KR20140135589A - Photosensitive resin composition for color filter and color filter using the same - Google Patents

Abstract

A photosensitive resin composition for a color filter including (A) a yellow or orange dye; (B) a dye combination including a cyanine dye represented by the following Formula 1 and a metal complex dye; (C) an acryl binder resin; (D) a photopolymerizable monomer; (E) a photopolymerization initiator; and (F) a solvent, and a color filter using the same are provided. [Formula 1] (In the above Formula 1, each substituent is the same as defined in the specification.).

Description

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

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

The liquid crystal display device, which is one of the display devices, has advantages of weight reduction, thinness, low cost, low power consumption driving, and bonding with excellent integrated circuits, and its use range is expanding for notebook computers, monitors and TV images. Such a liquid crystal display device includes a color filter in which unit pixels in which red (R), green (G), and blue (B) subpixels corresponding to the three primary colors of light are repeatedly formed. When the subpixels are arranged adjacent to each other and a color signal is applied to each subpixel to control the brightness, a specific color is displayed in the unit pixel by combining the three primary colors.

The color filter is made of dyes or pigments of red (R), green (G), and blue (B), and the dye material converts white light of the backlight unit into respective corresponding colors. The color purity is improved as the spectrum of the dye material has absorption bands having no unnecessary wavelengths other than the absorption wavelengths required, and narrow absorption bands. Also, it should have excellent heat resistance, light resistance, and chemical resistance that do not fade or discolor under ultraviolet, acid, and base conditions exposed in the etching process of a color resist.

In the case of a liquid crystal display device having a large screen, the concentration of the colorant of the photosensitive resin composition is increased in the production of a color filter in order to increase the color purity. In order to increase the productivity and yield in the production process, a photosensitive resin composition having a low developing speed and excellent sensitivity .

In general, a color filter can be manufactured by coating three or more kinds of hues on a transparent substrate by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, etc. Recently, a pigment dispersion method using a pigment- It accomplishes.

The pigment dispersion method is a method of forming a colored thin film by repeating a series of processes of coating-exposing-developing-thermally curing a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, The durability can be improved and the thickness of the film can be kept uniform. However, in spite of the advantages of the pigment dispersion method, in order to manifest color characteristics such as brightness and contrast ratio over the current level, there is a method of compensating the lowering of the contrast caused by the particleity of the dispersed pigment, Technology is required. As a method for further improving the color characteristics described above, it is necessary to introduce a high-durability dye having no particleity in a solution state or a very small primary particle diameter of less than several nanometers.

An embodiment of the present invention is to provide a photosensitive resin composition for a color filter having high absorbance, brightness, and contrast ratio and excellent in heat resistance and chemical resistance.

Another embodiment of the present invention is to provide a color filter manufactured using the photosensitive resin composition for a color filter.

One embodiment of the present invention is a dye-sensitized solar cell comprising (A) a yellow or orange dye; (B) a dye combination comprising a cyanine dye and a metal complex dye represented by the following formula (1); (C) an acrylic binder resin; (D) a photopolymerizable monomer; (E) a photopolymerization initiator; And (F) a solvent. The photosensitive resin composition for a color filter comprises:

[Chemical Formula 1]

In Formula 1,

X ₁ and X ₂ are each independently a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom,

R1 to R4 and R11 to R14 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 haloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, A substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted A substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, A C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group or a substituted or unsubstituted C1 to C20 alkyl (meth) acrylate group,

R5, R6, R8 and R9 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R7 and R10 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkyl (meth) acrylate group or a substituted or unsubstituted C6 to C30 aryl group,

n is an integer of 1 to 4,

a, b, c and d are each independently an integer of 0 or 1,

A is a halogen ion, ClO ₄ ^- represented by the formula A compound of the formula 2-2 ^{_{2-1 -, BF 4 -, SbF}} 6 -, CF 3 SO 3 -, N (SO 2 CF 3) 2 ≪ / RTI >

[Formula 2-1]

[Formula 2-2]

Wherein the yellow or orange dye contained in the photosensitive resin composition for color filters has a transmittance in a wavelength range of 380 nm to 500 nm of 0% to 40% and a transmittance in a wavelength range of 570 nm to 590 nm of 50% to 100 %. ≪ / RTI >

The yellow or orange dye may be a direct dye, an acid dye, a basic dye, an acid mordant dye, a sulfide dye, a reducing dye, an azo dye, a disperse dye, a reactive dye, an oxidizing dye, a useful dye, Dyes, carbonium ion dyes, phthalocyanine dyes, nitro dyes, quinoline dyes, cyanine dyes, methine dyes, and combinations thereof.

The yellow or orange dye may be selected from the group consisting of Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent Orange 62, Solvent Orange 99 and combinations thereof Can be selected from the group consisting of.

R5, R6, R8 and R9 of the cyanine dye represented by Formula 1 may each independently be a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

R7 and R10 of the cyanine dye represented by Formula 1 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkyl (meth) acrylate group, or a substituted or unsubstituted C1 to C20 alkyl Gt; C6-C30 aryl < / RTI >

A of the cyanine dye represented by Formula 1 may be CF ₃ SO ₃ ^- or N (SO ₂ CF ₃ ) ₂ ^- .

The cyanine dye represented by Formula 1 may have a wavelength of 400 nm to 700 nm.

The cyanine dye may be a yellow, orange, or red dye.

The metal complex dyes may have a maximum absorption peak at a wavelength of 200 nm to 650 nm.

The metal complex dye may include at least one metal ion selected from Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd and Fe.

The metal complex dyes include Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent Orange 62, Solvent Orange 99, Solvent Red 8, A complex of metal ions with at least one of Red 32, Solvent Red 109, Solvent Red 112, Solvent Red 119, Solvent Red 124, Solvent Red 160, Solvent Red 132 and Solvent Red 218.

The photosensitive resin composition for a color filter may further comprise a pigment.

The pigments may include red pigments, yellow pigments, orange pigments, or combinations thereof.

The red pigment may be C.I. Pigment red 242, C.I. Pigment red 214, C.I. Pigment red 221, C.I. Pigment red 166, C.I. Pigment red 220, C.I. Pigment red 248, C.I. Pigment red 262, C.I. Pigment red 254, C.I. Pigment red 177, C.I. Pigment red 270 and C.I. Pigment red 272. < RTI ID = 0.0 >

The yellow pigment may be C.I. Yellow pigment 139, C.I. Yellow pigment 138 and C.I. And yellow pigment 150. [0034]

The photosensitive resin composition for a color filter may contain the cyanine dye and the pigment in a weight ratio of about 1: 9 to about 9: 1.

Wherein the photosensitive resin composition for a color filter comprises 0.1 to 5% by weight of (A) the yellow or orange dye; 1 to 80% by weight of the dye (B) comprising the cyanine dye and the metal complex; 0.1 to 30% by weight of the acrylic binder resin (C); 0.1 to 30% by weight of the photopolymerizable monomer (D), 0.1 to 5% by weight of the photopolymerization initiator (E); And (F) the solvent balance.

Another embodiment of the present invention provides a color filter manufactured using the photosensitive resin composition for a color filter.

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

Since a photosensitive resin composition for a color filter exhibiting high luminance and contrast ratio is provided, a color filter excellent in heat resistance and chemical resistance can be realized. Such a photosensitive resin composition for a color filter can realize a high luminance while maintaining an appropriate contrast ratio particularly in an element having a low transmittance of short-wavelength light such as an LED light source.

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, "substituted" means that at least one hydrogen atom in the compound is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, A thio 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, an acid anhydride, an amide group, an azo group, an azido group, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, , A C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 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 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or a combination thereof.

Unless otherwise stated, the terms "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl" and "heterocycloalkylene" refer to cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkyl Means that at least one heteroatom of N, O, S or P is present in the ring compound of the ring.

As used herein, unless otherwise specified, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

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

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.

The photosensitive resin composition for a color filter according to one embodiment comprises (A) a yellow or orange dye; (B) a dye combination comprising a cyanine dye and a metal complex dye represented by the following formula (1); (C) an acrylic binder resin; (D) a photopolymerizable monomer; (E) a photopolymerization initiator; And (F) a solvent.

Each component will be described in detail below.

(A) Yellow or orange dye

The yellow or orange dye is a yellow or orange dye which has a transmittance in the 380 nm to 500 nm wavelength range of 0% to 40% and a transmittance in the 570 nm to 590 nm wavelength range of 50% to 100%. For example, the transmittance in the 570 nm to 590 nm wavelength region may be 90% to 100%.

For example, the yellow or orange dye may be a dye having a transmittance in a wavelength region of 380 nm to 450 nm of 0% to 1% and a transmittance in a wavelength region of 450 nm to 550 nm of 1% to 100%.

The yellow or orange dye may be a direct dye, an acid dye, a basic dye, an acid mordant dye, a sulfide dye, a reducing dye, an azo dye, a disperse dye, a reactive dye, an oxidizing dye, a useful dye, Dyes, carbonium ion dyes, phthalocyanine dyes, nitro dyes, quinoline dyes, cyanine dyes, methine dyes, or combinations thereof.

For example, the yellow or orange dye may be selected from the group consisting of Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent Orange 62, Solvent Orange 99, Lt; / RTI >

The yellow or orange dye may be contained in an amount of 0.1 to 5% by weight based on the total amount of the photosensitive resin composition. When the yellow and orange dyes are contained within the above range, a high luminance can be achieved in an LCD employing an LED backlight while maintaining an appropriate contrast ratio.

(B) Cyanine  Dyes and metals Complex  Dyes containing dyes Combination

(B-1) Cyanine  dyes

The cyanine dye may be a compound represented by the following formula (1).

[Chemical Formula 1]

(In the formula 1,

X ₁ and X ₂ are each independently a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom,

Wherein R1 to R4 and R11 to R14 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 haloalkyl group, a substituted or unsubstituted C1 to C20 alkyl group, C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted Or a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, Or an unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group.

R5, R6, R8, and R9 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group. Specifically, R5, R6, R8, and R9 are each independently A substituted or unsubstituted C1 to C20 alkyl group.

Wherein R7 and R10 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkyl (meth) acrylate group, or a substituted or unsubstituted C6 to C30 aryl And specifically, R7 and R10 may each independently be a substituted or unsubstituted C1 to C20 alkyl group.

In Formula 1, n may be an integer of 1 to 4.

In Formula 1, a, b, c, and d may be independently 0 or an integer of 1.

Wherein A is a halogen ion, ClO ₄ ^- , BF ₄ ^- , SbF ₆ ^- , CF ₃ SO ₃ ^- , N (SO ₂ CF ₃ ) ₂ ^- , a compound represented by the following formula -2, and specifically, A may be CF ₃ SO ₃ ^- or N (SO ₂ CF ₃ ) ₂ ^- .

[Formula 2-1]

[Formula 2-2]

The cyanine dye is a molecule that itself is dyed like ordinary dyes and absorbs light in the visible light portion of the spectrum. Unlike conventional dyes, however, it is a molecule that re-emits fluorescent light from a visible light spectrum at a wavelength greater than the wavelength of absorbed light. Specifically, the wavelength of light emitted from the cyanine dye may be 400 nm to 700 nm.

The cyanine dye may be a yellow, orange, or red dye. In one embodiment, the cyanine dye may be a red dye.

When the cyanine dye is used, a color filter having a high luminance can be realized as having a high transmittance. By introducing a terminal having a crosslinking property into the structure of the cyanine compound, the degree of curing is increased by thermal crosslinking and heat resistance and chemical resistance A composition for an excellent color filter can be provided.

(B-2) Metal Complex  dyes

The metal complex dye may be a compound having a maximum absorption peak in a wavelength region of 200 nm to 650 nm. If the compound has an absorption wavelength in the above range in order to adjust the color coordinates of a combination of dyes, Dyes can be used.

Specifically, the metal complex dyes include yellow dyes having the maximum absorption peak in the wavelength region of 200 nm to 400 nm, orange dyes having the maximum absorption peak in the wavelength region of 300 nm to 500 nm, A red dye having an absorption peak, or a combination thereof.

The metal complex dyes may be selected from the group consisting of direct dyes, acid dyes, basic dyes, acid mordant dyes, sulfide dyes, reducing dyes, azoic dyes, disperse dyes, reactive dyes, oxidation dyes, useful dyes, azo dyes, anthraquinone dyes, , Carbonium ion dyes, phthalocyanine dyes, nitro dyes, quinoline dyes, cyanine dyes, polymethine dyes, or combinations thereof.

The metal complex dye may include at least one metal ion selected from Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd and Fe.

The metal complex dyes include Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent Orange 62, Solvent Orange 99, Solvent Red 8, A complex of a metal ion with at least one of Red 32, Solvent Red 109, Solvent Red 112, Solvent Red 119, Solvent Red 124, Solvent Red 160, Solvent Red 132 and Solvent Red 218 can be used.

When a dye combination in which the cyanine dye and the metal complex dye are combined is used, not only high luminance but also high contrast ratio can be obtained at the same time.

The cyanine dye and the metal complex dye may be mixed in a weight ratio of 50: 1 to 1:50, and more specifically, they may be mixed in a weight ratio of 30: 1 to 1:30. More specifically, 1 to 1: 5 by weight. When mixed in the weight ratio range, the brightness and contrast ratio can be further improved.

Specifically, a color filter having a transmittance at 500 nm to 800 nm of 95% or more can be realized.

The cyanine dye and the metal complex dye may have a solubility of 5 or more in the solvent used in the photosensitive resin composition for a color filter according to one embodiment, that is, the solvent (F) described later, and specifically 5 to 10 days have. The solubility can be obtained in terms of the amount (g) of the dye dissolved in 100 g of the solvent. When the solubility of the cyanine dye and the metal complex dye is within the above range, compatibility and coloring power with other components constituting the photosensitive resin composition for a color filter according to one embodiment can be ensured and precipitation of the dye can be prevented have.

The solvent may be, for example, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone cyclohexanone, 3-methoxy-1-butanol, or a combination thereof.

The cyanine dye has high heat resistance. That is, when measured by a thermogravimetric analyzer (TGA), the thermal decomposition temperature may be 200 ° C or higher, for example, 200 ° C to 400 ° C.

As having the specific range, it can be usefully used for color filters such as LCDs and LEDs that exhibit high brightness and high contrast ratio in a desired color coordinate.

The dye combination including the cyanine dye and the metal complex dye may be contained in an amount of 1 to 80% by weight based on the total amount of the photosensitive resin composition, and specifically 1 to 20% by weight. When the dye combination comprising the cyanine dye and the metal complex dye is used in the above range, a high brightness and contrast ratio can be expressed in a desired color coordinate.

( B ' ) Pigment

The cyanine dye can be further mixed with the pigment, and thus the luminance and contrast ratio can be further improved.

The above-mentioned pigments may be specifically red, yellow, or orange pigments.

Specifically, the red pigment preferably has a color index of not less than the color index C.I. Pigment red 242, C.I. Pigment red 214, C.I. Pigment red 221, C.I. Pigment red 166, C.I. Pigment red 220, C.I. Pigment red 248, C.I. Pigment red 262, C.I. Pigment red 254, C.I. Pigment red 177, etc. These may be used alone or in combination of two or more.

The above-mentioned pigments are used as yellow pigments in order to secure a given color characteristic. Yellow pigment 139, C.I. Yellow pigment 138 and C.I. And yellow pigment 150. [0034]

The pigment may be contained in the photosensitive resin composition in the form of a dispersion. Such a pigment dispersion may be composed of the pigment, a solvent, a dispersing agent, a binder resin, and the like.

As the solvent used in the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, 3-methoxy-1-butanol and the like are used Specifically, propylene glycol methyl ether acetate can be used.

The dispersant used in the pigment dispersion helps to uniformly disperse the pigment in the dispersion, and any nonionic, anionic, or cationic dispersant may be used. Specific examples thereof include polyalkylene glycols or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxides Adducts, alkylamines, and the like, which may be used alone or in admixture of two or more.

The binder resin used for the pigment dispersion may be an acrylic resin containing a carboxyl group, which not only improves the stability of the pigment dispersion but also improves the patterning of pixels.

The primary particle diameter of the pigment may be from 10 nm to 70 nm. When the primary particle diameter of the pigment is within the above range, the stability in the pigment dispersion is excellent and the resolution of the pixel is also excellent.

The secondary particle diameter of the pigment is not particularly limited, but may be 200 nm or less, for example, 70 nm to 100 nm in consideration of resolution of a pixel.

When the cyanine dye and the pigment are mixed, they may be mixed in a weight ratio of 1: 9 to 9: 1, specifically 3: 7 to 7: 3. When mixed in the weight ratio range, a high luminance and a high contrast ratio can be obtained while maintaining color characteristics.

The dye combination including the cyanine dye and the metal complex dye may be contained in an amount of 1 to 80% by weight, specifically 5 to 50% by weight based on the total amount of the photosensitive resin composition for a color filter . When the colorant is used within the above range, a high luminance and a high contrast ratio can be exhibited in a desired color coordinate.

(C) Acrylic binder resin

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

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

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

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

Specific examples of the acrylic binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate And methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer. However, the present invention is not limited thereto, and they may be used alone or in combination of two or more.

The weight average molecular weight of the acrylic binder resin may be from 3,000 g / mol to 150,000 g / mol, such as from 5,000 g / mol to 50,000 g / mol, such as from 20,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the acrylic binder resin is in the range described above, it has good adhesion with the substrate, good physical and chemical properties, and good viscosity.

The acid value of the acrylic binder resin may be from 15 mgKOH / g to 60 mgKOH / g, such as from 20 mgKOH / g to 50 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, excellent pixel resolution can be obtained.

The acrylic binder resin may be contained in an amount of 0.1 to 30% by weight, for example, 5 to 20% by weight based on the total amount of the photosensitive resin composition for a color filter. When the acrylic binder resin is contained within the above range, the color filter is excellent in developability in the production of a color filter, and the cross-linkability is improved, whereby an excellent surface smoothness can be obtained.

(D) Photopolymerization  Monomer

As the photopolymerizable monomer, a polyfunctional monomer having two or more hydroxyl groups may be used. Specific examples of the photopolymerizable monomer include glycerol acrylate, dipentaerythritol hexaacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol acrylate, pentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, But are not limited to, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate , 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate There is a relay agent and the like.

The photopolymerizable monomer may be contained in an amount of 0.1% by weight to 30% by weight, for example, 5% by weight to 20% by weight based on the total amount of the photosensitive resin composition for a color filter. When the photopolymerizable monomer is contained within the above range, pattern characteristics and developability are excellent in the production of a color filter.

(E) Light curing Initiator

The photopolymerization initiator is a photopolymerization initiator generally used in a photosensitive resin composition for a color filter. Examples of the photopolymerization initiator include an acetophenone compound, a benzophenone compound, a thioxanone compound, a benzoin compound, a triazine compound, Or a combination thereof.

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

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, 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- Orcanthon and the like can be used.

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 type compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s- triazine, 2- (3 ', 4'-dimethoxy (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) 6-triazine, 2,3,4-trichloromethyl (4'-methoxystyryl) -6-triazine, and the like can be used.

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.

In addition to the above-described photopolymerization initiators, carbazole-based compounds, diketone compounds, sulfonium borate compounds, diazo compounds, and imidazole-based compounds can also be used as a photopolymerization initiator.

The photopolymerization initiator may be contained in an amount of 0.1 wt% to 5 wt%, for example, 1 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition for a color filter. When the photopolymerization initiator is contained within the above range, photopolymerization occurs sufficiently during exposure in the pattern formation process for producing a color filter, and the sensitivity is excellent and the transmittance is improved.

(F) Solvent

The solvent is not particularly limited, but specific examples thereof 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 methyl ether, ethylene glycol ethyl ether and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

In view of the miscibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether and the like; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol 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 as the balance relative to the total amount of the photosensitive resin composition for a color filter, for example, 20 wt% to 90 wt%. When the solvent is contained within the above range, the photosensitive resin composition is excellent in coating property and excellent flatness can be maintained in a film having a thickness of 3 m or more.

(G) Surfactant

The photosensitive resin composition for a color filter may further include a surfactant to uniformly disperse the pigment in the solvent and improve leveling performance.

The surfactant may be a fluorine-based surfactant.

Specific examples of the fluorine-based surfactant include F-482, F-484 and F-478 of DIC Company, but are not limited thereto.

The surfactant may be a silicone surfactant together with the fluorochemical surfactant.

Specific examples of the silicone surfactant include TSF400, TSF401, TSF410, and TSF4440 of Toshiba Silicones, but are not limited thereto.

The surfactant may be included in an amount of 0.01 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition for a color filter, specifically 0.1 part by weight to 2 parts by weight. When the surfactant is contained within the above range, generation of foreign matter after development is small.

(H) Other additives

The photosensitive resin composition for a color filter may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid to prevent spots, spots, leveling, 3-amino-1,2-propanediol; A silane-based coupling agent having a vinyl group or (meth) acryloxy group; And the like. The amount of these additives to be used can be easily controlled depending on the desired physical properties.

Further, the photosensitive resin composition for a color filter may further contain an epoxy compound as an additive for the purpose of improving adhesion and the like.

Examples of the epoxy compound include epoxy novolac acrylate carboxylate resin, orthocresol novolak epoxy resin, phenol novolak epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, or a combination thereof .

When the epoxy compound is further included, it may further include a radical polymerization initiator such as a peroxide initiator or an azobis-based initiator.

The epoxy compound may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition for a color filter. When the epoxy compound is contained within the above range, the adhesion and other properties can be improved in terms of storage stability and economy.

The method for producing the photosensitive resin composition for a color filter is not particularly limited, but specifically, the above-mentioned dye, acrylic binder resin, photopolymerization initiator, photopolymerizable monomer, solvent, A composition can be prepared.

According to another embodiment, there is provided a color filter manufactured using the photosensitive resin composition for a color filter.

The color filter may be prepared by a conventional method. Specifically, the photosensitive resin composition may be coated on a glass substrate at a thickness of 1.5 to 2.0 탆 by a suitable method such as spin coating, roller coating, or slit coating do. After the application, UV light, electron beam or X-ray is irradiated to form a pattern necessary for the color filter. Means that the UV light has a wavelength range of 190 nm to 450 nm, specifically 200 nm to 400 nm. Then, when the coating layer is treated with an alkali developing solution, the unexposed portions of the coating layer are dissolved and a pattern necessary for the image color filter is formed. By repeating this process according to the required number of R, G, and B colors, a color filter having a desired pattern can be obtained. Further, in the above process, the image pattern obtained by development may be further heated or cured by actinic ray irradiation or the like to further improve crack resistance, solvent resistance, and the like.

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.

(Preparation of Photosensitive Resin Composition for Color Filter)

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

(A) Yellow or orange dye

(A-1) Yellow dye

 Yellow 6G (Ranches Corporation) was used.

(A-2) Orange dye

 KCF 0009 (Gyeongin) was used.

(B-1) Cyanine  dyes

 KCF R038 (Gyeongin) was used.

(B-2) Metal Complex  dyes

 KCF R037 (Gyeongin) was used.

(C) Acrylic binder resin

 Methacrylic acid / benzyl methacrylate copolymer having a weight average molecular weight of 28,000 g / mol (mixing weight ratio 30/70) was used.

(D) Photopolymerization  Monomer

 Dipentaerythritol hexaacrylate was used.

(E) Light curing Initiator

 CGI-124 from Ciba Specialty Chemicals Co. was used.

(F) Solvent

 A mixture of propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate was used.

(G) Surfactant

A fluorine-based surfactant (F-482, DIC) was used.

Example  One

2 g of the photopolymerization initiator (D) was dissolved in 44.5 g of propylene glycol monomethyl ether acetate as the solvent (F) and 15 g of ethyl 3-ethoxypropionate, followed by stirring at room temperature for 2 hours. Subsequently, 0.2 g of the yellow dye (A-1), 2.7 g of the cyanine dye (B-1) and 0.1 g of the metal complex (B-2) were added and stirred for 30 minutes. 15 g of the acrylic binder resin (C) 20 g of the monomer (E) was added and the mixture was stirred at room temperature for 2 hours. Then 0.5 g of surfactant (G) was added and stirred for 1 hour at room temperature. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

Example  2

Except that 0.4 g was added instead of 0.2 g of the yellow dye (A-1) in Example 1 and 2.5 g was substituted for 2.7 g of the cyanine dye (B-1), the photosensitive resin composition .

Example  3

Except that 0.4 g of the orange dye (A-2) was added in place of the yellow dye (A-1) in Example 1 and the cyanine dye (B-1) was added. .

Comparative Example  One

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the yellow or orange dye (A) was not used and 2.9 g of cyanine dye (B-1) was used instead of 2.7 g of the cyanine dye (B-1).

Comparative Example  2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the yellow or orange dye (A) was not used and 0.2 g of the yellow pigment Y138 was further added.

(Property evaluation 1: luminance measurement)

The photosensitive resin compositions for color filters of Examples 1 to 3 and Comparative Examples 1 and 2 were applied on a 1 mm thick glass substrate degreased and cleaned to measure the luminance to a thickness of 1 탆 to 2 탆, And dried on a hot plate for 3 minutes to obtain a coating film. The obtained coating film was cooled, irradiated with light at an exposure dose of 100 mJ / cm ² (based on 365 nm), and then dried in a hot-air circulating drying oven at 230 ° C for 30 minutes. The luminance was measured through a spectrometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.), and the results are shown in Table 1 below.

Measurement of color coordinates (x and y) and luminance (Y): Measured using a colorimeter (Otsuka Co., Ltd., MCPD 3000), and converted to LED light source standard.

(Property evaluation 2: Measurement of contrast ratio)

The photosensitive resin composition for color filters of Examples 1 to 3 and Comparative Examples 1 and 2 was applied to a bare glass having a thickness of 1 mm and a width of 10 cm x 10 cm by degreasing to measure the contrast ratio, Spin-coated at a thickness of 2 탆 using Spin 8, soft-baked on a hot plate at 90 캜 for 90 seconds, and then cooled at room temperature for 1 minute. The contrast ratio was calculated according to the following equation (1) after measuring the amount of light when the polarizer was opened and closed by using a contrast tester CT-1 manufactured by Tsubosaka, a contrast ratio measuring instrument. The results of the contrast ratio measurement are shown in Table 1 below. The evaluation criteria for the contrast ratio are as follows.

<Criteria for contrast ratio evaluation>

○: Contrast ratio is over 15000

?: Contrast ratio from 5000 or more to less than 10000

X: Contrast ratio less than 10000

[Equation 1]

Contrast ratio = L _open / L _close

L _open : the amount of light when the polarizing plate is opened

L _close : the amount of light when the polarizing plate is closed

Color coordinates Luminance Contrast ratio x y Y Example 1 0.646 0.323 16.65 ○ Example 2 0.646 0.326 17.65 ○ Example 3 0.646 0.322 16.61 ○ Comparative Example 1 0.646 0.321 16.05 △ Comparative Example 2 0.646 0.322 15.90 ×

It can be seen from Table 1 that the luminance and contrast ratio of Examples 1 to 3 using yellow or orange dyes are high at the same time according to one embodiment. Also, it can be seen from Examples 1 to 3 that as the yellow and orange dyes increase and the content of cyanine dyes decreases, the luminance and contrast ratios become higher as the color coordinate y increases.

On the other hand, in Comparative Example 1 using only a cyanine dye and a metal complex, the color coordinates are different from those of conventional color targets and show low luminance.

Further, in the case of Comparative Example 2 using a yellow pigment, it can be seen that both the luminance and the contrast ratio are low.

Thereby, the photosensitive resin composition for a color filter according to an embodiment including a yellow or orange dye, together with a cyanine dye and a metal complex dye, can be used in combination with a dye combination including a cyanine dye and a metal complex dye And it is possible to realize a higher luminance than a photosensitive resin composition for a color filter containing no yellow or orange dye.

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 (19)

(A) yellow or orange dyes;
(B) a dye combination comprising a cyanine dye and a metal complex dye represented by the following formula (1);
(C) an acrylic binder resin;
(D) a photopolymerizable monomer;
(E) a photopolymerization initiator; And
(F) Solvent
A photosensitive resin composition for a color filter comprising:
[Chemical Formula 1]

In Formula 1,
X ₁ and X ₂ are each independently a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom,
Each of R1 to R4 and R11 to R14 independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 haloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, A substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C20 cycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group or a substituted or unsubstituted C1 to C20 alkyl (meth) acrylate group,
R5, R6, R8 and R9 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R7 and R10 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkyl (meth) acrylate group or a substituted or unsubstituted C6 to C30 aryl group,
n is an integer of 1 to 4,
a, b, c and d are each independently an integer of 0 or 1,
A is any one of a halogen ion, ClO ₄ ^- , BF ₄ ^- , SbF ₆ ^- , CF ₃ SO ₃ ^- , N (SO ₂ CF ₃ ) ₂ ^- , or a compound represented by the following formula .
[Formula 2-1]

[Formula 2-2]

The method according to claim 1,
Wherein the yellow or orange dye has a transmittance in a wavelength region of 380 nm to 500 nm of 0% to 40% and a transmittance in a wavelength region of 570 nm to 590 nm of 50% to 100%.
The method according to claim 1,
The yellow or orange dye may be a direct dye, an acid dye, a basic dye, an acid mordant dye, a sulfide dye, a reducing dye, an azo dye, a disperse dye, a reactive dye, an oxidizing dye, a useful dye, Wherein the photosensitive resin composition is selected from the group consisting of dyes, carbonium ion dyes, phthalocyanine dyes, nitro dyes, quinoline dyes, cyanine dyes, methine dyes, and combinations thereof.
The method according to claim 1,
The yellow or orange dye may be selected from the group consisting of Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent Orange 62, Solvent Orange 99 and combinations thereof Wherein the photosensitive resin composition is a photosensitive resin composition for a color filter.
The method according to claim 1,
Wherein the yellow or orange dye has a transmittance in a wavelength region of 380 nm to 450 nm of 0% to 1% and a transmittance in a wavelength region of 450 nm to 550 nm of 1% to 100%.
The method according to claim 1,
Wherein R5, R6, R8 and R9 are a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.
The method according to claim 1,
Wherein R7 and R10 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkyl (meth) acrylate group or a substituted or unsubstituted C6 to C30 aryl Based on the total weight of the photosensitive resin composition.
The method according to claim 1,
In the above formula (1), A represents CF ₃ SO ₃ ^- or N (SO ₂ CF ₃ ) ₂ ^- .
The method according to claim 1,
Wherein the cyanine dye has a wavelength of light of 400 nm to 700 nm re-emitted.
The method according to claim 1,
Wherein the cyanine dye is a red dye.
The method according to claim 1,
Wherein the metal complex dye has a maximum absorption peak in a wavelength region of 200 nm to 650 nm.
The method according to claim 1,
Wherein the metal complex dye comprises at least one metal ion selected from Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd and Fe.
The method according to claim 1,
The metal complex dyes include Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent Orange 62, Solvent Orange 99, Solvent Red 8, A complex of at least one of red 32, solvent red 109, solvent red 112, solvent red 119, solvent red 124, solvent red 160, solvent red 132, and solvent red 218 with a metal ion.
The method according to claim 1,
Wherein the photosensitive resin composition for a color filter further comprises a pigment.
15. The method of claim 14,
The pigments were CI Pigment Red 242, CI Pigment Red 214, CI Pigment Red 221, CI Pigment Red 166, CI Pigment Red 220, CI Pigment Red 248, CI Pigment Red 262, CI Pigment Red 254, CI Pigment Red 177 and CI Yellow And a pigment (150).
15. The method of claim 14,
Wherein the photosensitive resin composition for a color filter comprises the cyanine dye and the pigment in a weight ratio of 1: 9 to 9: 1.
The method according to claim 1,
The photosensitive resin composition for a color filter
(A) from 0.1% to 5% by weight of a yellow or orange dye;
1 to 80% by weight of a dye combination comprising (B) a cyanine dye and a metal complex dye;
0.1 to 30% by weight of the acrylic binder resin (C);
0.1% to 30% by weight of (D) the photopolymerizable monomer;
0.1 to 5% by weight of (E) the photopolymerization initiator; And
The amount of the solvent (F)
Wherein the photosensitive resin composition is a photosensitive resin composition for a color filter.
A color filter produced by using the photosensitive resin composition for a color filter according to any one of claims 1 to 17.
19. The method of claim 18,
Wherein the color filter is applied to an LED light source.