KR20110079198A - Photosensitive resin composition for color filter - Google Patents

Abstract

PURPOSE: A photo-sensitive resin composition for a color filter is provided to obtain the desired brightness and the contrast ratio using the mixture of cyanine-based violet-color dye and cyanine-based blue color dye with the specific chemical formulas. CONSTITUTION: A photo-sensitive resin composition for a color filter includes a cyanine-based violet-color dye, cyanine-based blue color dye, an alkaline soluble resin, a photo-polymerizable monomer, a photo-polymerizable initiator, and a solvent. The cyanine-based violet-color dye is represented by chemical formula 1, and the cyanine-based blue color dye is represented by chemical formula 2. In the chemical formula 1 and the chemical formula 2, the A, the A', the B, and the B' are a substituted or non-substituted benzene ring or a substituted or non-substituted alpha type or beta type naphthalene ring. The L1 and the L2 is alkenylene group containing one or more conjugated double bonds.

Description

Photosensitive resin composition for color filters {PHOTOSENSITIVE RESIN COMPOSITION FOR COLOR FILTER}

This substrate relates to the photosensitive resin composition for color filters.

The liquid crystal display device, which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption, and excellent bonding with an integrated circuit, and thus its use range is expanding for notebook computers, monitors, and TV images. The liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, an active circuit unit consisting of a liquid crystal layer, a thin film transistor, and a capacitor capacitor layer, and an upper substrate on which an ITO pixel electrode is formed. The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to shield boundaries between pixels, and a plurality of colors (typically red (R), green (G), and blue () to form each pixel. The three primary colors of B)) are arranged in such a manner that the pixel parts are arranged in order.

One of the methods for implementing color filters, the pigment dispersion method is to coat a photosensitive resin composition comprising a colorant and an alkali-soluble resin, a photopolymerization monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives on a transparent substrate provided with a black matrix. After the exposure of the pattern of the shape to be formed, a method of forming a colored thin film by repeating a series of processes to remove the non-exposed areas with a solvent and thermally cured, to manufacture LCDs of mobile phones, laptops, monitors, TVs, etc. It is actively applied. However, in recent years, even in the photosensitive resin composition for color filters using a pigment dispersion method having various advantages, not only excellent pattern characteristics but also high color reproducibility and improved performance such as high brightness and high contrast ratio are required.

An image sensor refers to a component of an image pickup device that generates an image from a mobile phone camera or a digital still camera (DSC). The image sensor is largely a charge coupled device (CCD) according to a manufacturing process and an application method thereof. The image sensor may be classified into a complementary metal oxide semiconductor (CMOS) image sensor. Color imaging devices used in solid-state imaging devices or complementary metal oxide semiconductor image sensors, etc., have filter segments of red, green, and blue additive mixed primary colors on the light receiving devices. It is common to install color filters separately and to separate them. The pattern size of the color filter mounted on the color image pickup device is 2 μm or less, which is 1/100 to 1/200 times of the color filter pattern for existing LCDs. Accordingly, the increase in resolution and the reduction of residues are important factors that determine the performance of the device.

In the color filter made of the pigment type photosensitive resin composition, there is a limit of brightness and contrast ratio due to the pigment particle size. In addition, in the case of a color imaging device for an image sensor, a smaller dispersion particle size is required for forming a fine pattern. In response to such a demand, there has been an attempt to implement a color filter having improved brightness and contrast ratio by preparing a photosensitive resin composition suitable for dyes by introducing a dye that does not form particles instead of a pigment (Patent Publication No. 1999-0007097, Patent Publication No. 2002-0015650, and Patent Publication No. 2005-0020653.

Cyanine compounds are known to have good solubility and excellent light resistance, and are mainly used for optical filters for image display devices, optical recording materials using laser light, and the like. The cyanine-based compound can adjust the spectral characteristics relatively freely by adjusting the intramolecular conjugation length, and by controlling various functional groups such as alkyl, allyl, organometallic, etc. at the terminals, the physical properties such as spectral properties and solubility can be controlled. In addition, it is possible to control heat resistance, chemical resistance and the like by variously changing the type of counter ion. Therefore, the cyanine-based compound has a wide candidate group for selecting a dye showing the desired performance.

Accordingly, in the present invention, when selecting a dye, the color of the color filter expressed by colorizing the selected dye is represented by color coordinates according to sRGB (Standard Red Green Blue), NTSC (National Television System Committee), and EBU (Europien Broadcasting Union) By providing a suitable spectral characteristics within the conditions, and having a high brightness and high contrast ratio performance in the desired color coordinates, by preparing a photosensitive resin composition suitable for the selected dyes, blue for LCD and image sensors showing a high brightness and high contrast performance in the desired color coordinates We want to implement a color filter.

The present invention is to provide a photosensitive resin composition that can implement a color filter with improved brightness and contrast ratio.

This invention also provides the color filter containing the pixel layer manufactured using the said photosensitive resin composition.

According to one embodiment of the invention (A) a mixture of a cyanine-based purple dye of formula (1) and a cyanine-blue dye of formula (2), (B) alkali-soluble resin, (C) photopolymerization monomer, (D) photopolymerization initiator, and (E) It provides the photosensitive resin composition containing a solvent.

[Formula 1]

[Formula 2]

(In Chemical Formulas 1 and 2,

A, A ', B and B' are the same or different from each other, each independently represent a substituted or unsubstituted benzene ring, or a substituted or unsubstituted alpha or beta type naphthalene ring,

L ₁ and L ₂ are the same or different from each other, and each independently an alkenylene group including one or more conjugated double bonds,

R ₁ to R ₆ and R ₁ ′ to R ₆ ′ are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group and a substituted or unsubstituted aryl group Selected,

X and Z are each independently selected from the group consisting of halogen anions, perhalogenate anions, fluoro complex anions, alkyl sulfate anions and sulfonate anions,

m is an integer of 1 to 3, n is an integer of 2 to 4).

In the cyanine-based violet dye of Formula 1 and the cyanine-based blue dye of Formula 2, L ₁ and L ₂ are the same or different from each other, and each independently represented by the following Formula A or B, m = 2, n = 3

[Formula A]

(In Formula A, Y is selected from the group consisting of hydrogen, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group.)

[Formula B]

　

(In Formula B, R ₇ and R ₈ are the same or different from each other, and each independently hydrogen, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group and a substituted or unsubstituted aryl And Y is selected from the group consisting of hydrogen, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group.)

The purple dye has a solubility of 1 to 5% by weight with respect to propylene glycol monomethylether acetate or cyclohexanone, and has a transmittance of 20% or less in the region of 530 to 580 nm in terms of spectral characteristics and 430 to 470 at a color concentration. The transmittance in the nm region may be 70% or more.

The purple dye may be a compound of Formula 3 below.

(3)

The blue dye has a solubility of 1 to 5% by weight with respect to propylene glycol monomethylether acetate or cyclohexanone, has a transmittance of 10% or less in the range of 580 to 630 nm in terms of spectral characteristics, and 450 to 490 nm at a color concentration. The transmittance of the region may be at least 70%.

The blue dye may be a compound of Formula 4 or 5 below.

[Formula 4]

[Chemical Formula 5]

The blue dye and purple dye may be included in a weight ratio of 4: 1 to 1: 1.

The mixture of the violet dye and the blue dye may be included in an amount of 0.1 to 20% by weight based on the total weight of the photosensitive resin composition.

According to another embodiment of the present invention, a color filter including a pixel layer formed using the photosensitive resin composition is provided.

Other specific details of embodiments of the present invention are included in the following detailed description.

By using the photosensitive resin composition for color filters according to the present invention it is possible to implement a color filter with improved brightness and contrast ratio.

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

Conventionally, a mixture of a phthalocyanine-based blue and a dioxazine-based purple pigment having a crystalline form was mainly used as a blue pigment. However, since the pigment is not dissolved in the solvent used in the photosensitive resin composition, even when fine dispersion is performed, a decrease in contrast ratio resulting from the pigment particles is caused. In addition, when the pigment is added so that light transmission in the green region is suppressed, there is a problem that the light transmission in the target blue region is also suppressed and the brightness is lowered.

On the other hand, the present invention can implement a color filter having improved luminance and contrast ratio by using the cyanine dye having the above spectral characteristics and excellent solubility in place of conventional blue and purple pigments.

That is, the photosensitive resin composition for color filters according to the embodiment of the present invention, (A) a mixture of the cyanine-based purple dye of the formula (1) and the cyanine-based blue dye of the formula (2), (B) alkali-soluble resin, (C) Photopolymerization monomer, (D) photoinitiator, and (E) solvent. In addition, the photosensitive resin composition may further include (F) other additives.

[Formula 1]

[Formula 2]

(In Chemical Formulas 1 and 2,

A, A ', B and B' are the same or different from each other, each independently represent a substituted or unsubstituted benzene ring, or a substituted or unsubstituted alpha or beta type naphthalene ring,

L ₁ and L ₂ are the same or different from each other, and each independently an alkenylene group including one or more conjugated double bonds,

R ₁ to R ₆ and R ₁ ′ to R ₆ ′ are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group and a substituted or unsubstituted aryl group Selected,

X and Z are each independently selected from the group consisting of halogen anions, perhalogenate anions, fluoro complex anions, alkyl sulfate anions and sulfonate anions,

m is an integer of 1 to 3, n is an integer of 2 to 4).

In this specification, unless specified otherwise, "substituted" means that at least one hydrogen of the compound is substituted with a substituent selected from the group consisting of halogen, alkyl group, cycloalkyl group, aryl group, alkoxy group, amino group and alkenyl group. do.

In the present specification, unless otherwise specified, "alkyl group" means an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and "cycloalkyl group" means a cycloalkyl group having 3 to 30 carbon atoms. Means, more preferably a cycloalkyl group having 3 to 18 carbon atoms, and an "alkoxy group" means an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 18 carbon atoms, and "aryl Group ”means an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, and“ alkenyl group ”means an alkenyl group having 2 to 30 carbon atoms, and more preferably 2 to 30 carbon atoms. An alkenyl group of 18 is used, and an "alkenylene group" means an alkenylene group having 2 to 30 carbon atoms, and more preferably an alkenylene group having 2 to 18 carbon atoms.

Hereinafter, each component of the photosensitive resin composition according to one embodiment of the present invention will be described in detail.

(A) dye

Dyes usable in the present invention include a mixture of a cyanine-based purple dye of formula (1) and a cyanine-based blue dye of formula (2).

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

A, A ', B and B' are the same or different from each other, each independently represent a substituted or unsubstituted benzene ring, or a substituted or unsubstituted alpha or beta type naphthalene ring,

R ₁ to R ₆ and R ₁ ′ to R ₆ ′ are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group and a substituted or unsubstituted aryl group Selected from hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an aryl group having 6 to 30 carbon atoms,

X and Z are each independently halogen anions such as chlorine anion, bromine anion, iodine anion and fluorine anion; Perhaloacid anions such as perchlorate anion, perbromate anion and periodate anion; Fluoro complex anions such as boron tetrafluoride anion, antimony hexafluoride anion and phosphorus hexafluoride anion; Alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; And sulfonate anions such as p-toluene sulfonate anion and p-chlorobenzene sulfonate anion,

m is an integer from 1 to 3, n is an integer from 2 to 4,

L ₁ and L ₂ are the same or different from each other, and each independently an alkenylene group including one or more conjugated double bonds, and may preferably be represented by the following Formula A or B.

[Formula A]

In Formula A, Y is selected from the group consisting of hydrogen, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group, preferably hydrogen, a halogen atom, a cyano group, 1 to 8 carbon atoms Alkyl groups and aryl groups having 6 to 30 carbon atoms.

[Formula B]

R ₇ and R ₈ in Formula B are the same or different from each other, and each independently hydrogen, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group and a substituted or unsubstituted aryl group Selected from the group, preferably selected from the group consisting of hydrogen, a halogen atom, a cyano group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an aryl group having 6 to 30 carbon atoms,

Y is selected from the group consisting of hydrogen, a halogen atom, a cyano group, a substituted or unsubstituted “alkyl group” and a “substituted or unsubstituted” aryl group, and preferably hydrogen, a halogen atom, a cyano group, an alkyl group having 1 to 8 carbon atoms and 6 carbon atoms. To 30 aryl groups.

Preferably, the purple dye has a carbon number of 3 to form a conjugated double bond of L ₁ , and is used for propylene glycol monomethyl ether acetate (PGMEA) or cyclohexanone (Anon). A dye having a solubility of 1 to 5% by weight, having a transmittance of 20% or less in the 530 to 580 nm region in terms of spectral characteristics, and a transmittance of 70% or more in the region of 430 to 470 nm in color saturation is preferable. Do. As a specific example, a purple color dye (CYD1006) of Chemical Formula 3 may be mentioned.

(3)

　

The blue dye has a carbon number of 5 to form a conjugated double bond of L ₂ , a solubility of 1 to 5% by weight with respect to PGMEA or Anon, and a transmittance of 10% in the range of 580 to 630 nm in terms of spectral characteristics. Below, the transmittance in the 450 to 490 nm region at a color concentration of 70% or more may be obtained excellent color characteristics. Specific examples thereof include blue color dyes (CYD 1014 and CY 680P) represented by Chemical Formulas 4 and 5.

[Formula 4]

　

[Chemical Formula 5]

The blue dye and the purple dye are preferably used in a weight ratio of 4: 1 to 1: 1.

The dye is included in an amount of 0.1 to 20% by weight based on the total weight of the photosensitive resin composition, and more preferably in the range of 1 to 10% by weight. When included in the above content range, it is possible to manufacture a pattern having excellent color reproducibility and color discrimination, and excellent light resistance and heat resistance.

(B) alkali soluble resin

The alkali-soluble resin is a carboxyl group-containing acrylic binder resin, which is a copolymer of a first ethylenically unsaturated monomer having one or more carboxyl groups and a second ethylenically unsaturated monomer copolymerizable therewith.

Examples of the first ethylenically unsaturated monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and the like, and the alkali-soluble resin includes at least one monomer thereof.

The first ethylenically unsaturated monomer may be included in 10 to 40% by weight based on the total weight of the alkali-soluble resin, preferably from 20 to 30% by weight. When included within the above content range, the acrylic binder resin has a suitable acid value, which is preferable because the developability of the alkaline developer can be improved and the dye dispersion can be stabilized.

Examples of the second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer include unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid amino alkyl ester compounds, carboxylic acid vinyl ester compounds, and unsaturated carboxylic acid glycidyl esters. A compound, a vinyl cyanide compound, an unsaturated amide compound, etc. are mentioned.

Specific examples of the unsaturated carboxylic acid ester compounds include styrene, α-methyl styrene, vinyltoluene, vinyl benzyl methyl ether, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl meta Acrylate, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyl acrylate, 2-hydroxy butyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate Cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate and the like; Specific examples of the unsaturated carboxylic acid amino alkyl ester compounds include 2-amino ethyl acrylate, 2-amino ethyl methacrylate, 2-dimethyl amino ethyl acrylate, 2-dimethyl amino ethyl methacrylate, and the like; Specific examples of the carboxylic acid vinyl ester compounds include vinyl acetate, vinyl benzoate, and the like; Specific examples of the unsaturated carboxylic acid glycidyl ester compound include glycidyl acrylate, glycidyl methacrylate, and the like; Specific examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the like; Specific examples of the unsaturated amide compounds include acryl amide, methacryl amide, and the like, but are not limited thereto. Moreover, the said alkali-soluble resin contains 1 or more types of the above-mentioned 2nd ethylenically unsaturated monomer.

Specific examples of the alkali-soluble resin include methacrylic acid / methyl methacrylate copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl Methacrylate / 2-hydroxy ethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxy ethyl methacrylate copolymer, and the like. It can mix and use on paper.

It is preferable that the said alkali-soluble resin has a weight average molecular weight (Mw) of 10,000-70,000, and it is more preferable to have a weight average molecular weight (Mw) of 20,000-50,000. It is preferable to obtain a high resolution pixel within the above range.

Moreover, it is preferable that it is 10-120 KOH mg / g, and, as for the acid value of the said alkali-soluble resin, it is more preferable that it is 90-120 KOH mg / g. Within the above range, the strength of the pattern forming portion can be sufficiently realized, and there is an advantage in that the developability of the non-exposed portion with respect to the alkaline developer is excellent.

The alkali-soluble resin is preferably included in 0.5 to 30% by weight based on the total weight of the photosensitive resin composition. When included in the content as described above, the development with respect to the alkaline developer is good, and exhibits excellent crosslinkability, thereby making it possible to manufacture a pixel layer having a low surface roughness.

(C) photopolymerizable monomer

As said photopolymerizable monomer, the acryl-type photopolymerizable monomer generally used for the photosensitive resin composition for color filters can be used. Specific examples include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, penta Erythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate , Trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanedioldi Methacrylate, 1, 6-hexanediol dimethacrylate, etc. are mentioned, One kind of these can be used singly or in combination of two or more kinds.

The photopolymerizable monomer is preferably included in 0.5 to 30% by weight based on the total weight of the photosensitive resin composition. When included in the amount as described above, exhibits excellent developability with respect to alkaline developer.

(D) photoinitiator

As said photoinitiator, the photoinitiator generally used for the photosensitive resin composition can be used. Specific examples thereof include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, and the like.

Specific examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylproriophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxycetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.

Specific examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-meth Oxybenzophenone, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4'-bis (diethyl amino) benzophenone, etc. are mentioned. have.

Specific examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2 -Chloro thioxanthone, etc. are mentioned.

Specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.

Specific examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4 '-Dimethoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-tri Azine, 2- (p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-tri Azine 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4 , 6-bis (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2,4-trichloro And methyl (piperonyl) -6-triazine, 2,4-trichloro methyl (4'-methoxy styryl) -6-triazine and the like.

In addition to the photoinitiators exemplified above, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, biimidazole compounds and the like can also be used as the photopolymerization initiator.

More preferably 2-piperoniro-4,6-bis (trichloromethyl) -1,3,5-triazine (TPP), 2- [4- (4-ethylphenyl) phenyl] -4,6 -Bis (trichloromethyl) -1,3,5-triazine (STR-2BP), 2- (2-methoxyphenyl) ethylene-4,6-bis (trichloromethyl) -1,3,5- It is preferable to use triazine (TOMS), 2- (4-methoxyphenyl) ethylene-4,6-bis (trichloromethyl) -1,3,5-triazine (TPMS) and mixtures thereof.

The photopolymerization initiator as described above is preferably included in 0.1 to 10% by weight based on the total weight of the photosensitive resin composition. When the photopolymerization initiator is included within the content range, sufficient photopolymerization may occur during exposure in the pattern forming process, and the unreacted initiator remaining after the photopolymerization is preferable because there is no fear of lowering the transmittance.

(E) solvent

As the solvent, one having compatibility with the alkali-soluble resin (A) but not reacting is preferable.

As the solvent, esters, ethers, alcohols, ketones, combinations thereof and the like can be used. Specific examples of the ester solvent include ethylene glycol acetate, ethyl-3-ethoxy propionate, propylene glycol methyl ether acetate, and the like, and specific examples of the ether solvent include ethyl cellosolve and propylene glycol methyl. Ether, and the like, and specific examples of the alcohol solvent include polyethylene glycol, and the like, and specific examples of the ketone solvent include cyclohexanone and the like.

The solvent may be used in the remainder in the photosensitive resin composition, and preferably may be included in 20 to 90% by weight. Within the said range, since the applicability | paintability of the photosensitive resin composition is excellent and flatness can be maintained in the film | membrane of 1 micrometer or more in thickness, it is preferable.

(F) other additives

The photosensitive resin composition according to an embodiment of the present invention, together with the components of the above (A) to (E), to prevent the generation of residues due to staining, spot formation prevention, leveling control, or non-development during coating Other additives such as a surfactant may be further included.

By the surfactant such as the BM Chemie Co. ^{BM-1000 ® BM-1100 ®} ; Mega Pack F142D ^® Mega Pack F172 ^® Mega Pack F173 ^® Mega Pack F183 ^® manufactured by Dai Nippon Ink Chemical Co., Ltd .; Florad FC-135 ^® Florad FC-170C ^® Florad FC-430 ^® Florad FC-431 ^®, etc. manufactured by Sumitomo 3M Corporation; Asahi Glass Co., Ltd. Suplon S-112 ^® Suplon S-113 ^® Suplon S-131 ^® Suplon S-141 ^® Suplon S-145 ^® Suplon S-382 ^® Suplon SC-101 ^® Supple Ron SC-102 ^® Suflon SC-103 ^® Suflon SC-104 ^® Suflon SC-105 ^® Suflon SC-106 ^® etc; F-Top EF301 ^® F-Top EF303 ^® F-Top EF352 ^{® manufactured} by Shinsei Kasei Co., Ltd .; A commercially available product such as SH-28PA ^® SH-190 ^® SH-193 ^® SZ-6032 ^® SF-8428 ^® manufactured by Toray Silicone Co., Ltd. may be used.

In addition, the photosensitive resin composition may further include additives such as an adhesion aid, a preservation stabilizer and a heat resistance improver, as necessary, within a range that does not impair the object of the present invention.

According to another embodiment of the present invention provides a color filter including a pixel layer manufactured using the photosensitive resin composition having the above configuration.

The color filter is coated with a photosensitive resin composition having the above structure on a wafer with a thickness of 0.5 to 1 μm using a suitable method such as spin coating or slit coating on a wafer as a substrate, and colored with respect to the applied photosensitive resin composition layer. Irradiating light to form a pattern required for the filter, and then treating the coating layer with an alkaline developer to form a color filter having a pattern necessary for the color filter by dissolving a non-exposed portion of the coating layer. Can be.

In this case, the substrate preferably includes silicon oxide (SiO ₂ ) or silicon nitride (SiN _x ), and as a light source used in the irradiation process, I-line light of 365 nm may be used. By repeating the above procedure according to the required number of R, G, and B colors, a color filter having a desired pattern can be obtained.

In addition, in the manufacturing process as described above, crack resistance, solvent resistance, and the like can be further improved by reheating the image pattern obtained by development or curing by actinic radiation.

As described above, the color filter manufactured by the photosensitive resin composition according to the present invention may exhibit high resolution when applied to an image sensor.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only preferred examples of the present invention, and the present invention is not limited to the following Examples.

≪ Example 1 >

To the blending ingredients and contents shown in Table 1 below to prepare a photosensitive resin composition.

TABLE 1

Blended raw materials content
(weight%) coloring agent Blue toning dye
(CYD 1014, manufactured by St-Jean Photochemicals Inc.) 1.6 Purple toning dye
(CYD 1006, manufactured by St-Jean Photochemicals Inc.) 1.1 Alkali soluble resin (A) / (B) = 15/85 (w / w), molecular weight (Mw) = 22,000
(A): methacrylic acid
(B): benzyl methacrylate 3.3 Photopolymerization monomer Dipentaerythritol hexaacrylate (DPHA) 7.7 Photopolymerization initiator 1,2-octanedione 0.8 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one 0.5 Fluorine
Surfactants F-475 (DIC Corporation) 0.02 solvent Cyclohexanone 80.05 PGMEA 4.93

<Example 2>

A photosensitive resin composition was prepared in the same manner as in Example 1 except that 1.35% by weight of a blue color dye and a violet color dye were used.

<Example 3>

To the blending ingredients and contents shown in Table 2 below to prepare a photosensitive resin composition.

TABLE 2

Blended raw materials content
(weight%) coloring agent Blue toning dye
(CY 680P, manufactured by St-Jean Photochemicals Inc.) 1.7 Purple toning dye
(CYD1006, manufactured by St-Jean Photochemicals Inc.) 1.2 Alkali soluble resin (A) / (B) = 15/85 (w / w), molecular weight (Mw) = 22,000
(A): methacrylic acid
(B): benzyl methacrylate 3.5 Photopolymerization monomer Dipentaerythritol hexaacrylate (DPHA) 8.2 Photopolymerization initiator 1,2-octanedione 0.8 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one 0.5 Fluorine
Surfactants F-475 (product made by DIC Corporation) 0.02 solvent Cyclohexanone 79.04 PGMEA 5.04

<Example 4>

A photosensitive resin composition was prepared in the same manner as in Example 3, except that 1.45 wt% of a blue crude dye and a violet crude dye were used.

Comparative Example 1

To the blending ingredients and contents shown in Table 3 below to prepare a photosensitive resin composition.

[Table 3]

Blended raw materials content
(weight%) coloring agent Blue tone pigment (C.I. Pigment Blue 15: 6) 1.6 Purple Toning Pigment (C.I. Pigment Violet 23) 1.1 Alkali soluble resin (A) / (B) = 15/85 (w / w), molecular weight (Mw) = 22,000
(A): methacrylic acid
(B): benzyl methacrylate 3.3 Photopolymerization monomer Dipentaerythritol hexaacrylate (DPHA) 7.7 Photopolymerization initiator 1,2-octanedione 0.8 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one 0.5 Fluorinated Surfactant F-475 (DIC Corporation) 0.02 solvent Cyclohexanone 80.05 PGMEA 4.93

<Property evaluation>

The photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Example 1 were each coated on a glass substrate having a thickness of 1 mm degreased and washed, and dried on a hotplate at 90 ° C. for 2 minutes. A coating film was obtained. Subsequently, the coating film was exposed to light using a high pressure mercury lamp having a wavelength of 365 nm, and then dried in a hot air circulation drying furnace at 160 ° C. for 20 minutes to form a pixel layer.

Color coordinates (x, y) and luminance (Y) were measured using a spectrophotometer (MCPD3000, manufactured by Otsuka electronic) on the manufactured pixel layer, and a polarizing plate using a contrast tester CT-1 (manufactured by Tsubosaka, Inc.). After measuring the amount of light at the time of closing and opening, the contrast ratio was calculated according to the following equation (1). The results are shown in Table 4 below.

[Equation 1]

Contrast ratio = L _Open / L _Close

[Table 4]

x y Y C / R Example 1 0.138

0.085 9.9 13500 Example 2 0.139 9.9 12700 Example 3 0.139 9.3 13400 Example 4 0.139 9.5 12200 Comparative Example 1 0.149 9.3 8300

As shown in Table 4, the pixel layer made of the photosensitive resin composition of Examples 1 to 4 according to the present invention comprising a mixture of blue and purple dyes is the photosensitive of Comparative Example 1 comprising a pigment mixture of blue and purple Compared with the pixel layer made of the resin composition, excellent luminance characteristics and contrast ratios were shown.

The present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. Do.

Claims (9)

(A) a mixture of a cyanine violet dye of formula (1) and a cyanine blue dye of formula (2), (B) alkali soluble resin, (C) photopolymerization monomer, (D) photoinitiator and (E) solvent Photosensitive resin composition for color filters comprising a. [Formula 1]

[Formula 2]

(In Chemical Formulas 1 and 2, A, A ', B and B' are the same or different from each other, each independently represent a substituted or unsubstituted benzene ring, or a substituted or unsubstituted alpha or beta type naphthalene ring, L ₁ and L ₂ are the same or different from each other, and each independently an alkenylene group including one or more conjugated double bonds, R ₁ to R ₆ and R ₁ ′ to R ₆ ′ are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group and a substituted or unsubstituted aryl group Selected, X and Z are each independently selected from the group consisting of halogen anions, perhalogenate anions, fluoro complex anions, alkyl sulfate anions and sulfonate anions, m is an integer of 1 to 3, n is an integer of 2 to 4). The method of claim 1, The L ₁ and L ₂ are the same or different from each other, and each independently represented by the formula A or B, m = 2, n = 3 photosensitive resin composition for a color filter. [Formula A] 　

(In Formula A, Y is selected from the group consisting of hydrogen, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group.) [Formula B] 　

(In Formula B, R ₇ and R ₈ are the same or different from each other, and each independently hydrogen, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group and a substituted or unsubstituted aryl And Y is selected from the group consisting of hydrogen, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group.) The method of claim 1, The violet dye has a solubility of 1 to 5% by weight with respect to propylene glycol monomethylether acetate or cyclohexanone, transmittance in the region of 530 to 580 nm in terms of spectral characteristics is 20% or less, and 430 to 470 at color concentration The photosensitive resin composition for color filters whose transmittance | permeability in a nm area is 70% or more. The method of claim 1, The photosensitive resin composition for color filters, wherein the purple dye is a compound of Formula 3 below. (3)

The method of claim 1, The blue dye has a solubility of 1 to 5% by weight with respect to propylene glycol monomethylether acetate or cyclohexanone, has a transmittance of 10% or less in the range of 580 to 630 nm in terms of spectral characteristics, and 450 to 490 nm at a color concentration. The photosensitive resin composition for color filters whose transmittance | permeability of an area | region is 70% or more. The method of claim 1, The photosensitive resin composition for color filters in which the said blue dye is a compound of following General formula (4) or (5). [Formula 4]

[Chemical Formula 5]

The method of claim 1, The blue dye and the purple dye is a photosensitive resin composition for a color filter is included in a weight ratio of 4: 1 to 1: 1. The method of claim 1, The mixture of the violet dye and the blue dye is a photosensitive resin composition for a color filter is contained in 0.1 to 20% by weight based on the total weight of the photosensitive resin composition. The color filter containing the pixel layer formed using the photosensitive resin composition of any one of Claims 1-8.