TWI519894B - Photosensitive resin composition for color filter and color filter using the same - Google Patents

Description

Photosensitive resin composition and color filter using the same [Related application cross-reference]

Priority is claimed on Korean Patent Application No. 10-2013-0055937, the entire disclosure of which is incorporated herein by reference.

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

Among a wide variety of displays, liquid crystal displays have the advantages of brightness, thinness, low cost, low operating power consumption, and improved adhesion to integrated circuits, and have been widely used in portable computers, monitors, and TV screens. The liquid crystal display is equipped with a color filter formed by repeating unit pixels in which three primary color sub-pixels of red (R), green (G), and blue (B) are combined. When each sub-pixel is arranged adjacently, and then a color signal is applied to each sub-pixel and each sub-pixel is controlled The brightness of the unit pixel due to the combination of the three primary colors displays a specific color. The color filter is made of a dye of red (R), green (G), and blue (B) colors or a pigment. These color materials function to change the white light in the backlight unit into respective corresponding colored lights. Since the color material has a spectrum which does not have an unnecessary wavelength other than the desired absorption wavelength and a small absorption band, the display performance of the color filter can be improved. Further, the color material is required to have excellent heat resistance, light resistance, and chemical resistance without being discolored or discolored under conditions of exposure to ultraviolet rays (UV), acids, and alkalis during color resist etching. In order to improve the color purity of a large-screen liquid crystal display (LCD), a color filter is manufactured using a photosensitive resin composition prepared by increasing a colorant concentration. Therefore, the photosensitive resin composition is required to have a reduced developing speed in the manufacturing process to improve productivity and yield, and it is required that the photosensitive resin composition has excellent sensitivity although it is rarely exposed. Generally, color filters are prepared by coating three or more colors on a transparent substrate by dyeing, electrophoretic deposition (EPD), printing, pigment dispersion, etc., and color resists using pigment dispersion have been more widely used recently. Pigment dispersion. The pigment dispersion method can form a colored film by repeating a series of processes such as coating, exposing, developing, and curing a photopolymer composition containing a colorant on a transparent substrate including a black matrix. The method can improve heat resistance and durability, is a very important characteristic of a color filter and can provide a uniform film thickness. However, despite its many advantages, the pigment dispersion method cannot achieve the existing level or higher level of color characteristics in terms of brightness, contrast, and the like. Therefore, a new method is required to compensate for contrast deterioration due to the particle characteristics of the dispersed pigment and additionally ensure high brightness. Further improvement in color characteristics can be achieved by introducing a dye having a small primary particle size of several nanometers or a particle-free and high durability in solution.

One embodiment of the present invention provides a photosensitive resin composition for a color filter which has high absorbance, brightness, and contrast, and excellent heat resistance and chemical resistance.

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

One embodiment of the present invention provides a photosensitive resin composition for a color filter comprising (A) a yellow or orange dye, (B) a dye of a cyanine dye and a metal complex dye represented by the following Chemical Formula 1 Combination, (C) acrylic binder resin, (D) photopolymerizable monomer, (E) photopolymerization initiator, and (F) solvent:

In the above Chemical Formula 1, X ₁ and X ₂ are each independently carbon, nitrogen, oxygen or sulfur, and R1 to R4 and R11 to R14 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20. An 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 to C20 cycloalkynyl 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, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or substituted Or an unsubstituted C1 to C20 alkyl (meth) acrylate group, each of R5, R6, R8 and R9 being independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, R 7 and R10 are 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 a substituted C6 to C3 aryl group, n is an integer from 1 to 4, a, b, c and d are each independently an integer 0 or 1, and A is a halogen ion, ClO ₄ ^- , BF ₄ ^- , SbF ₆ ^- , CF ₃ SO ₃ ^- , N(SO ₂ CF ₃ ) ₂ ^- or one of the compounds represented by the following chemical formulas 2-1 and 2-2:

The yellow or orange dye used in the photosensitive resin composition for the color filter may have a transmittance of about 0% to about 40% in a wavelength region of about 380 nm to about 500 nm, and a wavelength region of about 570 nm to about 590 nm. It has a transmittance of from about 50% to about 100%.

The yellow or orange pigment may be selected from direct dyes, acid dyes, basic dyes, acid mordant dyes, sulphur dyes, vat dyes, azoic dyes, disperse dyes, reactive dyes, Oxidation dyes, alcohol dyes, azo dyes, anthraquinone dyes, indigoid 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 their combination.

R5, R6, R8, and R9 of the cyanine dye represented by the above Chemical 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 the above Chemical Formula 1 may each independently be a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkyl group (A A acrylate group, or a substituted or unsubstituted C6 to C30 aryl group.

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

The cyanine dye represented by the above Chemical Formula 1 can re-emit light in a wavelength of from about 400 nm to about 700 nm.

The cyanine dye can be a yellow dye, an orange dye, or a red dye.

The metal complex dye may have a maximum absorption peak in a wavelength of from about 200 nm to about 650 nm.

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

The metal complex dye may include a combination of a metal ion and at least one 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, Solvent Red 8, Solvent 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 contain a pigment.

The pigment may include a red pigment, a yellow pigment, an orange pigment, or a combination thereof.

The red pigment may include a color selected from the group consisting of 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. At least one of CI Pigment Red 270, and CI Pigment Red 272.

The yellow pigment may include at least one selected from the group consisting of C.I. yellow pigment 139, C.I. yellow pigment 138, and C.I. yellow pigment 150.

The photosensitive resin composition may contain cyanine dyes and pigments in a weight ratio of from about 1:9 to about 9:1.

The photosensitive resin composition may comprise from about 0.1% by weight to about 5% by weight of a yellow dye or an orange dye (A), from about 1% by weight to about 80% by weight of a dye (B) comprising a cyanine dye and a metal complex, From about 0.1% by weight to about 30% by weight of the acrylic binder resin (C); from about 0.1% by weight to about 30% by weight of the photopolymerizable monomer (D), from about 0.1% by weight to about 5% by weight of the photopolymerization initiator (E), and the balance of solvent (F).

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

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

The photosensitive resin composition for a color filter has high brightness and contrast, so that it is possible to realize a color filter having excellent heat resistance and chemical resistance. Such a photosensitive resin composition for a color filter can achieve high luminance while maintaining an appropriate contrast, particularly a device having low transmittance in a short wavelength such as an LED light source.

Hereinafter, embodiments of the invention are described in detail. However, these embodiments are exemplary, and the present disclosure is not limited thereto.

As used herein, the term "substituted", when not specifically defined otherwise, may refer to replacing at least one hydrogen of a compound with a halogen atom (F, Cl, Br or I), a hydroxyl group, C1 to C20 alkoxy, nitro, cyano, amine, imino, azido, fluorenyl, fluorenyl, hydrazine, carbonyl, carbamoyl, fluorenyl, ester, ether, carboxyl or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, C6-C30 aryl, C3-C20 cycloalkyl, C3-C20 cycloalkenyl, C3-C20 cycloalkynyl, C2-C20 heterocycloalkyl, C2-C20 heterocycloalkenyl, C2-C20 heterocycloalkynyl Or a combination of them.

As used herein, the terms "heterocycloalkyl", "heterocyclenyl", "heterocycloalkynyl", "heterocycloalkylene" are used to encompass N, O, when no specific definition is provided. A cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkylene cyclic compound of at least one hetero atom in S or P.

As used herein, "(meth)acrylate" means "acrylate" and "methacrylate" when no specific definition is provided.

The photosensitive resin composition for a color filter according to one embodiment contains (A) a yellow or orange dye; (B) a dye combination of a cyanine dye and a metal complex dye represented by the following Chemical Formula 1; An acrylic binder resin; (D) a photopolymerizable monomer; (E) a photopolymerization initiator; and (F) a solvent.

Hereinafter, each component is described in detail.

(A) yellow or orange dye

The yellow or orange dye used in the photosensitive resin composition for the color filter may have a transmittance of about 0% to about 40% in a wavelength region of about 380 nm to about 500 nm, and a wavelength region of about 570 nm to about 590 nm. It may have a transmittance of from about 50% to about 100%. Specifically, the yellow or orange dye may have a transmittance of from about 90% to about 100% in a wavelength region of from about 570 nm to about 590 nm.

Specifically, the yellow or orange dye may have a transmittance of from about 0% to about 1% in a wavelength region of from about 380 nm to about 450 nm, and may have a transmission of from about 1% to about 100% in a wavelength region of from about 450 nm to about 550 nm. rate.

The yellow or orange dye may be selected from direct dyes, acid dyes, basic dyes, and acidic media. Dyes, sulphur dyes, vat dyes, ice dyes, disperse dyes, reactive dyes, oxidative dyes, alcohol dyes, azo dyes, anthraquinone dyes, indigo dyes, carbocation dyes, phthalocyanine dyes, nitro dyes, quinine Morphotic dyes, cyanine dyes, methine dyes, and combinations thereof.

Specifically, 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 their combination.

The yellow or orange dye may be contained in an amount of from about 0.1% by weight to about 5% by weight based on the total amount of the photosensitive resin component. When the yellow or orange dye is included in the range, high brightness can be obtained in an LCD including an LED backlight while maintaining proper contrast.

(B) Dye combination containing cyanine dye and metal complex dye (B-1) cyanine dye

As the cyanine dye, a compound represented by the following Chemical Formula 1 can be used.

In the above Chemical Formula 1, X ₁ and X ₂ are each independently carbon, nitrogen, oxygen or sulfur, and in the above Chemical Formula 1, R1 to R4 and R11 to R14 are each independently a hydrogen atom, a halogen atom, a substituted or not Substituted C1 to C20 alkyl group, substituted or unsubstituted C1 to C20 haloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted a 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 ring Alkenyl, substituted or unsubstituted C3 to C20 cycloalkynyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group.

Specifically, in the above Chemical Formula 1, R5, R6, R8 and R9 may each independently be a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and more specifically, each independently, substituted or not Substituted C1 to C20 alkyl.

In the above Chemical Formula 1, R7 and R10 may each independently be a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkyl (meth) acrylate group. A group, or a substituted or unsubstituted C6 to C30 aryl group, and specifically, R7 and R10 may each independently be a substituted or unsubstituted C1 to C20 alkyl group.

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

In the above Chemical Formula 1, a, b, c and d are independently an integer of 0 or 1.

In the above Chemical Formula 1, A may be a halogen ion, ClO ₄ ^- , BF ₄ ^- , SbF ₆ ^- , CF ₃ SO ₃ ^- , N(SO ₂ CF ₃ ) ₂ ^- or by the following chemical formulas 2-1 and 2-2 One of the compounds represented, and in particular, each independently is CF ₃ SO ₃ ^- or N(SO ₂ CF ₃ ) ₂ ^- .

[Chemical Formula 2-1]

Cyanine dyes are molecules that are themselves dyed and absorb light in the visible region of the spectrum, just like typical dyes. However, unlike typical dyes, a methine-based compound is a molecule that re-fluoresce a visible spectrum having a wavelength greater than the wavelength of the absorbed light. The wavelength of the re-emitted light of the cyanine dye can range from about 400 nm to about 700 nm.

The cyanine dye can be a yellow, orange, or red dye. In an exemplary embodiment, the cyanine dye may be a red dye.

When a cyanine dye is used, a color filter having high luminance can be realized due to high transmittance, and a color filter for excellent color heat resistance and chemical resistance can be provided by heat crosslinking by increasing the degree of curing. The composition is thermally crosslinked due to a crosslinking terminal introduced to the cyanine dye structure.

(B-2) metal complex dye

The metal complex dye may be a compound having a maximum absorption peak in a wavelength region of from about 200 nm to about 650 nm, and if it has an absorption wavelength within the range, the metal complex dye may be all soluble in an organic solvent. Any metal complex dye of color to adjust the color coordinates by a combination of dyes.

Specifically, the metal complex dye may include a wavelength region of from about 200 nm to about 400 nm. a yellow dye having a maximum absorption peak in the domain, an orange dye having a maximum absorption peak in a wavelength region of about 300 nm to about 500 nm, and a red dye having a maximum absorption peak in a wavelength region of about 500 nm to about 650 nm, and combinations thereof .

The metal complex may be a direct dye, an acid dye, a basic dye, an acid mordant dye, a sulphur dye, a vat dye, an ice dye, a disperse dye, a reactive dye, an oxidative dye, an alcohol dye, an azo dye, an anthraquinone dye. An indigo dye, a carbocation dye, a phthalocyanine dye, a nitro dye, a quinoline dye, a cyanine dye, a polymethine dye, or a combination thereof.

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

The metal complex dye may be 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 Solvent 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.

Dye compositions of cyanine dyes and metal complex dyes provide high contrast and high brightness.

The cyanine dye and the metal complex dye may be mixed in a weight ratio of from about 50:1 to about 1:50, specifically from about 30:1 to about 1:30, and more specifically from about 5:1 to about 1:5. . Brightness and contrast are further improved within the weight ratio range.

Specifically, the color filter has a transmittance of greater than or equal to about 95% from about 500 nm to about 800 nm.

Cyanine dyes and metal complex dyes for coloring according to one embodiment The solvent used in the photosensitive resin composition of the filter (i.e., the solvent (F) described below) may have a solubility of greater than or equal to 5, and specifically, may have a solubility of from about 5 to about 10. Solubility refers to the amount of dye dissolved in 100 g of solvent. When the solubility of the cyanine dye and the metal complex dye is in the above range, compatibility and coloring property with other components of the photosensitive resin composition for a color filter according to one embodiment can be ensured, And it can prevent the precipitation of dyes.

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

The cyanine dye can have high heat resistance. In other words, when measured with a thermogravimetric analyzer (TGA), the pyrolysis temperature may be higher than or equal to about 200 °C, and specifically from about 200 °C to about 400 °C.

Cyanine dyes having such characteristics can be effectively used in color filters (such as LCDs and LEDs) to produce high brightness and high contrast in desired color coordinates.

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

(B’) pigment

The pigment can be further mixed and used with the dye, in which case the brightness and contrast may be more improved.

The pigment may specifically use a red, yellow, or orange pigment.

The red pigment may specifically include 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 of color index. Pigment Red 254, CI Pigment Red 177, etc., and they may be used singly or as a mixture of two or more.

The pigment may include characteristics such as C.I. yellow pigment 139, C.I. yellow pigment 138, and at least one of the C.I. yellow pigments 150 to obtain a given color.

The pigment can be prepared as a dispersion and contained in a photosensitive resin composition. Such a pigment dispersion may contain a pigment and a solvent, a dispersant, a binder resin, and the like.

The solvent used in the pigment dispersion may be ethylene glycol acetate, ethyl cyproterone, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, 3-methyl Oxy-1-butanol or the like, and specifically, propylene glycol methyl ether acetate can be used.

The dispersant used in the pigment dispersion helps to uniformly disperse the pigment and may include a nonionic, anionic, or cationic dispersant. Examples of the dispersant include polyalkylene glycol or its ester, polyoxyalkylene, polyhydric alcohol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonate, sulfonic acid Salts, carboxylates, carboxylates, alkylguanamine alkylene oxide addition products, alkylamines, and they may be used singly or as a mixture of two or more.

The binder resin used in the pigment dispersion may be an acrylic resin containing a carboxyl group and may improve the patterning property of the pixel and the stability of the pigment dispersion.

The primary particle size of the pigment ranges from about 10 nm to about 70 nm. When the pigment has a primary particle diameter within the above range, it has excellent stability in the dispersion and can improve the resolution of the pixel.

The secondary particle diameter of the pigment is not particularly limited, but may have a secondary particle diameter of less than or equal to about 200 nm, specifically from about 70 nm to about 100 nm, when considering the resolution of the pixel.

The dyes and pigments are mixed in a weight ratio ranging from about 1:9 to about 9:1, and specifically, from about 3:7 to about 7:3. When mixed in the range, the composition can maintain not only color characteristics but also high brightness and contrast.

The dye combination of the cyanine dye and the metal complex dye may be from about 1% by weight to about 80% by weight, and specifically from about 5% by weight to about 50% by weight, based on the total amount of the photosensitive resin composition for the color filter. the amount. When a dye combination of a cyanine dye and a metal complex dye is used within the range, high brightness and contrast 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 monomer comprising at least one acrylic repeating unit. Resin.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer comprising at least one carboxyl group. Examples of the monomer 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 ranging from about 5 wt% to about 50 wt%, specifically, from about 10 wt% to about 40 wt%, based on the total amount of the acrylic binder resin.

Examples of the diene-based unsaturated monomer may include an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether or the like; an unsaturated carboxylic acid ester compound such as ( Methyl)methyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid 2-hydroxyethyl ester, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, etc.; unsaturated carboxylic acid aminoalkyl Ester compounds, such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, etc.; vinyl carboxylate compounds, such as vinyl acetate, vinyl benzoate, etc.; unsaturated A glycidyl carboxylate compound such as glycidyl (meth)acrylate or the like; an acrylonitrile compound such as (meth)acrylonitrile or the like; an unsaturated guanamine compound such as (meth)acrylamide or the like; and the like. They may be used singly or as a mixture of two or more.

Examples of the acrylic binder resin may include methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate/methacrylic acid 2-hydroxyethyl ester copolymer, methacrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, etc., but is not limited thereto. They may be used singly or in combination of two or more.

The acrylic binder resin may have from about 3000 g/mol to about 150,000 g/mol, and specifically, from about 5000 g/mol to about 50,000 g/mol, and more specifically, from about 20,000 g/mol to about 30,000. Weight average molecular weight of g/mol. When the acrylic binder resin has a weight average molecular weight within this range, the composition may have excellent close contact properties with the substrate, good physical and chemical properties, and a suitable viscosity.

The acid value of the acrylic binder resin may range from about 15 mgKOH/g to about 60 mgKOH/g, specifically, from about 20 mgKOH/g to about 50 mgKOH/g. When the acrylic binder resin has an acid value within this range, excellent pixel resolution can be brought about.

Acrylic acid may be included in an amount ranging from about 0.1 wt% to about 30 wt%, and specifically from about 5 wt% to about 20 wt%, based on the total amount of the photosensitive resin composition for the color filter. Binder-like resin. When the acrylic binder resin is included in the range, the composition can have excellent developability and improved crosslinkability, thereby having excellent surface flatness when manufactured as a color filter.

(D) Photopolymerizable monomer

The photopolymerizable monomer may include a polyfunctional monomer having two or more hydroxyl groups. Examples of the photopolymerizable monomer may be glycerin acrylate, dipentaerythritol hexaacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1 , 6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritoldiacrylate, pentaerythritoltriacrylate, pentaerythritol diacrylate, dipentaerythritol triacrylate Dipentaerythritolacrylate, pentaerythritolhexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolacpoxyacrylate, dimethacrylate Alcohol ester, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6 methacrylic acid - hexanediol ester or the like.

The photopolymerizable monomer may be contained in an amount ranging from about 0.1% by weight to about 30% by weight, and specifically from about 5% by weight to about 20% by weight, based on the total amount of the photosensitive resin composition for the color filter. When the photopolymerizable monomer is included in the range, the composition may have excellent pattern characteristics and developability.

(E) Photopolymerization initiator

The photopolymerization initiator may be used in a photosensitive resin composition for a color filter. The photopolymerization initiator used may include an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an anthraquinone compound, or a combination thereof.

The acetophenone compound may include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone (2-hydroxy-2- Methylpropinophenone), p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl 1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- Butan-1-one and the like.

The benzophenone compound may include benzophenone or benzamidine benzoic acid (benzoyl). Benzoyl acid), benzoyl benzoic acid methyl ester, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-double (two Methylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorodiphenyl Ketone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

The thioxanthone compound may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2 - chlorothioxanthone and the like.

The benzoin compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

Triazine compounds may 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(three Chloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-three Oxazine, 2-(naphthol-1-yl)-4,6-bis(trichloromethyl)-s- Triazine (2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine), 2-(4-methoxynaphthol-1-yl)-4,6-bis (three 2-(4-methoxynaphtho-1-yl-4,6-bis(trichloromethyl)-s-triazine), 2-3-4-trichloromethyl(piperidinyl)-6 Triazine, 2-4-trichloromethyl (4'-methoxystyryl)-6-triazine, and the like.

Terpenoids may include 2-(o-benzylidenyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-ethylindenyl)- 1-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone.

The photopolymerization initiator may include a carbazole compound, a diketone compound, a bismuth borate compound, a diazo compound, a diimidazole compound, and the like in addition to the above photopolymerization initiator.

The photopolymerization initiator may be contained in an amount ranging from about 0.1% by weight to about 5% by weight, and specifically from about 1% by weight to about 3% by weight, based on the total amount of the photosensitive resin composition for the color filter. When the photopolymerization initiator is included in the range, the composition can be subjected to sufficient photopolymerization upon exposure during the pattern forming process for preparing a color filter, achieving excellent sensitivity and improving transmittance.

(F) solvent

The solvent is not particularly limited, but examples of the solvent include alcohols such as methanol, ethanol, etc.; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, etc.; glycol ethers Such as ethylene glycol methyl ether, ethylene glycol ether, propylene glycol methyl ether, etc.; acetaminophen acetate, such as acetate celluloid, ethyl cellosolve acetate, diethyl celluloid Diethyl cellosolve acetate, etc.; carbitol, such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, etc.; Alcohol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; ketones, Such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-butanone, methyl n-butanone, methyl n-pentanone, 2-heptanone, etc.; saturated fat Group of monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; alkyl lactates such as methyl lactate, ethyl lactate, etc.; alkyl glycolic acid esters, such as hydroxyl groups Methyl acetate, ethyl hydroxyacetate, butyl glycolate, etc.; alkoxyalkyl acetates such as methoxymethyl acetate, methoxyethyl acetate, methoxyacetate Methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; alkyl 3-hydroxypropionate, such as methyl 3-hydroxypropionate, Ethyl 3-hydroxypropionate; etc.; alkyl 3-alkoxypropionate, such as methyl 3-methoxypropionate Ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-hydroxypropionate, such as methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; alkyl 2-alkoxypropionate, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropanoate, such as methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropionate; etc.; alkyl 2-alkoxy-2-methylpropanoate, such as methyl 2-methoxy-2-methylpropanoate (methyl 2- Methoxy-2-methylpropionate), 2-ethoxy-2-methylpropionate, etc.; esters, such as 2-hydroxyethyl propionate, 2-hydroxy-2-propionate 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutanoate, etc.; or keto ester compounds, such as Ethyl pyruvate. Further, the solvent may be N-methylformamide, N,N-dimethylformamide, N-methylformamide, N- Methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetamidine, isophorone, hexanoic acid, Octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, acrylic acid Propylene carbonate, phenyl cellosolve acetate, and the like. These solvents may be used singly or as a mixture of two or more.

The solvent may include glycol ethers such as ethylene glycol monoethyl ether or the like in view of compatibility, reactivity, etc.; ethylene glycol alkyl ether acetates such as ethyl cyproterone acetate; esters, Such as 2-hydroxyethyl propionate; diethylene glycols, such as diethylene glycol monomethyl ether; or propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate Wait.

The solvent may be contained in an amount of from about 20% by weight to about 90% by weight based on the balance, and specifically, based on the total amount of the photosensitive resin composition. When the solvent is included in this range, the photosensitive resin composition may have excellent coating properties and may maintain excellent flatness in a layer having a thickness of greater than or equal to about 3 μm.

(G) surfactant

The photosensitive resin composition for a color filter may further contain a surfactant to enable the pigment to be uniformly dispersed in a solvent and to improve leveling performance.

The surfactant may be a fluorosurfactant.

Examples of the fluorine-based surfactant may include F-482, F-484, F-478, and the like prepared by DIC Co., Ltd., but are not limited thereto.

Surfactants may include terpene surfactants as well as fluorosurfactants.

Examples of the terpene surfactant may include TSF400, TSF401, TSF410, TSF4440, etc., prepared by Toshiba Silicon Co., Ltd., but are not limited thereto. herein.

The surfactant may be contained in an amount ranging from about 0.01 to about 5 parts by weight, and more specifically, from about 0.1 to about 2 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the range, the composition may have a smaller amount of impurities generated after development.

(H) Other additives

The photosensitive resin composition for a color filter may further contain other additives such as malonic acid, 3-amino-1,2-propanediol, or a decane type having a vinyl group or a (meth)acryloxy group. The binder is used to prevent stains or spots during coating, to facilitate adjustment of the leveling (leveling) or to prevent pattern residue due to undeveloped. These additives can be adjusted in amounts depending on the desired properties.

Further, if necessary, the photosensitive resin composition for a color filter may additionally contain an epoxy compound to improve close contact and other characteristics.

The epoxy compound may include an epoxy novolac propylene carboxylate resin (epoxy) Novolac acryl carboxylate resin, ortho cresol novolac epoxy resin, phenol novolac epoxy resin, tetramethyl biphenyl epoxy resin ), a bisphenol A-type epoxy resin, an alicyclic epoxy resin, or a combination thereof.

When an epoxy compound is contained, a peroxide initiator or a radical polymerization initiator such as an azo initiator can be additionally contained.

The epoxy compound may be contained in an amount of from about 0.01 part by weight to about 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 in the When it is within the range, the storage property, the close contact force, and the like can be improved.

The photosensitive resin composition for a color filter is not particularly limited in terms of method, but may be a mixed dye, an acrylic binder resin, a photopolymerization initiator, a photopolymerizable monomer and a solvent, and an optional additive. To prepare.

According to another embodiment of the present invention, a color filter manufactured using a photosensitive resin composition is provided.

Such a color filter can be produced by a general method, but is specifically manufactured by spin coating, roll coating, slit coating or the like using a photosensitive resin composition to have a thickness in the range of about 1.5 μm to about 2.0 μm. After coating, the layers are irradiated with UV rays, electron beams or X-rays to form the desired pattern of color filters. The UV rays may have a wavelength region ranging from about 190 nm to about 450 nm, and specifically ranging from about 200 nm to about 400 nm. Then, when the coated layer is treated with an alkaline developer, the region in which it is not irradiated can be dissolved to form a pattern for the image color filter. The process is repeated depending on the necessary number of R, G, and B colors to produce a color filter having a desired pattern. Further, the image pattern obtained by development is cured by heat treatment, actinic ray irradiation or the like, and as a result, crack resistance, solvent resistance and the like are improved.

Hereinafter, the present invention will be more specifically described with reference to the embodiments. However, the examples are not to be construed as limiting the scope of the invention in any way.

( Preparation of a photosensitive resin composition for a color filter)

A photosensitive resin composition was prepared using the following components.

(A) yellow or orange dye (A-1) yellow dye

Use yellow 6G (Lanxess Corporate).

(A-2) orange dye

Use KCF O009 (Beijing Gosei, Kyung-In Synthetic Corporation).

(B-1) cyanine dye

Use KCF R038 ( Kyoto Corporation ).

(B-2) metal complex dye

Use KCF R037 (Kyoto Corporation).

(C) Acrylic binder resin

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

(D) Photopolymerizable monomer

Dipentaerythritol hexaacrylate was used.

(E) Photopolymerization 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 Co., Ltd.) was used.

Example 1

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

Example 2

A photosensitive resin composition was prepared according to the same method as Example 1, except that 0.4 g of a yellow dye (A-1) was used instead of 0.2 g, and 2.5 g instead of 2.7 g of a cyanine dye (B-1) was used instead. .

Example 3

A photosensitive resin composition was prepared according to the same method as Example 1, except that 0.4 g of an orange dye (A-2) was used instead of the yellow dye (A-1) and a cyanine dye (B-1) was used.

Comparative example 1

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

Comparative example 2

A photosensitive resin composition was prepared according to the same method as Example 1, except that 0.2 g of a yellow pigment Y138 was additionally used and a yellow or orange dye (A) was not used.

(Performance Evaluation 1: Brightness Measurement)

In order to measure the brightness, the photosensitive resin compositions for color filters according to Examples 1 to 3 and Comparative Examples 1 and 2 were respectively coated on a 1 mm-thick degreased glass substrate to a thickness of 1 μm to 2 μm and Drying on a hot plate at 90 ° C for 3 minutes gave each film. The obtained film was cooled, irradiated with an exposure dose of 100 mJ/cm ² (refer to 365 nm) and dried in a forced convection drying oven at 230 ° C for 30 minutes. The brightness was measured by using a spectrophotometer (Otsuka Electronics Co., Ltd., MCPD3000), and the results are shown in Table 1 below.

Color coordinates (x and y) and brightness (Y) were measured using a colorimeter (Otsuka Electronics Co., Ltd., MCPD3000) and referenced to LED light source conversion.

(Performance Evaluation 2: Measurement of Contrast)

In order to measure the contrast, a spin coater (K-rotation 8 of KDNS Co., Ltd.) was used on a degreased glass substrate (bare glass) having a thickness of 1 mm and a width of 10 cm × 10 cm, respectively, according to Examples 1 to 3 and Comparative Examples 1 to 2, respectively. The photosensitive resin composition for the color filter was spin-coated to a thickness of 2 μm, soft baked on a hot plate at 90 ° C for 90 seconds, and cooled to room temperature for 1 minute. Each light amount is measured by turning on and off a polarizer by using a contrast tester CT-1 manufactured by Tsubosaka Electric Co., Ltd., and is calculated according to the following Equation 1. Contrast. The measurement results of the contrast are shown in Table 1 below.

○: Contrast is greater than or equal to 15000

△: The contrast is greater than or equal to 5000 and less than 10000

X: The contrast is less than 10000

[Equation 1] Contrast = L _on / L _off

L _open : the amount of light when the polarizer is opened

L _off : the amount of light when the polarizer is off

As seen from Table 1, Examples 1 to 3 using a yellow or orange dye according to one embodiment simultaneously exhibited high brightness and contrast. From the results of Examples 1 to 3, as the amount of the yellow and orange dyes increased, and the amount of the cyanine dye decreased, the color coordinates y increased and the brightness and contrast became higher.

On the other hand, Comparative Example 1 using only the cyanine dye and the metal complex had a color coordinate different from the conventional color target and showed low luminance.

Comparative Example 2 using a yellow pigment showed low brightness and contrast.

From the results, compared to a photosensitive resin composition for a color filter which is combined with a dye containing only a cyanine dye and a metal complex dye without a yellow or orange dye, contains yellow or according to one embodiment The photosensitive resin composition for a color filter of an orange dye and a cyanine dye and a metal complex dye achieves further improved brightness while maintaining an appropriate contrast.

While the invention has been described in connection with what is considered to be illustrative embodiments of the present invention, it is understood that the invention is not limited to the disclosed embodiments. Various modifications and equivalent arrangements within the scope. Therefore, the above embodiments are to be considered as illustrative and not restrictive.

Claims (16)

A photosensitive resin composition for a color filter comprising: (A) a yellow or orange dye; (B) a dye combination of a cyanine dye and a metal complex dye represented by the following Chemical Formula 1; (C) acrylic acid a binder-like resin; (D) a photopolymerizable monomer; (E) a photopolymerization initiator; and (F) a solvent: Wherein, in the above Chemical Formula 1, X ₁ and X ₂ are each independently carbon, nitrogen, oxygen or sulfur, and R1 to R4 and R11 to R14 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted a 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 a 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 group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group a substituted, unsubstituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted 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, each of R5, R6, R8 and R9 being independently a hydrogen atom or a substituted or unsubstituted C1 to C20 a radical, R7 and R10 are, 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 from 1 to 4, a, b, c and d are each independently an integer of 0 or 1, and A is a halogen ion, ClO ₄ ^- , BF ₄ ^- , SbF ₆ ^- , CF ₃ SO ₃ ^- , N(SO ₂ CF ₃ ) ₂ ^- or one of the compounds represented by the following chemical formulas 2-1 and 2-2: Photosensitive for color filters as described in claim 1 A resin composition in which the yellow or orange dye has a transmittance of 0% to 40% in a wavelength region of 380 nm to 500 nm, and a transmittance of 50% to 100% in a wavelength region of 570 nm to 590 nm. The photosensitive resin composition for color filters according to claim 1, wherein the yellow or orange dye is selected from the group consisting of a direct dye, an acid dye, a basic dye, an acid mord dye, a sulphur dye, Reduction dyes, ice dyes, disperse dyes, reactive dyes, oxidation dyes, alcohol dyes, azo dyes, anthraquinone dyes, indigo dyes, carbocation dyes, phthalocyanine dyes, nitro dyes, quinoline dyes, cyanine dyes , methine dyes, and combinations thereof. The photosensitive resin composition for a color filter according to claim 1, wherein the yellow or orange dye has a transmittance of 0% to 1% in a wavelength region of 380 nm to 450 nm, and The transmittance in the wavelength region of 450 nm to 550 nm has a transmittance of 1% to 100%. The photosensitive resin composition for a color filter according to claim 1, wherein in the above Chemical Formula 1, A is CF ₃ SO ₃ ^- or N(SO ₂ CF ₃ ) ₂ ^- . The photosensitive resin composition for a color filter according to the above aspect of the invention, wherein the cyanine dye represented by the above Chemical Formula 1 re-emits light in a wavelength of from 400 nm to 700 nm. The photosensitive resin for a color filter according to claim 1, wherein the cyanine dye is a red dye. Photosensitive for color filters as described in claim 1 A resin composition in which the metal complex dye has a maximum absorption peak in a wavelength of from 200 nm to 650 nm. The photosensitive resin composition for a color filter according to claim 1, wherein the metal complex dye comprises at least one selected from the group consisting of Mg, Ni, Cu, Co, Zn, Cr, and Pt. Metal ions of Pd, Pd, and Fe. The photosensitive resin composition for a color filter according to claim 1, wherein the metal complex dye includes a metal ion and a complex selected from at least one of the following: solvent yellow 19, a 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, solvent 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 according to the first aspect of the invention, wherein the photosensitive resin composition for a color filter further contains a pigment. The photosensitive resin composition for a color filter according to claim 11, wherein the pigment comprises CI Pigment Red 242, CI Pigment Red 214, CI Pigment Red 221, CI Pigment Red 166, CI At least one of Pigment Red 220, CI Pigment Red 248, CI Pigment Red 262, CI Pigment Red 254, CI Pigment Red 177, and CI Yellow Pigment 150. The photosensitive resin composition for a color filter according to claim 11, wherein the photosensitive resin composition for a color filter comprises a weight ratio of 1:9 to 9:1. The cyanine dye and the pigment. Photosensitive for color filters as described in claim 1 a resin composition, wherein the photosensitive resin composition for a color filter comprises: 0.1% by weight to 5% by weight of the yellow or orange dye (A); and 1% by weight to 80% by weight of the cyanine dye Combination with the dye of the metal complex dye (B); 0.1% by weight to 30% by weight of the acrylic binder resin (C); 0.1% by weight to 30% by weight of the photopolymerizable monomer (D), 0.1% by weight to 5% by weight of the photopolymerization initiator (E); and the balance of the solvent (F). A color filter manufactured by using a photosensitive resin composition for a color filter according to the first aspect of the invention. The color filter of claim 15, wherein the color filter is applied to an LED light source.