KR102216426B1 - Photosensitive resin composition, photosensitive resin layer using the same, color filter and display device - Google Patents

Abstract

(A) acrylic binder resin; (B) photopolymerizable monomer; (C) photoinitiator; (D) a colorant and (E) a solvent, and the photopolymerization initiator includes a first photopolymerization initiator and a second photopolymerization initiator having different wavelengths at which the maximum absorption peak appears in a wavelength range of 300 nm to 400 nm, and the first photopolymerization The initiator is provided with a photosensitive resin composition having a shorter wavelength in which the maximum absorption peak appears in a wavelength range of 300 nm to 400 nm than the second photopolymerization initiator, a photosensitive resin film prepared using the photosensitive resin composition, and a color filter including the photosensitive resin film do.

Description

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

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

Currently, the flat panel display market has grown to an extent that it is difficult to support the demand, and at the center are the plasma display panel (PDP), liquid crystal display (LCD), organic light emitting display (OLED), and the touch display market using the same. . In particular, LCD is a major product in the flat display market, and consists of color filters, thin film transistors and liquid crystals. A color filter used in a color liquid crystal display device or an image pickup device is usually applied by spin coating a photosensitive resin composition containing a pigment corresponding to each color of red, green, and blue on a patterned substrate with a black matrix. It is manufactured by repeating the operation of exposing and developing the coating film formed by heat drying and further heating and curing as necessary for each color to form pixels of each color.

The photosensitive resin composition is an essential material for flat display panel materials such as a color filter, a liquid crystal display (LCD), an organic light-emitting display (OLED), and a plasma display panel (PDP), and according to the composition of the photosensitive resin composition, the color filter The quality will be different. Conventionally, studies on photosensitive resin compositions have been conducted in the direction of improving colorants such as binder resins and pigments, photopolymerizable monomers, and the like, but these research directions are facing limitations in recent years. Accordingly, efforts have been made to improve the physical properties of the photosensitive resin composition by improving other compositions constituting the photosensitive resin composition, such as a photopolymerization initiator.

One embodiment is to provide a photosensitive resin composition advantageous for pattern formation by improving sensitivity and adhesion to a substrate.

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

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

Another embodiment is to provide a display device including the color filter.

One embodiment is (A) an acrylic binder resin; (B) photopolymerizable monomer; (C) photoinitiator; (D) a colorant and (E) a solvent, and the photopolymerization initiator includes a first photopolymerization initiator and a second photopolymerization initiator having different wavelengths at which the maximum absorption peak appears in a wavelength range of 300 nm to 400 nm, and the first photopolymerization The initiator provides a photosensitive resin composition having a shorter wavelength in which a maximum absorption peak appears in a wavelength range of 300 nm to 400 nm than the second photopolymerization initiator.

The first photopolymerization initiator may be included in an amount higher than that of the second photopolymerization initiator.

The content of the first photopolymerization initiator may be 10 to 15 times the content of the second photopolymerization initiator.

The first photopolymerization initiator may include an α-amino ketone compound.

The α-amino ketone compound may be represented by Formula 1-1 below.

[Formula 1-1]

In Formula 1-1,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group, R ³ is a substituted C6 to C20 aryl group, and L ¹ and L ² are each independently substituted or unsubstituted C1 to C20 alkyl Ren group, and X ¹ is O or S.

For example, R ¹ and R ² are each independently a substituted or unsubstituted C1 to C10 alkyl group, R ³ is a C6 to C20 aryl group substituted with a C1 to C10 thioalkyl group, and L ¹ and L ² are each independently It is a substituted or unsubstituted C1 to C10 alkylene group, and X ¹ may be O.

The first photopolymerization initiator may include a compound represented by Formula 1-2 below.

[Formula 1-2]

In Formula 1-2,

L ³ is a substituted or unsubstituted C1 to C10 alkylene group, R ⁴ is a substituted or unsubstituted C3 to C20 cycloalkyl group, R ⁵ is a substituted or unsubstituted C6 to C20 aryl group, and R ⁶ is C6 to It is a C6 to C20 aryl group substituted with a C20 thioaryl group.

The second photopolymerization initiator may include a compound represented by Formula 2-1 below.

[Formula 2-1]

In Formula 2-1,

R ⁷ and R ⁸ are each independently a substituted or unsubstituted C1 to C20 alkyl group, and X ² is O or S.

The second photopolymerization initiator may include a compound represented by Formula 2-2 below.

[Formula 2-2]

In Formula 2-2,

R ⁹ to R ¹¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group, R ¹² is a nitro group, L ⁴ is a substituted or unsubstituted C6 to C20 arylene group, and L ⁵ is a substituted or unsubstituted It is a C1 to C20 alkylene group.

The colorant may include a green pigment and a yellow pigment.

The photosensitive resin composition may include 1% to 10% by weight of the binder resin based on the total amount of the photosensitive resin composition; 5% to 20% by weight of the photopolymerizable monomer; 0.1% to 5% by weight of the photopolymerization initiator; It may include 20% to 50% by weight of the colorant and 30% to 60% by weight of the solvent.

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

Another embodiment provides a photosensitive resin film prepared by using the photosensitive resin composition.

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

Another embodiment provides a display device including the color filter.

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

The photosensitive resin composition according to an embodiment is advantageous in forming a pattern by improving sensitivity and adhesion to a substrate, and is useful in manufacturing a color filter.

1 is a graph showing absorbance according to wavelength of a compound represented by Chemical Formula 1A.
2 is a graph showing absorbance according to wavelength of a compound represented by Formula 1B.
3 is a graph showing absorbance according to wavelength of a compound represented by Chemical Formula 2A.
4 is a graph showing absorbance according to wavelength of a compound represented by Chemical Formula 2B.

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

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

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

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

In addition, unless otherwise specified in the specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" refers to "acrylic acid" and "methacrylic acid. "It means both are possible.

Unless otherwise specified in the specification, "combination" means mixing or copolymerization.

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

Unless otherwise specified in the specification, the maximum absorbance range means a range within a region of 300 nm to 400 nm, and a range of less than 300 nm and more than 400 nm is not considered.

In addition, unless otherwise specified in the specification, "*" means a moiety connected with the same or different atoms or chemical formulas.

The photosensitive resin composition according to an embodiment includes (A) an acrylic binder resin; (B) photopolymerizable monomer; (C) photoinitiator; (D) a colorant and (E) a solvent, and the photopolymerization initiator includes a first photopolymerization initiator and a second photopolymerization initiator having different wavelengths at which the maximum absorption peak appears in a wavelength range of 300 nm to 400 nm, and the first photopolymerization The initiator has a shorter wavelength at which the maximum absorption peak appears in a wavelength range of 300 nm to 400 nm than the second photopolymerization initiator.

The photosensitive resin composition used to prepare a photosensitive resin film in a conventional color filter was used by modifying a binder resin or a pigment in order to have excellent pattern properties. However, there is a problem in that there is a fundamental limitation in improving the patternability only by modifying the binder resin or pigment.

However, the photosensitive resin composition according to an embodiment includes a first photopolymerization initiator having a short maximum absorption peak in a wavelength range of 300 nm to 400 nm and a second photo polymerization initiator having a long maximum absorption peak in a wavelength range of 300 nm to 400 nm. By mixing and using, it is possible to improve the sensitivity and adhesion to the substrate without modifying the binder resin or pigment, thereby improving the pattern property.

Hereinafter, each component will be described in detail.

(C) Light polymerization Initiator

The photosensitive resin composition according to an embodiment is a mixture of a first photopolymerization initiator having a short wavelength having a maximum absorption peak in a wavelength range of 300 nm to 400 nm and a second photo polymerization initiator having a long wavelength having a maximum absorption peak in a wavelength range of 300 nm to 400 nm use. 1 and 2 are absorbance graphs according to wavelengths of compounds usable as a first photopolymerization initiator (compounds represented by Chemical Formulas 1A and 1B), and FIGS. 3 and 4 are a compound usable as a second photopolymerization initiator (Formula 2A). And it is an absorbance graph according to the wavelength of the compound represented by Chemical Formula 2B).As can be seen from FIGS. 1 to 4, the wavelength at which the maximum absorption peak of the compound usable as the first photopolymerization initiator appears is the wavelength that can be used as the second photopolymerization initiator. It is different from the wavelength at which the maximum absorption peak of the compound appears.

When the first photopolymerization initiator and the second photopolymerization initiator are used in combination, the first photopolymerization initiator may be included in an amount higher than that of the second photopolymerization initiator. When the first photopolymerization initiator is used in an amount equal to or less than that of the second photopolymerization initiator, the sensitivity may be lowered, which may be undesirable.

For example, the content of the first photopolymerization initiator may be 10 to 15 times the content of the second photopolymerization initiator. When the content of the first photopolymerization initiator is less than 10 times the content of the second photopolymerization initiator, the effect of improving the sensitivity is insignificant, and it is uneconomical when the content of the first photopolymerization initiator is included in an amount greater than 15 times the content of the second photopolymerization initiator.

The first photopolymerization initiator may include an α-amino ketone compound. In this case, the effect of improving the sensitivity may be more excellent.

For example, the α-amino ketone compound may be represented by Formula 1-1 below.

[Formula 1-1]

In Formula 1-1,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ³ is a substituted C6 to C20 aryl group,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,

X ¹ is O or S.

For example, in Formula 1-1, R ¹ and R ² are each independently a substituted or unsubstituted C1 to C10 alkyl group, R ³ is a C6 to C20 aryl group substituted with a C1 to C10 thioalkyl group, L ¹ And L ² are each independently a substituted or unsubstituted C1 to C10 alkylene group, and X ¹ may be O.

For example, the α-amino ketone compound represented by Formula 1-1 may be represented by Formula 1A below.

[Formula 1A]

The first photopolymerization initiator may include a compound represented by Formula 1-2 below together with the α-amino ketone compound or separately from the α-amino ketone compound. That is, the first photopolymerization initiator may include a compound represented by Formula 1-1, a compound represented by Formula 1-2, or a combination thereof.

[Formula 1-2]

In Formula 1-2,

L ³ is a substituted or unsubstituted C1 to C10 alkylene group,

R ⁴ is a substituted or unsubstituted C3 to C20 cycloalkyl group,

R ⁵ is a substituted or unsubstituted C6 to C20 aryl group,

R ⁶ is a C6 to C20 aryl group substituted with a C6 to C20 thioaryl group.

For example, the compound represented by Formula 1-2 may be represented by the following Formula 1B.

[Formula 1B]

The second photopolymerization initiator may include a compound represented by Formula 2-1 below.

[Formula 2-1]

In Formula 2-1,

R ⁷ and R ⁸ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

X ² is O or S.

For example, the compound represented by Formula 2-1 may be represented by Formula 2A below.

[Formula 2A]

The second photopolymerization initiator may include a compound represented by the following Formula 2-2 together with the compound represented by Formula 2-1 or separately from the compound represented by Formula 2-1. That is, the second photopolymerization initiator may include a compound represented by Formula 2-1, a compound represented by Formula 2-2, or a combination thereof.

[Formula 2-2]

In Formula 2-2,

R ⁹ to R ¹¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ¹² is a nitro group,

L ⁴ is a substituted or unsubstituted C6 to C20 arylene group,

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

For example, the compound represented by Formula 2-2 may be represented by Formula 2B.

[Formula 2B]

On the other hand, the photopolymerization initiator may further include a compound conventionally used, such as a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, an acetophenone compound, or a combination thereof.

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

Examples of the thioxanthone-based compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- And chloro thioxanthone.

Examples of the benzoin-based 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)-s-triazine, 2-(3',4' -Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine , 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4 -Bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, 2-[4 -(4-ethylphenyl)-phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, etc. are mentioned.

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

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt -Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

In addition to the above compounds, the photoinitiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or a fluorene compound.

The photopolymerization initiator may be used together with a photosensitizer that absorbs light and becomes excited, and then transmits the energy to cause a chemical reaction.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, etc. Can be mentioned.

The photopolymerization initiator may be included in an amount of 0.1% to 5% by weight, such as 0.1% to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure in the pattern formation process to obtain excellent reliability, excellent heat resistance, light resistance, and chemical resistance of the pattern, excellent resolution and adhesion, and an unreacted initiator It can prevent the decrease in transmittance due to.

(A) Acrylic binder resin

The photosensitive resin composition according to an embodiment includes an acrylic binder resin.

The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin comprising at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxy 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% to 50% by weight, such as 10% to 40% by weight, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethylether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; Vinyl cyanide compounds such as (meth)acrylonitrile; Unsaturated amide compounds such as (meth)acrylamide; And the like, and these may be used alone 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-hydroxyethyl meth Acrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in combination of two or more. have.

The weight average molecular weight of the acrylic binder resin may be 3,000 g/mol to 150,000 g/mol, such as 5,000 g/mol to 50,000 g/mol, such as 20,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the physical and chemical properties of the photosensitive resin composition are excellent, the viscosity is appropriate, and adhesion with the substrate is excellent when manufacturing a color filter.

The acid value of the acrylic binder resin may be 15 mgKOH/g to 60 mgKOH/g, such as 20 mgKOH/g to 50 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 acrylic binder resin may be included in an amount of 1% to 10% by weight, such as 1% to 5% by weight, based on the total amount of the photosensitive resin composition. When the acrylic binder resin is included within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern may be obtained.

(B) Photopolymerization Monomer

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

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization can occur during exposure in the pattern formation process to form a pattern having excellent heat resistance, light resistance and chemical resistance.

The photopolymerizable monomer is, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di ( Meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritoldi(meth)acrylate, penta Erythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropanetri (meth) Acrylate, tris(meth)acryloyloxyethylphosphate, novolacepoxy(meth)acrylate　, or a combination thereof.

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

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

The photopolymerizable monomer may be included in an amount of 5% to 20% by weight, such as 5% to 10% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, 　 is sufficiently cured during exposure in the pattern formation process, resulting in excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, and excellent resolution and adhesion.

(D) colorant

The colorant in the photosensitive resin composition according to an embodiment may include a green pigment and a yellow pigment.

The colorant in the photosensitive resin composition according to an embodiment may include a red pigment and/or a blue pigment.

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

The green pigment is C.I. in the Color Index. Green pigment 59, C.I. Green pigment 58, C.I. Green pigment 36, C.I. Halogen-substituted copper phthalocyanine pigments such as green pigment 7 and the like may be used, and these may be used alone or in combination of two or more, but are not limited thereto.

The blue pigment is C.I. in the Color Index. Blue pigment 15:6, C.I. Blue pigment 15:0, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I blue pigment 15:6, C.I. Blue pigment 16 may be used, and these may be used alone or in combination of two or more, but are not limited thereto.

The yellow pigment is C.I. in the Color Index. Isoindolin-based pigments such as yellow pigment 139, C.I. Quinophthalone pigments such as yellow pigment 138, C.I. Nickel complex pigments such as yellow pigment 150, C.I. Yellow pigment 100 may be used, and these may be used alone or in combination of two or more, but are not limited thereto.

When using a pigment as the colorant, a dispersant may be used together to disperse the pigment. Specifically, the pigment may be previously surface-treated with a dispersant, or may be used by adding a dispersant together with the pigment when preparing the composition.

Nonionic dispersants, anionic dispersants, cationic dispersants, and the like may be used as the dispersant. Specific examples of the dispersant include polyalkylene glycol and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonate, carboxylic acid ester, carboxylate , Alkyl amide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more.

For example, the commercially available products of the dispersant are BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from EFKA Chemical; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; Alternatively, there are PB711 and PB821 of Ajinomoto.

The 　 dispersant may be included in an amount of 0.1% to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is included within the above range, stability, developability, and patternability are excellent when preparing a black column spacer according to the excellent dispersibility of the composition.

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

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

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

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

The pigment that has undergone the kneading step may have an average particle diameter of 5 nm to 200 nm, such as 5 nm to 150 nm. When the average particle diameter of the pigment is within the above range, the stability in the pigment dispersion is excellent, and there is no fear of lowering the resolution of the pixel.

Specifically, the pigment may be used in the form of a pigment dispersion comprising 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 included in an amount of 5% to 20% by weight, such as 8% to 15% by weight, based on the total amount of the pigment dispersion.

The colorant may be included in an amount of 20% to 50% by weight, such as 30% to 40% by weight, based on the total amount of the photosensitive resin composition. When the colorant is included within the above range, the coloring effect and development performance are excellent.

(E) solvent

The solvent may be materials that have compatibility with the colorant, the photopolymerization initiator, the photopolymerizable monomer, and the acrylic binder resin, but do not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether (EDM); Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol 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-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactate esters such as methyl lactate and ethyl lactate; Oxyacetate alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, and ethyl ethoxy acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methylpropionic acid esters such as 2-oxy-2-methylpropionate methyl and 2-oxy-2-methylethylpropionate, 2-methoxy-2-methylpropionate methyl, 2-ethoxy-2- Monooxymonocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methylpropionic acid such as ethyl methylpropionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid And high boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, in consideration of compatibility and reactivity, ketones such as cyclohexanone are preferred; Glycol ethers such as 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 included in a balance, such as 30% to 60% by weight, such as 35% to 55% 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 processability is excellent in manufacturing a color filter.

(F) other additives

Meanwhile, the photosensitive resin composition may further include an additive of malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a fluorine-based 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 to the substrate.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, and γ-gly Cidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.

The silane-based 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-based coupling agent is included within the above range, adhesion and storage properties are excellent.

In addition, the photosensitive resin composition may further include a surfactant, such as a fluorine-based surfactant, to improve coating properties and prevent defects from being generated, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Mechapack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^{® of} Dai Nippon Ink & Chemicals Co., Ltd.; 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 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is ensured, stains do not occur, and wettability to an IZO substrate or a glass substrate is excellent.

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

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

A method of forming a pattern in the photosensitive resin film is as follows.

(1) Application and film formation step

After applying the photosensitive resin composition to a desired thickness on a substrate such as a glass substrate or an IZO substrate subjected to a predetermined pretreatment using a spin or slit coating method, a roll coating method, a screen printing method, or an applicator method, VCD A photosensitive resin film is formed by heating at 70° C. to 100° C. for 1 to 10 minutes through a process or the like to remove the solvent.

(2) exposure step

In order to form a pattern required for the obtained photosensitive resin film, a mask composed of a half tone portion to implement a black matrix pattern and a full tone portion to implement a column spacer pattern are interposed, and then active rays of 200 nm to 500 nm are irradiated. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, X-rays, electron beams, etc.

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

(3) development stage

As a developing method, after the exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, so that only the exposed portions remain to form a pattern.

(4) Post-processing step

There is a post-heating process for obtaining an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, and storage stability for the image pattern obtained by development in the above process.

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

Another embodiment provides a display device including the color filter.

The display device may be, for example, a liquid crystal display device (LCD).

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

( Example )

(Production of photosensitive resin composition)

Example 1 to Example 5, Comparative example 1 and Comparative example 2

In the composition shown in Table 1 below, two types of photopolymerization initiators were added to a solvent, and stirred at room temperature for 1 hour to dissolve. Then, a binder resin and a photopolymerizable monomer were added, and the mixture was stirred at room temperature for 1 hour. Here, other additives were added and stirred at room temperature for 1 hour. Here, after adding a colorant and stirring at room temperature for 2 hours, the solution was filtered three times to remove impurities, and the photosensitive resin according to Examples 1 to 5, Comparative Examples 1 and 2 The composition was prepared. Components used in the preparation of the photosensitive resin composition are as follows.

(A) Acrylic binder resin

Acrylic binder resin (SP-RY16, Showadenko company)

(B) Photopolymerization Monomer

DPHA(Nippon KAYAKU社)

(C) Light polymerization Initiator

(C-1) First photoinitiator: compound represented by formula 1A

[Formula 1A]

(C-2) First photoinitiator: compound represented by formula 1B

[Formula 1B]

(C-3) Second photoinitiator: compound represented by formula 2A

[Formula 2A]

(C-4) Second photoinitiator: compound represented by formula 2B

[Formula 2B]

(D) colorant

(D-1) C.I. pigment green 58 (ENF company)

(D-2) C.I. pigment yellow 138 (ENF company)

(E) solvent

Propylene glycol monomethyl ethyl acetate (PGMEA, sigma-aldrich company)

(G) other additives

Fluorine surfactant (F-554, DIC company)

(Unit: wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 (A) Acrylic binder resin 4.57 4.57 4.57 4.57 4.57 4.57 4.57 (B) photopolymerizable monomer 8.70 8.70 8.70 8.70 8.70 8.70 8.70 (C) photopolymerization initiator (C-1) 0.56 - 0.45 0.3 0.05 - - (C-2) - 0.56 - - - 0.61 - (C-3) 0.05 - 0.05 0.3 0.56 - - (C-4) - 0.05 - - - - 0.61 (D) colorant (D-1) 26.40 26.40 26.40 26.40 26.40 26.40 26.40 (D-2) 11.80 11.80 11.80 11.80 11.80 11.80 11.80 (E) solvent 47.90 47.90 48.01 47.91 47.90 47.90 47.90 (F) other additives 0.02 0.02 0.02 0.02 0.02 0.02 0.02

Evaluation 1: Pattern And adhesion evaluation

The photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were coated using a MIKASA coating machine at an rpm capable of exhibiting a constant thickness for each specimen, and then a 90°C hot plate Pre-baking was performed at, and pattern exposure was performed under the exposure conditions of Dose: 40mJ and Gap: 200µm in the exposure machine, and development to display the pattern was performed. The developer was used by diluting a Na ₂ CO ₃ solution, and the time (second) (BP) of the pattern appearance was measured. At this time, the BP should be at least 40 seconds or less. Pattern formation was completed by baking the pattern substrate on which development was completed at 230° C. for 20 minutes. The completed pattern was zoomed 500 times through an optical microscope to measure the width of the confirmed pattern. The pattern to be confirmed was carried out by measuring the size with an optical microscope at 100 μm wide, and the results are shown in Table 2 below. In Table 2, peeling refers to the number of portions from which the pattern has been torn off, as determined through an optical microscope.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 CD(㎛) 104.2 103.8 103.1 108.4 110.8 102.5 112.8 peeling (pcs) One 3 3 5 6 8 20

Evaluation 2: Sensitivity evaluation

The photosensitive resin composition according to Examples 1 to 5, Comparative Example 1 and Comparative Example 2 was applied to 10cm*10cm ITO glass (resistance 30Ω), heated on a hot plate at 100°C for 1 minute in proxy type, and then again A 1.2 µm-thick photosensitive resin film was formed by heating in contact type for 1 minute. After exposing the substrate coated with the photosensitive resin film with a varying amount of exposure with an exposure machine (UX-1200SM-AKS02 of Ushio) using masks with patterns of various sizes, 2.38% TMAH solution (aqueous developer) at room temperature ) To dissolve and remove the exposed portion, and then washed with pure water for 50 seconds to form a pattern.

Sensitivity was evaluated by checking the energy at which a 20 μm pattern was implemented based on the pattern size measured using the MX51T-N633MU of Olympus, and the results are shown in Table 3 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Sensitivity (mJ/cm ² ) 30 30 40 30 30 60 50

Through the Tables 2 and 3, when the first photopolymerization initiator and the second photopolymerization initiator having different wavelengths at which the maximum absorption peak appears in the wavelength range of 300nm to 400nm are mixed, the first photopolymerization initiator and the second photopolymerization initiator It can be seen that the patternability and sensitivity are better than when used alone. Furthermore, the more the content of the first photopolymerization initiator having a short wavelength at which the maximum absorption peak appears in the wavelength range of 300 nm to 400 nm is greater than the content of the second photo polymerization initiator having a long wavelength at which the maximum absorption peak appears in the wavelength range of 300 nm to 400 nm, As a result, it can be seen that when the content of the first photopolymerization initiator is 10 times or more of the content of the second photopolymerization initiator, the effect of simultaneously improving patternability and sensitivity can be maximized.

The present invention is not limited to the above embodiments, but may be manufactured in a variety of different forms, and those of ordinary skill in the art to which the present invention pertains may It will be appreciated that it can be implemented with. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting.

Claims (15)

(A) acrylic binder resin;
(B) photopolymerizable monomer;
(C) photoinitiator;
(D) a colorant and
(E) solvent
Including,
The photopolymerization initiator is composed of a first photopolymerization initiator and a second photopolymerization initiator having different wavelengths at which the maximum absorption peak appears in a wavelength range of 300nm to 400nm,
The first photopolymerization initiator has a shorter wavelength at which the maximum absorption peak appears in a wavelength range of 300 nm to 400 nm than the second photopolymerization initiator,
The first photopolymerization initiator is included in an amount higher than that of the second photopolymerization initiator,
The second photopolymerization initiator is represented by the following formula 2-2,
A photosensitive resin composition in which the content of the first photopolymerization initiator is 10 to 15 times the content of the second photopolymerization initiator:
[Formula 2-2]

In Formula 2-2,
R ⁹ to R ¹¹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,
R ¹² is a nitro group,
L ⁴ is a substituted or unsubstituted C6 to C20 arylene group,
L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group.
delete delete The method of claim 1,
The first photopolymerization initiator is a photosensitive resin composition containing an α-amino ketone compound.
The method of claim 4,
The α-amino ketone compound is a photosensitive resin composition represented by the following formula 1-1:
[Formula 1-1]

In Formula 1-1,
R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group,
R ³ is a substituted C6 to C20 aryl group,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,
X ¹ is O or S.
The method of claim 5,
R ¹ and R ² are each independently a substituted or unsubstituted C1 to C10 alkyl group,
R ³ is a C6 to C20 aryl group substituted with a C1 to C10 thioalkyl group,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C10 alkylene group,
X ¹ is O photosensitive resin composition.
The method of claim 1,
The first photopolymerization initiator is a photosensitive resin composition comprising a compound represented by the following formula 1-2:
[Formula 1-2]

In Formula 1-2,
L ³ is a substituted or unsubstituted C1 to C10 alkylene group,
R ⁴ is a substituted or unsubstituted C3 to C20 cycloalkyl group,
R ⁵ is a substituted or unsubstituted C6 to C20 aryl group,
R ⁶ is a C6 to C20 aryl group substituted with a C6 to C20 thioaryl group.
delete delete The method of claim 1,
The colorant photosensitive resin composition comprising a green pigment and a yellow pigment.
The method of claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition
1% to 10% by weight of the binder resin;
5% to 20% by weight of the photopolymerizable monomer;
0.1% to 5% by weight of the photopolymerization initiator;
20% to 50% by weight of the colorant and
30% to 60% by weight of the solvent
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition further comprises an additive of malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.
A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1, 4 to 7, and 10 to 12.
A color filter comprising the photosensitive resin film of claim 13.
A display device comprising the color filter of claim 14.

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