KR20180080507A - Photosensitive resin composition, photosensitive resin layer using the same and display device - Google Patents

Abstract

Provided are a photosensitive resin composition excellent in developing margin, heat resistance, outgas characteristics, and taper characteristics, a photosensitive resin film manufactured using the same, and a display device including the photosensitive resin film. The photosensitive resin comprises: (A) a binder resin including a polyimide-polyamic acid copolymer resin; (B) a photopolymerizable monomer; (C) a photopolymerizable initiator; (D) a black colorant; and (E) a solvent. The photosensitive resin composition includes a first photopolymerizable monomer and a second photopolymerizable monomer different from the first photopolymerizable represented by a chemical formula 1.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a photosensitive resin film using the same, and a display device using the same. BACKGROUND ART [0002]

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

The photosensitive resin composition is an indispensable material for the production of light-shielding films and barrier rib materials for display elements such as color filters, liquid crystal display materials, organic light emitting devices (EL), and display panel materials. For example, a color filter such as a color liquid crystal display requires a light-shielding film or a barrier rib material at a boundary portion between colored layers such as red, green, and blue in order to enhance display contrast and coloring effect , And such a light-shielding film or barrier rib material is mainly formed by using a photosensitive resin composition containing a black coloring agent. As the black colorant, carbon black is the most commonly used. In addition, RGB mixed black, a perylene compound, cobalt oxide, and lactam-based organic black may be used. On the other hand, since the pixel barrier layer used as the barrier rib material and the planarization layer of an organic light emitting device such as an OLED is a transparent material, light coming from the outside is reflected by a metal to generate high external light reflection, And there is a demand for improvement thereof.

Specifically, a positive photosensitive resin composition is required for producing a photosensitive resin film, particularly, a black pixel partition wall layer. The use of a polyimide precursor and / or an aromatic polybenzoxazole precursor as the binder resin in the positive photosensitive resin composition It was common. The polyimide precursor and / or aromatic polybenzoxazole precursor is a typical polymer based on a rigid aromatic main chain and has excellent heat resistance, low outgassing, chemical resistance, weather resistance, and shape stability.

However, as described above, there has recently been a problem such as external light reflection and outdoor visibility, and there has been a demand for developing a black pixel barrier wall layer having a high developing margin and maintaining and improving the conventional merits such as high heat resistance and low outgassing It is surging.

For example, attempts have been made to increase the optical density by applying carbon black or an organic black pigment to a positive photosensitive resin composition, but there is a limit. As another example, attempts have been made to apply the carbon black or the organic black pigment to a negative-type photosensitive resin composition that is not a positive type, but there is also a limit in expressing high heat resistance and low outgassing characteristics.

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

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

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

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

[Chemical Formula 1]

In Formula 1,

R ¹ to R ⁴ each independently represent the following formula (2)

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

(2)

In Formula 2,

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

s is an integer of 1 to 3;

Each of o and p is independently an integer of 1, and each of q and r may independently be an integer of 0.

The first photopolymerizable monomer may be represented by the following general formula (3).

(3)

In Formula 3,

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

[Chemical Formula 4]

In Formula 4,

t is an integer of 1 or 2;

The second photopolymerizable monomer may be represented by the following general formula (5) or (6).

[Chemical Formula 5]

[Chemical Formula 6]

In the above 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 each independently represent 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.

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

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

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

The unsaturated double bond may be derived from any one of compounds represented by the following formulas (7) to (10).

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above 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 general formula (11).

(11)

In Formula 11,

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

L 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 cadmium binder resin, or a combination thereof.

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

Wherein the photosensitive resin composition comprises 1 to 20% by weight of the binder resin (A) relative to the total amount of the photosensitive resin composition; 0.5 to 10% by weight of the photopolymerizable monomer (B); 0.1 to 5% by weight of the photopolymerization initiator (C); (D) 1 to 20% by weight of a black colorant and (E) the balance of the solvent.

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

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

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

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

The photosensitive resin composition according to one embodiment is excellent in pattern formation property in an alkali developing solution by using a photopolymerizable monomer containing a binder resin containing a polyimide-polyamic acid copolymer resin and a compound having an acrylate substituent group in a bisfluorene matrix So that the developing margin is excellent, and the heat resistance, outgas characteristics, and taper characteristics can be improved as well.

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

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

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

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

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

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

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

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

In the present specification, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following formulas (14-1) to (14-11) is contained in the main backbone of the resin.

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

The black photosensitive resin composition according to one embodiment comprises (A) a binder resin comprising a polyimide-polyamic acid copolymer resin; (B) a photopolymerizable monomer comprising a first photopolymerizable monomer represented by the following general formula (1) and a second photopolymerizable monomer different from the first photopolymerizable monomer; (C) a photopolymerization initiator; (D) a black colorant; And (E) a solvent.

[Chemical Formula 1]

In Formula 1,

R ¹ to R ⁴ each independently represent the following formula (2)

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

(2)

In Formula 2,

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

s is an integer of 1 to 3;

Conventionally, in order to secure heat resistance, a cadmium-based binder resin has been used alone as an alkali-soluble resin constituting a photosensitive resin composition. However, when the cationic resin alone is used, it is difficult to satisfy a desired high heat resistance, There is a problem that when a composition including an alkali-soluble resin such as polyimide or polybenzoxazole precursor is used for securing, the pattern flows after curing and the taper angle is lowered.

However, the photosensitive resin composition according to one embodiment uses a polyimide-polyamic acid copolymer resin as an alkali-soluble resin, and further uses a first photopolymerizable monomer represented by the above-described formula (1) and a second photopolymerizable monomer different from the first photopolymerizable monomer By using the synthetic monomers together, it is possible to maintain excellent heat resistance even at a high temperature of 250 DEG C or more without peeling of the pixel even when processed into a pattern while exhibiting an appropriate optical density at the time of forming a photosensitive resin film. Accordingly, the photosensitive resin film can function as a protective film, a light-shielding film, a black pixel partition wall layer, an insulating film, a light-shielding film, and a support spacer for holding a cell gap in a display process. In addition, since it has high heat resistance characteristics, it can be used for a substrate employed between a glass and an active layer or between gate electrodes.

Hereinafter, each component constituting the photosensitive resin composition will be described in detail.

(B) Photopolymerization  Monomer

Wherein the photopolymerizable monomer further comprises a second photopolymerizable monomer different from the first photopolymerizable monomer, wherein the second photopolymerizable monomer comprises a first photopolymerizable monomer represented by the general formula (1) That is, a pattern having an excellent developing margin can be realized.

The first photopolymerizable monomer is represented by the formula (1), so that the development property is easily controlled. Further, when cured at a temperature of 250 DEG C or higher, the flowability of the pattern can be improved together with the binder described later to have a taper angle of 25 DEG to 53 DEG, for example 25 DEG to 45 DEG, and the content of the first photopolymerizable monomer So that a desired taper angle can be formed within the above range. In addition, the second photopolymerizable monomer, which is a polyfunctional monomer having a high crosslinking property, is used to control the residual film and scum, so that a pattern having excellent shape stability can be realized.

The optimum development time is preferably 30 seconds to 150 seconds, for example, 50 seconds to 100 seconds, and the pattern line width is preferably +/- 2 占 퐉 based on 20 占 퐉. For example, if a pattern is formed within a developing time of 30 seconds or less, the critical dimension (CD) and the taper angle may be changed even if the developing time is slightly changed during the process of manufacturing the panel, and thus the developing margin is poor. In addition, if a pattern is formed at a development time of 150 seconds or more, the unit process time for manufacturing the panel becomes long, and the process margin is not good in terms of manufacturing.

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

For example, the first photopolymerizable monomer may be represented by the following general formula (3).

(3)

In Formula 3,

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

[Chemical Formula 4]

In Formula 4,

t is an integer of 1 or 2;

For example, the second photopolymerizable monomer may be represented by the following general formula (5) or (6).

[Chemical Formula 5]

[Chemical Formula 6]

In the above 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 each independently represent 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 is a substituted or unsubstituted C1 to C10 alkylene group, and L ⁹ and L ¹⁰ each independently represent a substituted or unsubstituted C6 to C20 arylene group.

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

Examples of the second photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate such as glycidyl (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 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 treated with an acid anhydride to give better developing properties.

The photopolymerizable monomer may be contained in an amount of 0.5 wt% to 10 wt%, for example, 1 wt% to 7 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern forming step, and therefore, the photopolymerizable monomer is excellent in reliability and developability in an alkaline developer.

(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.

The alkali-soluble resin constituting the photosensitive resin composition according to one embodiment has a high heat-resistant photosensitive resin film, which is difficult to implement conventionally by simultaneously having a polyimide unit having a solubility in an organic solvent and a polyamic acid unit having a polyimide precursor structure, For example, a high heat-resistant light-shielding film.

In order to prevent overcharging characteristics of polyamic acid, which is a polyimide precursor, in alkaline aqueous solution, polyimide, which is a main structure of the polymer, is copolymerized to control the solubility, so that a proper difference in solubility between the exposed and non- As a result, a photosensitive resin film having excellent heat resistance and pattern forming property, for example, a light-shielding film can be realized.

The copolymer resin may have at least one terminal, for example, an unsaturated double bond at both terminals. The unsaturated double bond may be present in the chain of the copolymer resin besides the terminal of the copolymer resin. The unsaturated double bond at the terminal (and / or in the middle of the chain) acts as a crosslinkable functional group and can improve the crosslinking property of the copolymer resin. That is, in order to impart the crosslinking property by exposure of the copolymer resin itself, a monomer capable of crosslinking by a photoinitiator is introduced into the terminal group (and / or the middle of the chain) of the main structure to realize a photosensitive resin composition having a superior contrast And the monomer capable of crosslinking by the photoinitiator may be any one selected from the group consisting of the following formulas (7) to (10).

For example, the unsaturated double bond may be derived from any one of compounds represented by the following formulas (7) to (10), but the present invention is not limited thereto.

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above 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 property of the copolymer resin becomes excellent. In other words, when the polyimide and the polyamic acid in the copolymer resin are out of the above range, that is, when the polyimide is contained in excess of the polyamic acid, the developability of the composition is deteriorated, and the polyamic acid becomes excessively larger than the polyimide The developability is excessively improved and the pattern formability is significantly lowered.

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

For example, the copolymerization may be represented by the following general formula (11), but is not limited thereto.

(11)

In Formula 11,

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

L 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).

(A)

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

[Chemical Formula B]

In the above formula (B)

And 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 an excellent pattern forming property and the produced thin film can have excellent mechanical and thermal properties.

When the binder resin according to one embodiment contains only the polyamide acid-polyimide copolymer resin alone, the melting property may be lowered. Therefore, the binder resin may contain, in addition to the polyamide acid-polyimide copolymer resin, , An acrylic binder resin and / or a cadmium binder resin.

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

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

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

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

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

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

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

The cationic binder resin may be represented by the following chemical formula (14).

[Chemical Formula 14]

In Formula 14,

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

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

Z ¹ is a single bond, O, CO, SO ₂ , CR ⁵⁵ R ⁵⁶ , SiR ⁵⁷ R ⁵⁸ (wherein R ⁵⁵ to R ⁵⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) Is a linking group represented by the following formulas (14-1) to (14-11)

[Formula 14-1]

[Formula 14-2]

[Formula 14-3]

[Chemical Formula 14-4]

[Formula 14-5]

(In the above 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.

[Chemical Formula 14-6]

[Chemical Formula 14-7]

[Chemical Formula 14-8]

[Chemical Formula 14-9]

[Chemical Formula 14-10]

[Chemical Formula 14-11]

Z ² is an acid anhydride residue,

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

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

The cadmium-based binder resin may include a functional group represented by the following formula (15) in at least one of the two terminals.

[Chemical Formula 15]

In Formula 15,

Z ³ may be represented by the following general formulas (15-1) to (15-7).

[Formula 15-1]

(Wherein 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]

[Chemical Formula 15-4]

[Formula 15-5]

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

[Formula 15-6]

[Formula 15-7]

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

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

The content of the acrylic binder resin or the cadmium binder resin in the binder resin may be lower than the content of the polyamide acid-polyimide copolymer resin. For example, the content of the polyamic acid-polyimide copolymer may be 2 to 3 times the content of the acrylic binder resin or the cadmium-based binder resin. When the content of the acrylic binder resin or the cadmium binder resin is less than the content of the polyamic acid-polyimide copolymer, heat resistance and outgas characteristics can be further improved with excellent developability.

The binder resin may be contained in an amount of 1 wt% to 20 wt%, for example, 3 wt% to 15 wt% with respect to the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

(C) Light curing Initiator

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

Examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

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

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

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

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like. .

Examples of the oxime compounds include O-acyloxime compounds, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Etc. may be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- -Oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) Acetate, and the like, but the present invention is not limited thereto.

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

The photopolymerization initiator may 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 can increase the surface hardening rate as a short wavelength initiator. The second photopolymerization initiator improves the internal hardening speed, not the surface, as a long wavelength initiator to enhance adhesion to the lower substrate, can do.

For example, the first photopolymerization initiator may be represented by the following general formula (12) and the second photopolymerization initiator may be represented by the following general formula (13).

[Chemical Formula 12]

[Chemical Formula 13]

In the above formulas (12) and (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,

and n5 and n6 are integers of 0 to 5.

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

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy. That is, the black photosensitive resin composition may further include a photosensitizer.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like But the present invention is not limited thereto.

The photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, for example, 0.5 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, it is possible to obtain sufficient reliability due to sufficient curing during exposure in the pattern formation step, to have excellent heat resistance, light resistance and chemical resistance, excellent resolution and adhesion, It is possible to prevent the transmittance from being lowered.

(D) a black colorant

The photosensitive resin composition according to one embodiment includes a black colorant, 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, and the pigment dispersion may include a solid pigment, a dispersant, a solvent, and the like. In this case, the pigment of solid content relative to the total amount of the pigment dispersion may be 8 wt% to 30 wt%, for example 8 wt% to 15 wt%, for example 8 wt% to 12 wt%. 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-based organic black, RGB black, carbon black, . ≪ / RTI > Specifically, the organic black pigment may be a lactam-based organic black represented by the following formula (C).

≪ RTI ID = 0.0 &

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

When the black pigment contains carbon black, it is excellent in light shielding property, surface smoothness, dispersion stability, compatibility with the binder resin, and the like. On the other hand, when the black pigment is used, it may be used in combination with a color correcting agent such as an anthraquinone pigment, a perylene pigment, a phthalocyanine pigment or an azo pigment.

The primary particle diameter of the black pigment may be from 10 nm to 80 nm, for example, from 10 nm to 70 nm. When the primary particle diameter is within the above-mentioned particle diameter range, the stability in the pigment dispersion is excellent and there is no fear of deterioration of the resolution of the pixel, which is preferable.

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 may be used Among them, propylene glycol monomethyl ether acetate can 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 wt% to 30 wt%, but is not limited thereto.

The solvent may be present in an amount of from 30% by weight to 90% by weight, such as from 40% by weight to 90% by weight, such as from 50% by weight to 90% by weight, such as from 60% by weight to 90% 70% to 90% by weight, such as 80% to 90% by weight.

In addition, the pigment dispersion may further include a dispersant. As the dispersing agent, nonionic, anionic or cationic dispersing agents can be used. Examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts , A sulfonic acid ester, a sulfonic acid salt, a carboxylic acid ester, a carboxylate, an alkylamide alkylene oxide adduct, and an alkylamine. These dispersants may be used singly or in combination of two or more.

For example, the black pigment may be BK-6912, BK-6913, BK-6616 manufactured by Tokushiki; TCD-006H of Nippon Steel Corporation; But are not limited to, CI-M 390, CI-M 391, CI-M 395, CI-M 400, CI-M 402, CI-M408 or combinations thereof.

For example, the black colorant may include both an organic black pigment that increases the transmittance in the infrared region and aline in the patterning process, and carbon black that increases the light shielding property in the visible light region.

For example, the black dye may be at least one selected from the group consisting of acridine dyes, anthraquinone dyes, arylmethane dyes, diarylmethane dyes, 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, The present invention relates to a dyestuff composition comprising at least one selected from the group consisting of dyes (oxazin dyes), oxazone dyes, thiazin dyes, thiazole dyes, xanthene dyes, fluorene dyes, (Pyronin dyes), rhodamine dyes and the like can be used. It is not limited.

The black colorant may be contained in an amount of 1% by weight to 20% by weight, for example, 2% by weight to 15% by weight based on the total amount of the photosensitive resin composition. For example, the black colorant may be contained in an amount of 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 contained within the above range, the brightness, color reproducibility, pattern curability, heat resistance, and adhesion are excellent.

(E) Solvent

The solvent may be a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a material that has compatibility with a black colorant and does not react with the binder resin according to one 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, diisobutyl 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 methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl 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- ; 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; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl 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 also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate and 3-methoxybutyl acetate.

Of these, glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol dimethyl ether are preferable in view of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; 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 contained in an amount of from about 40% by weight to about 80% by weight based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability in the production of the color filter is excellent.

(F) Other additives

In order to prevent spots or spots during coating and to improve the leveling performance and to prevent the formation of residues due to unexposed phenomenon, the photosensitive resin composition is preferably prepared by adding malonic acid, 3-amino-1,2-propanediol, Or other additives such as a silane-based 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 trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used singly or in combination of two or more.

As the surfactant, a fluorochemical surfactant may be used. Examples of the fluorine-based surfactant, BM Chemie Corporation ^{BM-1000 ®, BM-1100} ® , and the like; Mecha Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; M. Sumitomo Co., Inc. Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Inc. Saffron S-112 ^®, the same S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; 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 desired properties.

The photosensitive resin composition may further include an epoxy compound to improve adhesion with the substrate.

Examples of the epoxy compound include a phenol novolak epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

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

The black photosensitive resin composition may be a negative type black photosensitive resin composition. The photosensitive resin composition has a positive type in which the exposed portion is dissolved by development and a negative type in which the exposed portion is cured, and a photosensitive resin composition containing the above-mentioned black colorant is used to prepare a photosensitive resin film such as a light- In case of the positive type, the transmittance of ultraviolet rays is reduced, and it may be difficult to realize a fine pattern.

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

The photosensitive resin film may be, for example, a light-shielding film or a black pixel barrier layer.

The method of producing the photosensitive resin film is as follows.

(1) Coating and Film Formation Step

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

(2) Exposure step

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

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

(3) Development step

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

(4) Post-treatment step

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

Another embodiment provides a display device comprising the photosensitive resin film.

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

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

( Example )

(Copolymer resin synthesis)

Synthetic example  1: Synthesis of copolymer resin

86.6 g of N-methyl-2-pyrrolidone (NMP) was put into a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injector and a condenser while nitrogen was passed through the flask. O-isopropylidene) diphthalic anhydride (6-FDA) were added and dissolved. When the solid was completely dissolved, 3.25 g of 3-aminophenylsulfone (3-DAS) was added, and the mixture was stirred at room temperature for 2 hours. After the temperature was raised to 90 ° C, 5.6 g of pyridine and 2.05 g of acetone hydride (A ₂ CO) were added and stirred for 3 hours. After the temperature in the reactor was cooled to room temperature, 1.6 g of 2-hydroethyl methacrylate (HEMA) was added and stirred for 6 hours. Then, 3.25 g of 3-aminophenylsulfone (3-DAS) was added and reacted for 6 hours to complete the reaction. The reaction mixture was poured into water to form a precipitate, and the precipitate was filtered and sufficiently washed with water. After repeating the precipitation / washing / filtering four times, it was dissolved in 3-methoxybutyl acetate, and the water content was controlled to be not more than 1000 ppm by a distill process at a temperature of 40 캜 to prepare a polyamic acid-polyimide copolymer resin . The copolymer had a weight average molecular weight of 7,500 g / mol determined by GPC (Gel Permeation Chromatography) standard polystyrene conversion and a degree of dispersion of 1.75. (Molar ratio of polyimide unit and polyamic acid unit = 50: 50)

(Preparation of photosensitive resin composition)

Example  1 to Example  6 and Comparative Example  1 to Comparative Example  5

Using the following components, 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.

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

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

(A) Binder resin

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

(A-2) Cadmium binder resin (V259ME, NSSC)

(B) Photopolymerization  Monomer

1st Photopolymerization  Monomer

(B-1) 9,9-bis [4- (2-acryloyloxyethyloxy) phenyl] fluorene (PN6310, Polynetron)

Second Photopolymerization  Monomer

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

(B-3) a compound represented by the formula (X) (ABPE, Shin-Nakamura)

(X)

(In the formula X, m1 + m2 = 20.)

(C) Light curing Initiator

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

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

(D) a 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-methoxybutyl acetate (3-MBA, Sigma-aldrich)

(F) Other additives

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

(Unit: wt%) 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) a 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) a 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: wt%) 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) a photopolymerizable monomer B-1 - - 5 - - B-2 5 - - 5 - B-3 - 5 - - 5 (C) a 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 of Examples 1 to 6 and Comparative Examples 1 to 5 were coated on a 10 cm * 10 cm ITO glass (resistance 30 Ω) and heated on a hot plate at 100 ° C. for 1 minute to form 1.2 μm Thick coating film was formed. The substrate coated with the coating film was exposed to a varying amount of exposure with an I-line stepper (NSR i10C, Nikon) using a mask having a pattern of various sizes, and then exposed to 2.38% TMAH aqueous solution at room temperature for 10 seconds to 120 The unexposed portion was dissolved (removed) through a puddle process, and then washed with DIW for 30 seconds. Subsequently, the obtained pattern was cured by using an oven at an oxygen concentration of 1000 ppm or less at 250 DEG C for 60 minutes to obtain a pattern.

Development margin (pattern Line width  Measure)

Sensitive sensitivities of the photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 were examined and the developing time was progressed from 10 seconds to 120 seconds. Subsequently, the line width of the 20 mu m hole pattern in the patterns of various sizes obtained was measured by optical equipment, and the results are shown in Table 3 below.

Developing margin
Pattern line width (탆) at TMAH (2.38%) 10 seconds 20 seconds 30 seconds 40 seconds 50 seconds 60 seconds 70 seconds 80 seconds 90 seconds 100 seconds 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 compositions according to Examples 1 to 6 including the first photopolymerizable monomer represented by the formula (1) and the second photopolymerizable monomer different from the first photopolymerizable monomer according to Comparative Examples 1 to 5 It can be confirmed that the developing margin is superior to the resin composition. Further, it can be confirmed that the case where the first photopolymerizable monomer and the second photopolymerizable monomer are contained in a weight ratio of 1: 3 to 3: 1 is more excellent than a case where the weight ratio is out of the range.

Heat resistance

TGA analysis was conducted on the photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 to determine a 1 wt% loss temperature. The results are shown in Table 4 below.

Taper  Angle

The patterned coating films prepared using the photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 were measured with FE-SEM equipment (S-4300, hitachi) Are shown in Table 4 below.

Out gas

The patterned coating film prepared using the photosensitive resin composition according to Examples 1 to 6 and Comparative Examples 1 to 5 was cut into 5 cm x 5 cm and analyzed by TD-GC / MS to obtain outgas (ng / cm < ² >). The results are shown in Table 4 below. The method of analysis is as follows.

<Procedure>

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

2) Qualify the gas in the TD tube (Tenax TA) after setting the conditions of TD (MARKES UNITY2) -GC / MS (Thermo ISQ LT) according to the following measurement conditions.

<Measurement Conditions>

TD

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

GC / MS

Column DB-5MS? 30 m 0.25 mm 0.25 占 퐉 (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. (° C) 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 compositions according to Examples 1 to 6 including the first photopolymerizable monomer represented by the formula (1) and the second photopolymerizable monomer different from the first and second photopolymerizable monomers described in the comparative examples 1 to 5 It can be confirmed that the resin composition is superior in heat resistance, outgas characteristics and taper characteristics. Furthermore, it can be confirmed that the case where the first photopolymerizable monomer and the second photopolymerizable monomer are contained in a weight ratio of 1: 3 to 3: 1 is superior to the case where the weight ratio is out of the range. In the case of Example 5, the taper angle is somewhat low, which may cause the pattern to collapse. In the case of Example 6, the taper angle is somewhat high, so it is difficult to form the pattern stably.

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

Claims (17)

(A) a binder resin comprising a polyimide-polyamic acid copolymer resin;
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) a black colorant; And
(E) Solvent
Lt; / RTI &gt;
Wherein the photopolymerizable monomer comprises a first photopolymerizable monomer represented by the following general formula (1) and a second photopolymerizable monomer different from the first photopolymerizable monomer:
[Chemical Formula 1]

In Formula 1,
R ¹ to R ⁴ each independently represent the following formula (2)
o, p, q and r each independently represents an integer of 0 or 1,
(2)

In Formula 2,
L ¹ is a substituted or unsubstituted C1 to C10 alkylene group,
s is an integer of 1 to 3;
The method according to claim 1,
Each of o and p is independently an integer of 1,
And q and r are each independently an integer of 0.
3. The method of claim 2,
Wherein the first photopolymerizable monomer is represented by the following Formula 3:
(3)

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

In Formula 4,
t is an integer of 1 or 2;
The method according to claim 1,
Wherein the second photopolymerizable monomer is represented by the following Chemical Formula 5 or Chemical Formula 6:
[Chemical Formula 5]

[Chemical Formula 6]

In the above 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 each independently represent 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.
5. The method of claim 4,
L ⁸ is a substituted or unsubstituted C1 to C10 alkylene group,
Wherein L ⁹ and L ¹⁰ are each independently a substituted or unsubstituted C6 to C20 arylene group.
The method according to claim 1,
Wherein the first photopolymerizable monomer and the second photopolymerizable monomer are contained in a weight ratio of 1: 3 to 3: 1.
The method according to claim 1,
Wherein the copolymer resin has an unsaturated double bond at at least one terminal thereof.
8. The method of claim 7,
Wherein the unsaturated double bond is derived from any one compound selected from the group consisting of the following formulas (7) to (10):
(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above 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 according to claim 1,
Wherein the copolymer resin comprises polyimide and polyamic acid in a molar ratio of 40:60 to 60:40.
The method according to claim 1,
Wherein the polyimide in the copolymer resin is represented by the following Formula 11:
(11)

In Formula 11,
X ¹ and X ² are each independently a substituted or unsubstituted quadrivalent alicyclic organic group or a substituted or unsubstituted quadrivalent aromatic organic group,
L 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 according to claim 1,
Wherein the copolymer resin has a weight average molecular weight of 3,000 g / mol to 100,000 g / mol.
The method according to claim 1,
Wherein the binder resin further comprises an acrylic binder resin, a cadmium binder resin, or a combination thereof.
The method according to claim 1,
Wherein the black colorant is at least one of an aniline black pigment, a perylene black pigment, a titanium black pigment, a cyanine black pigment, a lignin black pigment, a lactam-based organic black pigment, a RGB black pigment, a carbon black pigment, a black dye, Composition.
The method according to claim 1,
The above-mentioned photosensitive resin composition is characterized in that the total amount of the photosensitive resin composition
1 to 20% by weight of the binder resin (A);
0.5 to 10% by weight of the photopolymerizable monomer (B);
0.1 to 5% by weight of the photopolymerization initiator (C);
1 to 20% by weight of (D) black colorant and
The amount of the solvent (E)
.
The method according to claim 1,
Wherein the photosensitive resin composition further comprises additives such as malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a fluorine-based surfactant, or a combination thereof.
A photosensitive resin film produced by using the photosensitive resin composition of any one of claims 1 to 15.
A display device comprising the photosensitive resin film of claim 16.