparative Example 5 18.30 20.06 21.65

From the above Table 3, the photosensitive resin composition according to Examples 1 to 6 comprising the first photopolymerizable monomer represented by the formula (1) and the second photopolymerizable monomer different from this, the photosensitive according to Comparative Examples 1 to 5 It can be confirmed that the development margin is superior to the resin composition. Furthermore, the case where the first photopolymerizable monomer and the second photopolymerizable monomer are included in a weight ratio of 1: 3 to 3: 1 can be confirmed that the development margin is superior to the case where the weight ratio deviates from the weight ratio.

Heat resistance

TGA analysis was performed with the photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 to obtain a 1 wt% loss temperature, and the results are shown in Table 4 below.

Taper  Angle

The patterned coating film prepared using the photosensitive resin composition according to Examples 1 to 6 and Comparative Examples 1 to 5 was measured by FE-SEM equipment (S-4300, hitachi, Inc.), and the results were measured. It is shown in Table 4 below.

Outgas

The patterned coating film prepared using the photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 was cut to 5 cm × 5 cm and then subjected to TD-GC / MS analysis for outgas (ng / cm ² ) content was obtained, and the results are shown in Table 4 below. The analysis method is as follows.

Experimental sequence

1) Collect outgas into TD tube using FD-4000 at 150 ℃ / 30 minutes.

2) The TD (MARKES UNITY2) -GC / MS (Thermo ISQ LT) conditions are set as follows, and the gas in the TD tube (Tenax TA) is qualitatively analyzed.

<Measurement condition>

TD

Method Air purge Purgea & trap Desorb Analysis 1 min 10 minutes 10 minutes 41 minutes Tube, Sample Temperature 25 ℃ 300 ℃ 320 ℃ Trap temperature 0 ℃ 0 ℃ 320 ℃

GC / MS

Column DB-5MS → 30m 0.25㎜ 0.25㎛ (5% phenylmethylpolysiloxane) Mobile phase He Flow 1.45 mL / min (Average velocity = 32 cm / s) Split Split ratio = 70: 1 Method 50 ° C (3 minutes)-10 ° C / minute → 200 ° C (10 minutes)-10 ° C / minute → 320 ° C (3 minutes) Detector MSD

1 wt% loss temp. (℃) Outgas (ng / cm ² ) Tapered angle (°) Example 1 379 8 39 Example 2 371 9 45 Example 3 380 7 35 Example 4 378 9 40 Example 5 380 7 32 Example 6 371 10 53 Comparative Example 1 245 30 20 Comparative Example 2 230 45 10 Comparative Example 3 381 6 30 Comparative Example 4 370 11 55 Comparative Example 5 367 10 50

From the above Table 6, the photosensitive resin composition according to Examples 1 to 6 comprising the first photopolymerizable monomer represented by the formula (1) and the second photopolymerizable monomer different from this, the photosensitive according to Comparative Examples 1 to 5 It can be confirmed that heat resistance, outgas characteristics, and taper characteristics are superior to the resin composition. In addition, it can be seen that the case where the first photopolymerizable monomer and the second photopolymerizable monomer are included in a weight ratio of 1: 3 to 3: 1 is superior to the taper property when the weight ratio is out of the weight ratio. In the case of Example 5, the taper angle is slightly low, so the pattern may be collapsed. In the case of Example 6, the taper angle is slightly high, so that it may be difficult to stably form the pattern.

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 (17)

(A) Binder resin containing polyimide polyamic-acid copolymer resin;
(B) photopolymerizable monomers;
(C) photoinitiator;
(D) a black colorant; And
(E) solvent
Including,
The photopolymerizable monomer includes a first photopolymerizable monomer represented by Formula 1 and a second photopolymerizable monomer represented by Formula 5 or Formula 6 below,
The first photopolymerizable monomer and the second photopolymerizable monomer are included in a weight ratio of 3.5: 1.5 to 1.5: 3.5:
[Formula 1]

In Chemical Formula 1,
R ¹ to R ⁴ are each independently represented by the following formula (2),
o, p, q and r are each independently an integer of 0 or 1,
[Formula 2]

In Chemical Formula 2,
L ¹ is a substituted or unsubstituted C1 to C10 alkylene group,
s is an integer of 1 to 3,
[Formula 5]

[Formula 6]

In Chemical Formulas 5 and 6,
L ² to L ⁷ are each independently a substituted or unsubstituted C1 to C10 alkylene group,
L ⁸ to L ¹² are each independently a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,
n1 and n2 are each independently an integer of 1 to 19, provided that 2 ≦ n1 + n2 ≦ 20.
The method of claim 1,
O and p are each independently an integer of 1,
Q and r are each independently an integer of 0, the photosensitive resin composition.
The method of claim 2,
The first photopolymerizable monomer is a photosensitive resin composition represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
R ⁵ and R ⁶ are each independently represented by the following formula (4),
[Formula 4]

In Chemical Formula 4,
t is an integer of 1 or 2.
delete The method of claim 1,
L ⁸ is a substituted or unsubstituted C1 to C10 alkylene group,
L ⁹ and L ¹⁰ are each independently a substituted or unsubstituted C6 to C20 arylene group photosensitive resin composition.
delete The method of claim 1,
The copolymer resin is a photosensitive resin composition having an unsaturated double bond at at least one end.
The method of claim 7, wherein
The unsaturated double bond is a photosensitive resin composition which is derived from any one compound selected from the group consisting of Formula 7 to Formula 10:
[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Chemical Formulas 7 to 9,
R ⁷ to R ¹¹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹³ to L ¹⁷ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
The method of claim 1,
The copolymer resin is a photosensitive resin composition containing polyimide and polyamic acid in a molar ratio of 40:60 to 60:40.
The method of claim 1,
The polyimide in the copolymer resin is a photosensitive resin composition represented by the following formula (11):
[Formula 11]

In Chemical Formula 11,
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 ¹⁸ and L ¹⁹ 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 ¹² is a substituted or unsubstituted acrylic group, a substituted or unsubstituted methacryl group, or a substituted or unsubstituted norbornene group,
n3 and n4 are each independently an integer of 1 to 100,000.
The method of claim 1,
The copolymer resin is a photosensitive resin composition having a weight average molecular weight of 3,000 g / mol to 100,000 g / mol.
The method of claim 1,
The binder resin further comprises an acrylic binder resin, a cardo binder resin, or a combination thereof.
The method of claim 1,
The black colorant is a photosensitive resin including aniline black pigment, perylene black pigment, titanium black pigment, cyanine black pigment, lignin black pigment, lactam organic black pigment, RGB black pigment, carbon black pigment, black dye, or a combination thereof. Composition.
The method of claim 1,
The said photosensitive resin composition is with respect to the said total photosensitive resin composition total amount.
1% to 20% by weight of the (A) binder resin;
0.5 to 10 wt% of the (B) photopolymerizable monomer;
0.1 wt% to 5 wt% of the (C) photopolymerization initiator;
1% to 20% by weight of the black colorant (D) and
Residual amount 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 fluorine-based surfactant, or a combination thereof.
The photosensitive resin film manufactured using the photosensitive resin composition of any one of Claims 1-3, 5 and 7-15.
A display device comprising the photosensitive resin film of claim 16.