KR20190001819A - Photosensitive resin composition, black photosensitive resin layer using the same and color filter - Google Patents

Abstract

Provided are a photosensitive resin composition, a black photosensitive resin layer manufactured by using the photosensitive resin composition, and a color filter having the black photosensitive resin layer, wherein the photosensitive resin composition comprises: (A) binder resin having cardo-based resin; (B) a photopolymerizable monomer discolored at 200-400°C; (C) a photopolymer initiator; (D) a black coloring agent; and (E) a solvent.

Description

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

The present invention relates to a photosensitive resin composition, a black photosensitive resin film and a color filter using the same.

The photosensitive resin composition is an indispensable material for the production of display devices such as color filters, liquid crystal display materials, organic light emitting devices, and display panel materials. For example, a color filter such as a color liquid crystal display requires a black matrix at a boundary portion between coloring layers such as red, green, and blue in order to enhance display contrast and coloring effect, The black matrix is mainly formed of a photosensitive resin composition.

Recently, efforts have been made to use the black matrix material as a column spacer supporting between two TFTs and a C / F substrate existing between the liquid crystal layers, and the column spacer is referred to as a black column spacer.

In the case of the black column spacer, the step of the pattern must be formed due to the difference in the transmittance of the photomask, and at the same time, not only the compressive displacement, the elastic recovery rate and the breaking strength which are functions of the column spacer but also the light- Should be high enough. In addition, since the column spacer and the black matrix layer are formed at the same time, the step height of the column spacer with a high height and the relatively low black matrix must be realized by using a half tone mask. Since the black column spacer is a layer that directly contacts the liquid crystal, unlike a general black matrix, a reliability characteristic capable of minimizing liquid crystal contamination is required, and the chemical resistance of the solution for the solvent and rework of the upper layer polyimide Is also essential.

However, the conventional photosensitive resin composition for a black column spacer has a problem of low optical density, low exposure margin and low developing margin.

Therefore, studies for developing a photosensitive resin composition for a black column spacer taking such characteristics into consideration have continued.

One embodiment is to provide a photosensitive resin composition having high optical density and shrinkage ratio after curing.

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

Another embodiment is to provide a color filter comprising the black photosensitive resin film.

One embodiment includes (A) a binder resin comprising a cardade resin; (B) a photopolymerizable monomer which is discolored at 200 ° C to 400 ° C; (C) a photopolymerization initiator; (D) a black colorant; And (E) a solvent.

The photopolymerizable monomer may have a yellow index of 2.9 to 7.0 after heat treatment at 200 ° C to 400 ° C.

The photopolymerizable monomer may be any one of compounds represented by the following formulas (A) to (D).

(A)

[Chemical Formula B]

≪ RTI ID = 0.0 &

[Chemical Formula D]

In the above Formulas A to D,

R ³ to R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ to L ⁴ each independently represent a substituted or unsubstituted C1 to C10 alkylene group,

L ⁵ is a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C6 to C20 arylene group.

The black colorant may include a red pigment, a blue pigment, and a violet pigment.

The black colorant may include 40% by weight to 60% by weight, 30% by weight to 50% by weight and 10% by weight to 20% by weight of red pigment, blue pigment and violet pigment, respectively, relative to the total amount of black colorant.

The red pigment may include a compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C10 alkyl group.

The blue pigment may include a phthalocyanine compound.

The violet pigment may comprise a perylene compound.

Wherein the binder resin further comprises a copolymer, and the copolymer includes a structural unit represented by the following formula (6), wherein the copolymer has a structural unit represented by the following formula (7) or a structural unit represented by the following formula .

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 6 to 8,

R ¹⁰¹ to R ¹⁰³ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁰⁴ to R ¹⁰⁷ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,

Each of R ¹⁰⁵ to R ¹⁰⁷ may be independently present or may combine with each other to form a ring.

The copolymer resin may include the structural unit represented by the formula (6), the structural unit represented by the formula (7), and the structural unit represented by the formula (8).

The structural unit represented by the formula (6) and the structural unit represented by the formula (7) and the structural unit represented by the formula (8) may be contained in the copolymer resin in a molar ratio of 50:50 to 80:20.

The copolymer resin may have a weight average molecular weight of 3,000 g / mol to 300,000 g / mol.

Wherein the photosensitive resin composition comprises 1 to 10% by weight of the binder resin (A) relative to the total amount of the photosensitive resin composition; 1 to 10% by weight of the photopolymerizable monomer (B); 0.1 to 5% by weight of the photopolymerization initiator (C); 30% to 50% by weight of (D) black colorant; And (E) the solvent balance.

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

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

The black photosensitive resin film may be a black column spacer.

The black column spacer may include a main column spacer and a sub column spacer.

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

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

The photosensitive resin composition according to one embodiment can provide a black column spacer having a high optical density after curing and excellent in exposure margin and development margin, including a photopolymerizable monomer which is discolored at 200 ° C to 400 ° C.

1 is a graph showing exposure margins of the photosensitive resin compositions according to Examples 1 and 2 and Comparative Example 1. Fig.
Fig. 2 is a graph showing the developing margin of the photosensitive resin composition according to Example 1, Example 2, and Comparative Example 1. Fig.

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 Chemical Formulas (2-1) to (2-11) 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 photosensitive resin composition according to one embodiment comprises (A) a binder resin comprising a camidic resin; (B) a photopolymerizable monomer which is discolored at 200 ° C to 400 ° C; (C) a photopolymerization initiator; (D) a black colorant; And (E) a solvent.

In the case of a black column spacer, it has a function of a light-shielding portion (black matrix) having a sufficiently high optical density and a column spacer for maintaining a cell gap. In forming the pattern of such a black column spacer, it is necessary to keep a light-shielding portion of uniform thickness on the entire surface of the substrate. If the thickness of the light-shielding portion is reduced to a certain level or less, the optical density is decreased together with the result that the light-shielding defects may occur, the uniformity of the stepped portions in the substrate may be varied, and the cell gap and the liquid crystal margin may be defective . In order to improve such a step margin, light must reach the deep portion of the light-shielding portion. However, if the light-shielding portion has sufficient optical density, light can not be transmitted and surface hardening is limited.

The photosensitive resin composition according to one embodiment overcomes the above limitations by using a photopolymerizable monomer which is discolored (browning or yellowing) at a certain temperature, that is, a photopolymerizable monomer having a high yellow index and a high hardening shrinkage. Since the photopolymerizable monomer is colorless or off-color at the time of exposure, the transparency of light is increased to increase the step margin, and after post-baking (curing), yellowing and browning are possible, thereby making it possible to manufacture a black column spacer having sufficient light-

Each component will be described in detail below.

(B) Photopolymerization  Monomer

Examples of the photopolymerizable monomer in the conventional photosensitive resin composition include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) (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 It is common to use a recall monomethyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.

However, compounds conventionally used as photopolymerizable monomers in photosensitive resin compositions are compounds which prevent discoloration (browning or yellowing) at maximum at a certain temperature or higher.

As described above, the photosensitive resin composition for a black column spacer must have a sufficiently high optical density and a uniform thickness throughout the entire substrate after post-baking (curing). If the optical density is not sufficiently high and the pattern does not have a uniform thickness , The step margins become poor, light can not reach the deep portion, and only surface hardening occurs. When the photosensitive resin composition according to one embodiment is used, the step between the main spacer and the sub-spacer of the black column spacer does not greatly vary according to the time and the exposure amount, and the thickness is maintained before the post baking (curing) Using a specific photopolymerizable monomer so as to yellow and browse after curing (curing), an excellent step margin and sufficient light shielding properties can be obtained.

The photopolymerizable monomer may have a yellow index of 2.9 to 7.0 after heat treatment at 200 ° C to 400 ° C.

The photopolymerizable monomer may be any one of compounds represented by the following formulas (A) to (D).

(A)

[Chemical Formula B]

≪ RTI ID = 0.0 &

[Chemical Formula D]

In the above Formulas A to D,

R ³ to R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ to L ⁴ each independently represent a substituted or unsubstituted C1 to C10 alkylene group,

L ⁵ is a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C6 to C20 arylene group.

For example, each of R ³ to R ⁷ may independently be a hydrogen atom, and each of L ¹ to L ⁵ may independently be a substituted or unsubstituted C 1 to C 5 alkylene group.

For example, the photopolymerizable monomer may be any one of compounds represented by the following formulas (A-1) to (D-1).

[A-1]

[Formula B-1]

[Chemical formula C-1]

[Formula D-1]

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

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

(A) Binder resin

The binder resin includes a cardade resin.

The use of a caprolactone resin in a photosensitive resin composition for the production of a black column spacer generally decreases the break point (BP) with time, and thus the line width is reduced. In the case of a black column spacer, The height of the matrix tends to be lowered. In order to improve this, a method of excluding the use of a cardo-based resin is usually used. However, when a general acrylic resin is used, fine patterning characteristics (fixed definition) are insufficient, or in the case of a black column spacer, a solvent for a polyimide film, N- methyl pyrrolidine) due to the lack of chemical resistance caused by the side effects such as pattern damage.

In order to minimize the above-mentioned side effects, an acrylic binder resin containing an epoxy group rather than a cadmium resin may be used. In this case, the chemical resistance to NMP is improved and the taper characteristic However, the BP (break point) gradually increases with time, which causes a side effect in which the phenomenon occurs even though the development time is appropriate.

In view of the above-mentioned side effects, the photosensitive resin composition according to an embodiment may further include a copolymer described later together with a cadmium resin as a binder resin. In this case, the heat resistance can be further improved.

The cation resin may include a repeating unit represented by the following formula (2).

(2)

In Formula 2,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ¹³ and R ¹⁴ 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 ⁸ R ⁹ , SiR ¹⁰ R ¹¹ (wherein R ⁸ to R ¹¹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) Is any one of the linking groups represented by formulas (2-1) to (2-11)

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

(In the above Formula 2-5,

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 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

[Chemical Formula 2-9]

[Chemical Formula 2-10]

[Chemical Formula 2-11]

Z ² is an acid anhydride residue,

m1 and m2 are each independently an integer of 0 to 4;

The cadmium-based binder resin may include a functional group represented by the following formula (3) on at least one of both terminals.

(3)

In Formula 3,

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

[Formula 3-1]

(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 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

(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 alkenylamine group).

[Chemical Formula 3-6]

[Chemical Formula 3-7]

Examples of the cadid-based resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride , Tetrahydrofuran tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride and the like; 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.

The weight average molecular weight of the cardade 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 carded resin is within the above range, pattern formation is good without residue in the production of a black column spacer, no loss of film thickness during development, and a good pattern can be obtained.

The copolymer usable with the cationic binder resin may include a structural unit represented by the following formula (6).

[Chemical Formula 6]

The copolymer may further comprise a structural unit represented by the following formula (7) or a structural unit represented by the following formula (8).

(7)

[Chemical Formula 8]

In the above Chemical Formulas 6 to 8,

R ¹⁰¹ to R ¹⁰³ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁰⁴ to R ¹⁰⁷ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,

Each of R ¹⁰⁵ to R ¹⁰⁷ may be independently present or may combine with each other to form a ring.

For example, the copolymer resin may be represented by the following formula (9) or (10).

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas (9) and (10)

R ¹⁰¹ to R ¹⁰³ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁰⁴ to R ¹⁰⁷ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,

R ¹⁰⁵ to R ¹⁰⁷ may be independently present or may combine with each other to form a ring,

1, m, and n are each independently an integer of 1 or more, for example, 1 or more and 1000 or less, for example, 1 or more and 500 or less,

The copolymer resin further contains the structural unit represented by the formula (7) or the structural unit represented by the formula (8), whereby the chemical resistance is excellent.

The structural unit represented by Formula 6 and the structural unit represented by Formula 7 may be contained in the copolymer resin in a molar ratio of 50:50 to 80:20, for example, 50:50 to 70:30. That is, in the above formula (9), 1: m may be 50:50 to 80:20, such as 50:50 to 70:30.

The structural unit represented by the formula (6) and the structural unit represented by the formula (8) may be contained in the copolymer resin in a molar ratio of 50:50 to 80:20, for example, 50:50 to 70:30. That is, in Formula 10, 1: n may be 50:50 to 80:20, for example, 50:50 to 70:30.

The copolymer resin may include the structural unit represented by the formula (6), the structural unit represented by the formula (7), and the structural unit represented by the formula (10).

For example, the copolymer resin may be represented by the following general formula (11).

(11)

In Formula 11,

R ¹⁰¹ to R ¹⁰³ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁰⁴ to R ¹⁰⁷ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,

R ¹⁰⁵ to R ¹⁰⁷ may be independently present or may combine with each other to form a ring,

l, m and n are each independently an integer of 1 or more, for example, 1 or more and 1000 or less, such as 1 or more and 500 or less, such as 1 or more and 100 or less.

In this case, the "structural unit represented by the formula (6)" and the "structural unit represented by the formula (7) and the structural unit represented by the formula (8)" may be in a molar ratio of 50:50 to 80:20, Lt; RTI ID = 0.0 > 30. ≪ / RTI > That is, in Formula 11, 1: (m + n) may be 50:50 to 80:20, such as 50:50 to 70:30.

When the structural units of the formulas (6) to (8) have the number of moles in the above range, that is, when l, m and n fall within the above ranges, the resolution, chemical resistance, and sensitivity of the photosensitive resin composition are improved.

The copolymer resin strongly interacts with the above-mentioned photopolymerizable monomer to improve the resolution. Further, when the photosensitive resin composition containing the copolymer resin is cured, it can be imidized and the heat resistance can be improved as well.

The copolymer resin may have a thermally polymerizable functional group derived from a reactive terminal blocking monomer on one or both ends of the terminal. The reactive end blocking monomers are preferably monoamines having carbon-carbon double bonds, monoanhydrides, or a combination thereof. Examples of the monoamines include, but are not limited to, toluidine, dimethyl aniline, ethyl aniline, aminophenol, aminobenzyl alcohol, aminoindan, aminoacetone phenone, and combinations thereof.

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

The binder resin may be contained in an amount of 1% by weight to 10% by weight based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, the color filter is excellent in developing property and the crosslinking property is improved, whereby excellent surface smoothness can be obtained.

(D) a black colorant

The black colorant may include a red pigment, a blue pigment, and a violet pigment.

Since the black column spacer must be able to function as a black matrix and a column spacer, it must have a function of blocking light emitted from the backlight and a function of supporting the top plate and the bottom plate. In addition, the column spacer and the black matrix portion Should be clearly distinguished. However, when a black column spacer is implemented using an existing material such as an inorganic black pigment such as carbon black or an organic black pigment, since the light transmittance is low and only the film surface is cured, it is difficult to form a step.

However, according to one embodiment, by using a mixture of a red pigment, a blue pigment and a violet pigment without using an inorganic black pigment such as carbon black or an organic black pigment alone as a black colorant, So that the black column spacer step can be easily formed.

For example, the red pigment may include a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C10 alkyl group.

For example, R ¹ and R ² each independently may be a methyl group.

Generally, in the case of a black column spacer, a polyimide film is formed thereon, and therefore, it is required that the polyimide film has excellent solvent resistance to NMP which is a solvent of polyimide. By using the compound represented by the above formula (1) as the red pigment, for example, it is possible to easily control the content-releasing property, for example, the releasability to NMP can do.

The black colorant may include 40% by weight to 60% by weight, 30% by weight to 50% by weight and 10% by weight to 20% by weight of red pigment, blue pigment and violet pigment, respectively, relative to the total amount of black colorant. When the red pigment, the blue pigment, and the violet pigment are included in the above content range, a pattern favorable for the formation of a step can be formed as the transmittance in the short wavelength region is maximized, and the transmittance in the visible light region is minimized, It is possible to maximize the optical density, which is an intrinsic property.

The blue pigment may include a phthalocyanine compound. For example, the blue pigment may be a phthalocyanine compound.

For example, the blue pigment may be represented by the following formula (4).

[Chemical Formula 4]

The violet pigment may comprise a perylene compound. For example, the violet pigment may be represented by the following general formula (5).

[Chemical Formula 5]

The black colorant may further include an inorganic black pigment.

For example, the inorganic black pigment may include carbon black, titanium black, perylene black, aniline black, or a combination thereof. For example, the inorganic black pigment may be carbon black.

The inorganic black pigment may be contained in an amount of 3% by weight to 8% by weight based on the total weight of the black colorant. An inorganic black pigment such as carbon black may have a problem that the dielectric constant increases due to its electrical conductivity and may deteriorate the electrical characteristics of the black photosensitive resin film produced using the black photosensitive resin composition. The carbon black is preferably included in the above content range.

A dispersing agent may be used together to disperse the pigment. Specifically, the pigment may be surface-treated in advance with a dispersant, or a dispersant may be added to the pigment together with the pigment when the composition is prepared.

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

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

The dispersant may be contained in an amount of 0.1 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersing agent is contained within the above range, the dispersibility of the composition is excellent, so that the stability, developability and patternability of the black column spacer are excellent.

The pigment may be used by pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used by the pretreatment, the average particle diameter of the pigment can be made smaller.

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

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

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

The pigment after the kneading step may have an average particle diameter of 5 nm to 200 nm, for example, 5 nm to 150 nm. When the average particle diameter of the pigment is within the above range, the stability in the pigment dispersion is excellent and there is no fear of deterioration of the resolution of the pixels.

Specifically, the pigment may be used in the form of a pigment dispersion including the dispersant and a solvent described later, and the pigment dispersion may include a solid pigment, a dispersant, and a solvent. The solid pigment may be contained in an amount of 5 to 20% by weight, for example 8 to 15% by weight based on the total weight of the pigment dispersion.

The black colorant may be contained in an amount of 30% by weight to 50% by weight, for example, 35% by weight to 45% by weight based on the total amount of the photosensitive resin composition. When the black colorant is contained within the above range, the coloring effect and developing performance are excellent.

(C) Light curing Initiator

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

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

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

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

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

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

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.

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

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

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

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

(E) Solvent

The solvent may be a material which has compatibility with the black colorant, the photopolymerization initiator, the photopolymerizable monomer, and the binder resin but does not react.

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, ethylene glycol monoethyl ether and ethylene glycol dimethyl ether (EDM); 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, and phenyl cellosolve acetate.

Among them, ketones such as cyclohexanone and the like are preferably used in consideration of compatibility and reactivity; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether and ethylene glycol diethyl ether; 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 30% by weight to 70% by weight based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability in the production of the black column spacer is excellent.

(F) Other additives

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

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

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

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

The above-mentioned photosensitive resin composition may further contain a surfactant such as a fluorine-based surfactant for the purpose of improving coatability and preventing defect formation, if necessary.

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

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

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

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

The black photosensitive resin film may be a black column spacer.

The black column spacer may include a main column spacer and a sub column spacer.

Since the black column spacer also functions as a black matrix, the optical density after curing at a coating thickness of 1 to 2 탆 can be 2.5 or more.

The black photosensitive resin film production method is as follows.

(1) Coating and Film Formation Step

The photosensitive resin composition is coated on a substrate such as a glass substrate or an IZO substrate subjected to a predetermined pretreatment to a desired thickness by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method or the like, Deg.] C to 100 [deg.] C for 1 minute to 10 minutes to remove the solvent to form a coating film.

(2) Exposure step

A full tone portion for implementing a half-tone portion and a main column spacer pattern for implementing a black matrix and a sub-column spacer pattern is formed on the coating film obtained above, And then an active line of 200 nm to 500 nm is 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 the developing solution after the above-mentioned exposure step, so that only the exposed portion is left to form a pattern and BP (Break Point) is measured.

(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 can be heated in a convection oven at 230 캜 for 30 minutes.

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

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 )

(Preparation of Copolymer Resin)

Manufacturing example  One

In a flask made of nitrogen atmosphere, 100 parts by weight of the monomer was added so that the molar ratio of the monomer represented by the following formula (P), the monomer represented by the following formula (Q) and the monomer represented by the following formula R was 50:30:20 (1) of propylene glycol methyl ether acetate was prepared.

100 g of propylene glycol methyl ether acetate solution (2) was prepared by adding 2,2'-azobisisobutyronitrile as an initiator to 10% by weight of the total amount of monomers.

50 g of propylene glycol methyl ether acetate was added to a separate flask in a nitrogen atmosphere and the mixture was heated to 80 DEG C and then the monomer solution (propylene glycol methyl ether acetate solution (1)) and initiator solution (propylene glycol methyl ether acetate solution 2)) was added dropwise simultaneously over 4 hours. After completion of the dropwise addition, stirring was continued for 2 hours and then cooled to room temperature. The resulting polymerization solution was added dropwise to stirred methanol, and the precipitated copolymer was filtered to prepare a copolymer resin (weight average molecular weight: 9,000 g / mol).

[Chemical Formula P]

[Chemical formula (Q)

[Chemical formula R]

( Photopolymerization  Monomer production)

Manufacturing example  2

(1) A 2-mercaptobenzothiazole (16.7 g, 100 mmol), paraformaldehyde (3.9 g, 120 mmol) and NaOAc (0.82 g, 10 mmol) were added to a round bottom flask, and 200 ml of chlorobenzene was added thereto. Lt; 0 > C for 2 hours. When the reaction was completed, the temperature was lowered to room temperature and the filtrate was removed through a filter. The filter above solid compound extracted with methylene chloride and water and saturated NaHCO ₃ Aqueous solution. After removing the solvent, 15 g of a compound represented by the following formula (M-1) was synthesized using color chromatography.

[M-1]

¹ H NMR 7.48 (d, 1 H), 7.42 (t, 1 H), 7.36 (d, 1 H), 7.29

(2) 6.1 g of the compound represented by the above formula (M-1) was added to a round bottom flask, and 50 g of dichloromethane was added thereto, followed by stirring while lowering the temperature to 10 ° C. 3.48 g (34.4 mmol) of triethylamine was added, and a solution of 3.12 g of acryloyl chloride in 10 g of dichloromethane was slowly added dropwise over 30 minutes, and the mixture was stirred for 1 hour. When the reaction was completed, the dichloromethane layer was washed with 10% aqueous HCl solution and 10% aqueous NaOH solution, and was washed with water. Water was removed from the obtained dichloromethane layer with MgSO ₄ , filtered and concentrated to obtain 6.4 g of a compound represented by the following formula (D-1).

[Formula D-1]

(Preparation of photosensitive resin composition)

Example  1 to Example  5 and Comparative Example  One

Using the following components, photosensitive resin compositions according to Examples 1 to 5 and Comparative Example 1 were prepared with the compositions shown in Table 1 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. Subsequently, a black 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) Cadocase resin (V259ME, Shinil Chemical Co., Ltd.)

(A-2) The copolymer resin of Production Example 1

(B) Photopolymerization  Monomer

(B-1) dipentaerythritol hexa (meth) acrylate (DPHA, sartomer)

(B-2) DPCA120 (represented by the following formula A-1)

[A-1]

(B-3) DPCA20 (manufactured by Nippon Shokuhin Co., Ltd.) (represented by the following formula B-1)

[Formula B-1]

(B-4) PE044 (represented by the formula (C-1) shown below)

[Chemical formula C-1]

(B-5) The photopolymerizable monomer of Production Example 2

(C) Light curing Initiator

OXE01 (BASF)

(D) a black colorant

(D-1) C.I. Millbase dispersion with Red pigment 179 (SANYO)

(D-2) C.I. Blue pigment 15: 6 with millbase dispersion (SAKATA Inc.)

(D-3) C.I. Violet pigment 29 millbase dispersion (SANYO)

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA, Sigma-aldrich)

(F) Other additives

γ-glycidoxypropyltrimethoxysilane (S-510, Chisso)

(Unit: g) Kinds Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 (A) Binder resin A-1 3.700 3.700 3.700 3.700 1.85 3.700 A-2 - - - - 1.85 - (B) a photopolymerizable monomer B-1 - - - - - 3.700 B-2 3.700 - - - 3.700 - B-3 - 3.700 - - - - B-4 - - 3.700 - - - B-5 - - - 3.700 - - (C) a photopolymerization initiator 0.402 0.402 0.402 0.402 0.402 0.402 (D) a black colorant D-1 16.9259 16.9259 16.9259 16.9259 16.9259 16.9259 D-2 13.8131 13.8131 13.8131 13.8131 13.8131 13.8131 D-3 6.5157 6.5157 6.5157 6.5157 6.5157 6.5157 (E) Solvent 55.2921 55.2921 55.2921 55.2921 55.2921 55.2921 (F) Other additives 0.0532 0.0532 0.0532 0.0532 0.0532 0.0532

(evaluation)

The photosensitive resin compositions of Examples 1 to 5 and Comparative Example 1 were coated on a predetermined pretreated glass substrate by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, or the like to a desired thickness After coating, the solvent was removed by heating at 70 ° C to 100 ° C for 1 minute to 10 minutes to form a coating film. In order to form a pattern necessary for the obtained coating film, a mask composed of a halftone portion (having a transmittance of 20%) for implementing a black matrix pattern and a full tone portion for implementing a column spacer pattern is interposed, And exposed at an exposure amount of 50 mJ to 150 mJ. After the above-described exposure step, development was performed using an alkaline aqueous solution (developer), followed by washing with distilled water to form a pattern. The patterned substrate was cured by heating in an oven at 230 캜 for 30 minutes to obtain a final pattern.

Yellowness and hardness Contraction ratio

For the substrate on which the final pattern was formed, the Yellow Index was obtained, and the results are shown in Table 2 below.

Yellowness Cure shrinkage (%) Example 1 6.7 3.3 Example 2 2.9 7.8 Example 3 4.7 6.2 Example 4 7.8 4.9 Example 5 6.7 3.3 Comparative Example 1 2.8 3.3

It can be seen from Table 2 that the photosensitive resin compositions according to Examples 1 to 5 have higher yellowing degree after curing than the photosensitive resin composition according to Comparative Example 1 in which DPHA is contained as a photopolymerizable monomer, And it is also possible to confirm that the hardening shrinkage is excellent.

Exposure margin, developing margin

The substrate on which the final pattern was formed was measured with a non-contact type thickness measuring instrument (3-D profiler; nanoview, nanosystem), and the result was measured once more after 10 days. The results are shown in FIGS. 1 and 2.

1 and 2, it can be confirmed that the photosensitive resin composition according to Examples 1 to 5 is superior in exposure margin and developing margin as compared with the photosensitive resin composition according to Comparative Example 1 in which DPHA is contained as a photopolymerizable monomer .

Optical density

The photosensitive resin compositions of Examples 1 to 5 and Comparative Example 1 were coated on a predetermined pretreated glass substrate by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, or the like to a desired thickness After coating, the coating film was formed by removing the solvent by heating at 70 to 100 ° C for 1 to 10 minutes, and then the optical density was measured with X-rite. Optical density was measured again after post-bake The optical densities before and after the discoloration were compared and the results are shown in Table 3 below. The optical density is based on a thickness of 1 mu m.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Immediately after exposure 1.73 1.52 1.58 1.68 1.69 1.52 Post-Immediately after bake 2.89 2.51 2.66 2.99 2.79 2.33

From Table 3, it can be seen from Figs. 1 and 2 that the photosensitive resin composition according to Examples 1 to 5 is higher in optical density after curing than the photosensitive resin composition according to Comparative Example 1 comprising DPHA as a photopolymerizable monomer It can be confirmed that it has a sufficient light shielding property.

Heat resistance

The photosensitive resin composition prepared in Examples 1 to 5 and Comparative Example 1 was applied on a 1 mm thick glass substrate having a thickness of 1 to 3 占 퐉 and washed on a hot plate at 90 占 폚 for 2 minutes And dried to obtain a coating film (250 rpm to 350 rpm). Subsequently, the coating film was subjected to front exposure (exposure condition: 50 mJ / cm ² ) using a high-pressure mercury lamp having a main wavelength of 365 nm, and then developed with a 111-fold KOH developer in a developing machine under the condition of water / developing solution = 1 / 0.8 Second, and then rinsed again for 60 seconds to give a development history. Thereafter, it was dried in a hot-air circulating drying oven at 230 ° C for 20 minutes to prepare a color sample. The color specimen was further dried at 230 DEG C for 60 minutes using a convection oven and the color change before and after drying was measured using a spectrophotometer (MCPD3000, Otsuka electronic) (based on C light source) The heat resistance of the specimen was measured (calculated as [Delta] Eab * value) and is shown in Table 4 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Heat resistance 2.9 3.1 3.3 3.2 2.3 3.1

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 (18)

(A) a binder resin comprising a cardo-based resin;
(B) a photopolymerizable monomer which is discolored at 200 ° C to 400 ° C;
(C) a photopolymerization initiator;
(D) a black colorant; And
(E) Solvent
.
The method according to claim 1,
Wherein the photopolymerizable monomer has a yellow index of 2.9 to 7.0 after heat treatment at 200 ° C to 400 ° C.
The method according to claim 1,
Wherein the photopolymerizable monomer is any one of compounds represented by the following Chemical Formulas A to D:
(A)

[Chemical Formula B]

≪ RTI ID = 0.0 &

[Chemical Formula D]

In the above Formulas A to D,
R ³ to R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ to L ⁴ each independently represent a substituted or unsubstituted C1 to C10 alkylene group,
L ⁵ is a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C6 to C20 arylene group.
The method according to claim 1,
Wherein the black colorant comprises a red pigment, a blue pigment, and a violet pigment.
5. The method of claim 4,
Wherein the black colorant comprises 40 wt% to 60 wt%, 30 wt% to 50 wt%, and 10 wt% to 20 wt% of red pigment, blue pigment, and violet pigment, respectively, relative to the total amount of black colorant.
5. The method of claim 4,
Wherein the red pigment comprises a compound represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
R ¹ and R ² are each independently a substituted or unsubstituted C1 to C10 alkyl group.
5. The method of claim 4,
Wherein the blue pigment comprises a phthalocyanine compound.
5. The method of claim 4,
Wherein the violet pigment comprises a perylene compound.
The method according to claim 1,
Wherein the binder resin further comprises a copolymer,
Wherein the copolymer comprises a structural unit represented by the following formula (6)
Wherein the copolymer further comprises a structural unit represented by the following formula (7) or a structural unit represented by the following formula (8)
[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 6 to 8,
R ¹⁰¹ to R ¹⁰³ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R ¹⁰⁴ to R ¹⁰⁷ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,
Each of R ¹⁰⁵ to R ¹⁰⁷ may be independently present or may combine with each other to form a ring.
10. The method of claim 9,
Wherein the copolymer resin comprises the structural unit represented by the formula (6), the structural unit represented by the formula (7), and the structural unit represented by the formula (8).
11. The method of claim 10,
The structural unit represented by the formula (6) and the structural unit represented by the formula (7) and the structural unit represented by the formula (8) are contained in the copolymer resin in a molar ratio of 50:50 to 80:20.
10. The method of claim 9,
Wherein the copolymer resin has a weight average molecular weight of 3,000 g / mol to 300,000 g / mol.
The method according to claim 1,
The photosensitive resin composition preferably contains, relative to the total amount of the photosensitive resin composition,
1 to 10% by weight of the binder resin (A);
1 to 10% by weight of the photopolymerizable monomer (B);
0.1 to 5% by weight of the photopolymerization initiator (C);
30% to 50% 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 coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator or a combination thereof.
A black photosensitive resin film produced by using the photosensitive resin composition of any one of claims 1 to 14.
16. The method of claim 15,
The black photosensitive resin film is a black column spacer.
17. The method of claim 16,
The black column spacer includes a main column spacer and a sub column spacer.
A color filter comprising the black photosensitive resin film of claim 15.

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