JP5707105B2 - Yellow coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a yellow coloring composition for a color filter used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed using the same.

A color liquid crystal display device is basically sealed between a first transparent substrate on which a first transparent electrode layer is formed, a second transparent substrate on which a second transparent electrode layer is formed, and a gap between them. The color filter is usually formed between the second transparent substrate and the second transparent electrode. First and second polarizing plates are provided outside the first and second transparent substrates, respectively, and a backlight unit including a backlight light source is provided outside the first polarizing plate. .
In such a liquid crystal display device, the voltage applied between the first and second transparent electrode layers is adjusted for each filter segment, and the degree of polarization of light from the backlight unit that has passed through the first polarizing plate is controlled. The display is performed by controlling the amount of light passing through the second polarizing plate. Therefore, the color characteristics of the color filter and the polarizing plate are important factors that determine the color characteristics of the liquid crystal display device.

  A color filter has a black matrix, which is a light shielding pattern, and red, green, and blue fine band (striped) filter segments arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or a fine filter. It is composed of filter segments arranged in a constant arrangement. The filter segment or black matrix that constitutes the color filter is coated with a photosensitive material on a glass substrate, etc., dried and removed excess solvent, and then exposed through a photomask for pixel formation (ultraviolet light source exposure), etc. In general, it is formed by a so-called photolithography method by irradiating with an active energy ray, curing (negative type) or increasing alkali solubility (positive type), and removing a portion dissolved by an alkaline solution or the like. By repeating this for each color, a color filter is produced.

  In the production of color filters, spinners, bar coaters or roll coaters as conventional coating devices have been used, but in recent years it has been possible to reduce the consumption of coating liquid and improve the physical properties of the coating film. The use of a die coater is being considered. Die coaters have been widely used for thick film coating and continuous application of high-viscosity paints. When forming a coating film using a die coater, a coating method such as the bead method is used. Is known. In the bead method, paint is discharged from a slit provided in a die coater die, and a paint reservoir called a bead is formed between the die and a material to be moved relatively at a constant interval. This is a method of forming a coating film by drawing out the paint as the material to be coated runs in the state. In this method, there is almost no waste of paint, and since the paint liquid supply path is sealed until it is discharged from the slit, it is possible to prevent paint deterioration and contamination, and to improve the quality of the obtained coating film. Highly maintainable.

  However, in the production of a color filter, when the coating film is a thin film having a dry film thickness of 10 μm or less, when trying to apply such a thinner coating film, the volume of the bead becomes small. Stability is impaired, and there is a high possibility of occurrence of horizontal stripe unevenness that occurs in a direction perpendicular to the traveling direction of the die on the coating film surface. Since the coating film in which such unevenness has occurred cannot be used as a colored layer in a color filter, it has been desired to form a colored layer with little occurrence of such unevenness.

  In recent years, liquid crystal display devices have been evaluated for space saving, light weight, and power saving due to their thinness, and their applications are rapidly expanding to large televisions and monitors. The demand for higher brightness, higher color reproducibility, and higher contrast is increasing for color filters that determine the color characteristics.

As a means for high color reproduction, it is effective to provide a color filter with a fourth filter segment in addition to the red, green, and blue filter segments. It is advantageous to use an advantageous yellow filter segment.
By reproducing the color with four color filter segments, the color reproduction range can be expanded compared to the color filter composed of three colors, and the color filter can be obtained by adding yellow, which has higher luminance than red, green and blue. Higher brightness is being studied.
However, in the conventional yellow filter segment, the contrast ratio and brightness are insufficient at present.

JP 2008-096470 A JP 2008-052239 A JP 2009-008920 A

  Accordingly, the present invention provides a yellow coloring composition used for the manufacture of a color filter having a high contrast ratio, high brightness, and a wide color reproduction region, and a liquid crystal display capable of expressing sharp and vivid colors using the same. An object is to provide an apparatus.

The yellow coloring composition of the present invention contains a dye (a), a binder resin (b), an organic solvent (c), an active energy ray polymerization initiator (d), and an active energy ray curable monomer (e). In this coloring composition, the dye (a) is a main dye (a1) which is an azo yellow pigment having a specific surface area of 90 m ² / g or more by BET method, and other yellow pigments or orange pigments. A toning dye (a2), and the content of the toning dye (a2) is 0.07 wt% or more and less than 20 wt% in a total of 100 wt% of the dye (a), and When a coating film is formed using the coloring composition so that the spectral transmittance at 470 nm is 1% or less, the spectral transmittance at 520 nm of the coating film is 80% or less, and the spectral transmittance at 540 nm is 75% or more. And at 600nm Spectral transmittance is equal to or less than 90%.

In the present invention, the main pigment (a1) is C.I. I. The yellow coloring composition for a color filter, which is CI Pigment Yellow 150.
In the present invention, the toning pigment (a2) is C.I. I. Pigment yellow 139 or C.I. I. It is a pigment orange 38, It is related with the said yellow coloring composition for color filters characterized by the above-mentioned.
The present invention also relates to a color filter comprising a filter segment formed from the yellow coloring composition for a color filter.
The present invention also relates to a color filter including a red filter segment, a green filter segment, a blue filter segment, and a yellow filter segment, wherein the yellow filter segment is formed of the yellow coloring composition for the color filter. .

  The yellow filter segment using the yellow coloring composition of the present invention is excellent in contrast ratio and brightness, and the color filter comprising the yellow filter segment, the red filter segment, the green filter segment, and the blue filter segment is Further, it is possible to provide a liquid crystal display device which is a color filter having a high contrast ratio, a high brightness, and a wide color reproduction region, and capable of expressing sharp and vivid colors.

It is the figure which showed the transmittance | permeability spectrum of the filter from the emission spectrum and yellow of a general pseudo white LED backlight.

First, various components of the yellow coloring composition for a color filter of the present invention will be described.
In addition, “CI” described below means a color index (CI).

The yellow coloring composition for a color filter of the present invention comprises a dye (a), a binder resin (b), an organic solvent (c), an active energy ray polymerization initiator (d), and an active energy ray curable monomer (e ) Containing a main coloring matter (a1), wherein the coloring matter (a) is an azo-based yellow pigment having a specific surface area of 90 m ² / g or more according to the BET method; A toning dye (a2) which is a yellow pigment or an orange pigment, and the content of the toning dye (a2) is 0.07% by weight or more in a total of 100% by weight of the dye (a). When the coating film is formed so that the spectral transmittance at 470 nm is 1% or less using the coloring composition, the spectral transmittance at 520 nm of the coating film is 80% or less, and Spectral transmission at 540 nm There more than 75%, and the spectral transmittance at 600nm is 90% or more.
The yellow coloring composition for a color filter of the present invention is a color filter excellent in the balance of characteristics such as high contrast ratio, high brightness, and wide color reproduction region because the coating film has the specific spectral characteristics. can get. In particular, when a coating film having a film thickness of 2.5 μm or less after drying was formed using the colored composition so that the spectral transmittance at 470 nm was 1% or less, the spectrum at 520 nm of the coating film was If the transmittance is 80% or less, the spectral transmittance at 540 nm is 75% or more, and the spectral transmittance at 600 nm is 90% or more, it is possible to cope with the thinning and high brightness demanded in recent years. Moreover, it is preferable from the viewpoint of energy saving and resource saving.

<Dye (a)>
The yellow coloring composition for a color filter of the present invention includes a main coloring matter (a1) which is an azo-based yellow pigment having a specific surface area of 90 m ² / g or more by the BET method and other yellow pigments or orange pigments as the coloring matter (a). And a toning pigment (a2). In the present invention, a dye having the largest weight percentage in the total dye (a) is a main dye, and a dye having a weight percentage less than the main dye in the total dye (a) is a toning dye.

  Further, the content of the toning dye (a2) which is another yellow pigment or an orange pigment is 0.07% by weight or more and less than 20% by weight in the total 100% by weight of the dye (a). Features.

  The preferable concentration of the dye (a) in all the non-volatile components of the yellow coloring composition for a color filter according to the present invention is 5 to 80% by weight, more preferably 10 to 70% by weight from the viewpoint of obtaining sufficient color reproducibility. %, Most preferably 15 to 60% by weight. When the concentration of the dye (a) is less than 5% by weight, sufficient color reproducibility cannot be obtained, and when it exceeds 80% by weight, the storage stability of the colored composition is deteriorated, or by the photolithography method. Problems occur in the formation of filter segments.

[Main pigment (a1)]
The main coloring matter (a1) in the present invention is an azo yellow pigment having a specific surface area of 90 m ² / g or more by BET method. Further, preferably 90m ² / g or more ~175m ² / g or less, and most preferred is 95 m ² / g or more ~165m ² / g or less. On the other hand, if it is 175 m ² / g or more, the pigment is fine and nitrogen gas cannot be completely adsorbed, and accurate measurement may not be possible. However, there is no problem in using it for the yellow coloring composition for color filters of the present invention.

  As a method for adjusting the specific surface area, a known method can be used. For example, a salt milling process is mentioned. Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water.

  In addition, the specific surface area by BET method is a specific surface area measured in accordance with “Measurement method of gas adsorption amount by one-point method” defined in Appendix 2 of Japanese Industrial Standard JIS Z8830-1990.

Examples of the azo yellow organic pigment include C.I. I. Pigment Yellow 1, 3, 9, 12, 13, 14, 17, 55, 74, 81, 83, 87, 93, 94, 95, 97, 98, 116, 117, 128, 132, 150, 155, 167, 168, 169, 183, 191, 194, 198, 199, 203, 213, 214 and the like.
Among these, C.I. I. Pigment Yellow 13, 83, 150, 213, 214 and the like are more preferable in terms of good color characteristics. Among them, C.I. I. Pigment Yellow 150 is most preferred.
In addition, two or more of the above azo yellow organic pigments can be mixed and used.

  The content of the main dye (a1) may be the largest if the weight% in the total dye (a) is the largest, but is preferably 50% by weight or more and 99.93% by weight or less in the total 100% by weight of the dye (a). . If it exceeds 99.93% by weight, the effect of the toning pigment is not exhibited, and if it is less than 50% by weight, the contrast ratio and color characteristics may be deteriorated. More preferably, when it exceeds 80% by weight, excellent effects can be confirmed in all of the brightness, contrast ratio, and color reproduction region. More preferably, it is 83 weight% or more.

[Toning dye (a2)]
As the toning dye (a2), a yellow pigment different from an azo yellow organic pigment having a specific surface area of 90 m ² / g or an orange pigment is used to obtain a desired hue.
Examples of yellow pigments include C.I. I. Pigment Yellow 2, 4, 5, 6, 10, 12, 15, 16, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 60, 61, 62, 63, 65, 73, 77, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 118, 119, 120, 123, 126, 127, 129,138,139,147,151,152,153,154,156,161,162,164,166,170,171,172,173,174,175,176,177,179,180,181,182, 185, 187, 188, 193 and the like, and a dye different from the main dye (a1) can be a toning dye. Among these, C.I. I. Pigment Yellow 139, 185 and the like are more preferable in terms of good color characteristics. Among them, C.I. I. Pigment Yellow 139 can be most preferably used as the toning yellow pigment (a2).
Also, C.I. having a specific surface area of less than 90 m ² / g. I. Pigment Yellow 150 corresponds to the toning dye (a2), but is less preferred as the toning dye because of its small spectral characteristics and hue shift effect.

  Examples of the orange pigment for toning include C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73, 80, etc. can be used, but C.I. I. Pigment Orange 38 is more preferable.

  The content of the toning pigment (a2) is 0.07 wt% or more and less than 20 wt% in the total 100 wt% of the pigment (a). If it is 20% by weight or more, the contrast ratio and brightness may be lowered depending on the toning pigment. If it is less than 0.07% by weight, the effect of improving the color characteristics is small, which is not preferable. Preferably they are 1.0 weight% or more and 15 weight% or less.

  In particular, when the toning dye (a2) is Pigment Yellow 139, 1.0 to 15% by weight is more preferable in the total 100% by weight of the dye (a), and the most preferable range is 1.5. % By weight or more and less than 10% by weight. When the toning dye (a2) is Pigment Orange 38, the amount is more preferably 0.07 wt% or more and less than 5 wt% based on the total amount of the dye, and the most preferable range is 1.0 wt% or more and less than 3 wt%. It is. When the amount is less than the above range, the effect of the toning dye is not observed, and when the amount is large, the brightness and contrast decrease greatly.

[Other toning dyes]
The yellow coloring composition for a color filter of the present invention may further contain other toning pigments such as a yellow dye and an orange dye. A particularly preferable dye is an organic solvent-soluble dye, and the contrast can be increased and the brightness can be increased by dissolving the dye in the organic solvent in the colored composition of the present invention.
Examples of the chemical structure of the dye include azo dyes and thiazole dyes.
In the following, usable dyes are exemplified by color index (CI) numbers, but not limited thereto.
Examples of the azo direct dye include CI Direct Yellow 2, 33, 34, 35, 39, 50, 69, 70, 71, 86, 93, 94, 95, 98, 102, 109, 129, 136. 141; CI Direct Orange 41, 46, 56, 61, 64, 70, 96, 97, 106, 107.
Examples of the thiazole-based direct dye include CI Direct Yellow 54.
Other direct dyes include CI Direct Yellow 38, 43, 47, 58, 68, 108, 138; CI Direct Orange 34, 39, 50, 52, 57, 65, 68; It is done.
As an acid dye other than the direct dye, an azo acid dye, a quinoline acid dye, or the like can be used.
Examples of the azo acid dyes include CI Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; CI Acid Yellow 1, 17, 18 , 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151.
Examples of quinoline acid dyes include CI Acid Yellow 3 and 5.
Furthermore, it can have both high heat resistance and light resistance by salting an acidic dye. Two or more of the above dyes can be mixed and used.

<Binder resin (b)>
The binder resin (b) is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The binder resin (b) includes a thermoplastic resin, a thermosetting resin, and a photosensitive transparent resin, and these can be used alone, but are preferably used in combination of two or more.

  The binder resin (b) can be used in an amount of 3 to 2000 parts by weight with respect to 100 parts by weight of the total weight of the pigment (a). If it is less than 3 parts by weight, the developability, film formability and various resistances tend to be insufficient, and if it exceeds 2000 parts by weight, the colorant concentration is low and color characteristics cannot be expressed. The amount is preferably 10 to 1000 parts by weight.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like.
Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a phenol resin, a melamine resin, and a urea resin.

  The photosensitive transparent resin is a resin having an ethylenically unsaturated double bond, for example, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an aldehyde group, an epoxy group. A functional group having an ethylenically unsaturated double bond, such as a (meth) acryloyl group or a styryl group, by reacting a (meth) acrylic compound having a reactive substituent such as a carboxyl group or cinnamic acid. Introduced resin is mentioned. Specifically, a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond are added to a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group and another ethylenically unsaturated monomer. Some of them are obtained by reacting the compounds they have. Examples of the functional group capable of reacting with a hydroxyl group include an isocyanate group and a carboxyl group, but an isocyanate group is particularly preferred in terms of reactivity, and specifically, a compound having an isocyanate group and an ethylenically unsaturated double bond. , 2-acryloyl ethyl isocyanate, 2-methacryloyl ethyl isocyanate and the like. In addition, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

<Organic solvent (c)>
In the yellow coloring composition for a color filter of the present invention, a pigment is sufficiently dispersed in the composition, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easy to form, an organic solvent (c) can be contained.

The organic solvent (c) is preferably used in an amount of 65 to 95% by weight in 100% by weight of the colored composition. If it is less than 65% by weight, the fluidity is poor and unevenness is likely to occur during coating. If it exceeds 95% by weight, it takes a long time to dry after coating. More preferably, it is 70 to 93% by weight to 100% by weight of the coloring composition.
Examples of the organic solvent (c) include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, and 2-heptanone. 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,5,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1, 3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl Benzene, ethyl ethoxypropionate, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotarsia Libutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Ter, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol Methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, include dibasic acid esters such as, used these alone or in mixtures.

<Active energy ray polymerization initiator (d)>
The yellow coloring composition for a color filter of the present invention contains an active energy ray polymerization initiator (d) for forming a filter segment by a photolithography method.
As the active energy ray polymerization initiator (d), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2- Acetophenone compounds such as morpholinopropan-1-one, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin compounds such as tellurium and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl- 4,6-bis (trichloromethyl) -s-tria 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy) -Naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) Triazine compounds such as -6-triazine, 1- [4- (phenylthio) phenyl] -octane-1-one-2-oneoxime-O-acetate, 1- [4- (2-methylphenylthio) phenyl]- Octane-1-one-2-one oxime-O-acetate, 1- [4- (2,4,6-trimethylphenylthio) phenyl] -octane-1-one-2-one Xime-O-acetate, 1- [4- (2-ethylphenylthio) phenyl] -octane-1-one-2-oneoxime-O-acetate, 1- [4- (phenylthio) phenyl] -octane-1- On-2-one oxime-O-benzoate, 1- [4- (2-methylphenylthio) phenyl] -octane-1-one-2-one oxime-O-benzoate, 1,2-octadion-1- [4- (Phenylthio) phenyl-, 2- (O-benzoyloxime)], 1- [4- (2,4,6-trimethylphenylthio) phenyl] -octane-1-one-2-oneoxime-O-benzoate, 1 -[4- (2-Ethylphenylthio) phenyl] -octane-1-one-2-oneoxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9 . H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2,4,6-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O Oxime ester compounds such as -acetyloxime), phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrene Examples include quinone compounds such as quinone, camphorquinone, and ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, and titanocene compounds. These photopolymerization initiators can be used alone or in combination.

  Of these, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H An oxime ester compound such as -carbazol-3-yl]-, 1- (O-acetyloxime) is preferred because of its high sensitivity.

  The content of the active energy ray polymerization initiator (d) is preferably 0.3 to 200 parts by weight with respect to 100 parts by weight of the dye (a). If it is out of the range, problems may occur in the formation of filter segments by photolithography.

  The active energy ray polymerization initiator (d) can be used in combination with a sensitizer. Examples of the sensitizer include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone. Thioxanthone compounds such as 2,4-diethylthioxanthone, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid 2-dimethylaminoethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone Amine compounds such as 4,4'-bis (ethylmethylamino) benzophenone. These sensitizers can be used individually by 1 type or in mixture of 2 or more types. The content of the sensitizer is preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the active energy ray polymerization initiator (d).

<Active energy ray-curable monomer (e)>
The yellow coloring composition for a color filter of the present invention contains an active energy ray-curable monomer (e) for forming a filter segment by a photolithography method. The active energy ray-curable monomer (e) is a compound having an ethylenically unsaturated double bond. Examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meta ) Acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) Acrylic esters and methacrylic esters such as acrylate and epoxy (meth) acrylate, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, Examples include acrylonitrile. The active energy ray-curable monomer (e) preferably has 4 to 12 ethylenically unsaturated double bonds, and more preferably 6 to 12 from the viewpoint of increasing the sensitivity of the colored composition. The active energy ray-curable monomer (e) can be used alone or in combination of two or more compounds having an ethylenically unsaturated double bond.

  The content of the active energy ray-curable monomer (e) is preferably 1 to 300 parts by weight with respect to 100 parts by weight of the dye (a). If it is out of the range, problems may occur in the formation of filter segments by photolithography.

<Optional component>
The yellow coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.
Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. Etc. A storage stabilizer can be used in the quantity of 0.1-10 weight part with respect to 100 weight part of pigment | dye (a) in a coloring composition.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the dye (a) in the coloring composition.

  When a pigment is used for the dye (a) and the pigment is dispersed in the binder resin (b), a dispersant such as a surfactant, a resin-type pigment dispersant, and a dye derivative can be appropriately used. The dispersant is excellent in dispersion of the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when the pigment is dispersed in the binder resin (b) and the organic solvent (c) using the dispersant, transparency is obtained. An excellent color filter can be obtained. The dispersant can be used in an amount of 0.1 to 200 parts by weight, preferably 0.1 to 150 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

  Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate. , Anionic surface activity such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Agents: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxy Nonionic surfactants such as ethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethyl Examples include amphoteric surfactants such as alkylbetaines such as aminoacetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

  Resin-type pigment dispersants are resins that have a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the transparent resin, and stabilize the dispersion of the pigment into the transparent resin by adsorbing to the pigment. It works to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 3184, manufactured by Japan Lubrizol Corporation EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400405, manufactured by Efka Chemicals, etc. 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503 and the like.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Such organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

  The yellow colored composition for a color filter of the present invention may contain a polyfunctional thiol for improving sensitivity in a photolithography method. For example, it may be a compound having two or more thiol groups such as hexanedithiol, Decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, tri Methylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Lis (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s- Examples include triazine. These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.

  The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the pigment.

<The manufacturing method of a coloring composition>
As a method for producing a yellow colored composition for a color filter of the present invention, a dye (a), a binder resin (b), an organic solvent (c), an active energy ray polymerization initiator (d), and an active energy ray-curable single monomer. The body (e) is mixed with other dispersion aids, additives and the like, if necessary, and adjusted as a solvent developing type or alkali developing type photosensitive coloring composition (resist material).
At this time, first, a known dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, or an attritor is used in the binder resin (b) and the organic solvent (c) together with a dispersing agent if necessary. The active energy ray polymerization initiator (d), the active energy ray-curable monomer (e), other additives, and the like can be mixed after being finely dispersed and used as a pigment dispersion.

  The pigment dispersion can also be dispersed by mixing two or more pigments that are the main pigment (a1) and the toning pigment (a2), and each pigment is separately dispersed in the binder resin (b) and Although it can be produced by mixing finely dispersed organic solvents (c), it is preferable from the standpoint of stability of the dye dispersion to prepare and mix individual dye dispersions.

  In addition, the dispersed particle size of the pigment dispersion can be measured by a dynamic light scattering method (FFT power spectrum method), and the dispersed particle size can be adjusted by changing the type of dispersing machine and operating conditions described above. it can.

  The dispersion particle diameter D50 of the dye dispersion containing the main dye (a1) measured by the dynamic light scattering method is preferably 40 nm or more and less than 200 nm from the viewpoint of brightness and contrast ratio. When the dispersion particle diameter D50 of the dye dispersion is less than 40 nm, the dispersion particle system is small and stability is lowered by reaggregation, which is not preferable. On the other hand, when the thickness is 200 nm or more, the brightness and contrast ratio are lowered, which is not preferable.

  Further, the dispersion particle diameter D50 of the dye dispersion containing the toning dye (a2) measured by the dynamic light scattering method is more preferably 40 nm or more and less than 200 nm from the viewpoints of brightness and contrast ratio. When the dispersion particle diameter D50 of the dye dispersion is less than 40 nm, the dispersion particle system is small and stability is lowered by reaggregation, which is not preferable. On the other hand, when the thickness is 200 nm or more, the brightness and contrast ratio are lowered, which is not preferable.

  Note that the same result may not be obtained even if the same particle size is measured depending on the measurement principle, apparatus, sample preparation method, parameter setting, etc., but in the present invention, the dynamic light scattering method is used. Using Nikkiso Microtrack UPA-EX150 adopting (FFT power spectrum method), the particle permeability was absorption mode, the particle shape was non-spherical, and D50 was the average diameter.

The content of the pigment (a) in the colored composition of the present invention is preferably 0.4% by weight or more and 18% by weight or less, and more preferably 1.0% by weight or more and 15% by weight or less.
Moreover, it is preferable that content of the pigment | dye (a) in the non volatile matter in a coloring composition is 5 to 60 weight%. If it is less than 5% by weight, the film thickness becomes too thick in order to obtain desired spectral characteristics. When the amount is more than 60% by weight, the storage stability of the colored composition may deteriorate. More preferably, it is 10 to 50 weight%.

  The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

<Color filter>
The color filter of the present invention comprises a yellow filter segment formed from the yellow coloring composition for a color filter of the present invention on a substrate.
Furthermore, the color filter preferably includes the yellow filter segment, the red filter segment, the green filter segment, and the blue filter segment.

  Next, specific examples of usable organic pigments for the red, green, and blue coloring compositions used as the color filter segment together with the yellow coloring composition for the yellow filter segment are shown by color index numbers.

  Examples of the red photosensitive coloring composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, Red pigments such as 255, 264, 272, and 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red photosensitive coloring composition.

Examples of the yellow pigment that can be used in combination with the red pigment in the red photosensitive coloring composition include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17 6, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213 or 214 can be used.
Moreover, these yellow pigments can be used for the yellow photosensitive coloring composition for forming a yellow filter segment individually or in combination of 2 or more types.

Examples of the orange pigment that can be used in combination with the red pigment in the red photosensitive coloring composition include C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73 or 80 can be used.
Moreover, these orange pigments can be used for the orange photosensitive coloring composition for forming an orange filter segment individually or in combination of 2 or more types.

Examples of the green photosensitive coloring composition for forming the green filter segment include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, 37 or 58 can be used. In addition to this green pigment, the yellow pigment can be used in combination with the green photosensitive coloring composition.
Examples of the blue photosensitive coloring composition for forming the blue filter segment include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or 80 can be used. In addition to this blue pigment, C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42 or 50 can be used in combination.

  In the red, green, and blue coloring compositions, the binder resin, organic solvent, active energy ray polymerization initiator, active energy ray-curable monomer, and optional components can be used as components that can be contained in the yellow coloring composition. .

Next, a method for manufacturing the color filter of the present invention will be described.
The method for producing a color filter of the present invention includes a step of forming a colored coating film on a substrate using the yellow colored composition for a color filter of the present invention, or the red, green, and blue colored compositions for a color filter, It has the process of irradiating and curing the active energy ray to the part used as the filter segment of the said colored coating film, and the process of forming the filter segment by removing the uncured part of the said colored coating film.
Moreover, the color filter manufactured by the method of the present invention comprises a yellow filter segment and red, green, and blue filter segments formed from the yellow coloring composition for a color filter of the present invention on a substrate. Moreover, you may have a black matrix as a partition of each color filter segment.

(Colored coating film forming process)
In the colored coating film forming step, the yellow coloring composition for color filters of the present invention or the red, green, and blue coloring compositions for color filters of the present invention are applied by spin coating or die coating, and an extra solvent is added as necessary. By removing, a colored coating film is formed on the substrate.
Color filter substrates include glass plates such as soda-lime glass, low alkali borosilicate glass, and non-alkali aluminoborosilicate glass that have a high transmittance for visible light, and resins such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. A plate is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

(Exposure and curing process)
In the exposure / curing step, the colored coating film formed on the substrate is irradiated with an active energy ray through a photomask to cure a portion to be a filter segment of the colored coating film. As the active energy rays, electron beams, ultraviolet rays, visible light of 400 to 500 nm, and various lasers can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source. Examples of the ultraviolet ray and visible light source (light source) of 400 to 500 nm include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and gallium. A lamp, a xenon lamp, a carbon arc lamp, or the like can be used. As the laser, a semiconductor laser, a YAG (solid) laser, a gas laser (argon laser, helium neon laser, carbon dioxide laser, excimer laser) or the like can be used.

(Uncured part removal process)
In the uncured portion removing step, the uncured portion of the colored coating film is removed to form a filter segment. When removing the uncured portion, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  The color filter of the present invention is preferably used in combination with a pseudo white LED light source (backlight light source or front light light source). The pseudo white LED light source is a white light source that combines a blue LED and a phosphor that absorbs blue light and emits fluorescence such as yellow. The pseudo-white LED light source has strong and sharp light emission in the blue wavelength region and light emission that is weaker and broader than blue light emission in the longer wavelength region (green to red wavelength region). Generally, it has two emission peaks of a blue region and a green to red region, but there are also some having a plurality of peaks from a green region to a red region. The pseudo white LED is available from NSPA 300BS, NSPW310BS, NSPW312BS, NSPW315BS, NSPW500BS, NEPW500, etc. manufactured by Nichia Corporation. By using the pseudo white LED light source in combination with the color filter of the present invention, the color reproduction region of the liquid crystal display device can be further expanded, and the utilization efficiency of the backlight light can be increased. The emission spectrum of a general pseudo white LED backlight and the transmittance spectrum of a yellow color filter are shown in FIG.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. However, the present invention is not limited to the following examples unless it exceeds the gist.

In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. Moreover, the measuring method of the polymerization average molecular weight (Mw) of a resin, the refinement | miniaturization degree of a pigment, the contrast ratio of a coating film, and the dispersion particle diameter of a pigment | dye dispersion is as follows.

<Resin polymerization average molecular weight (Mw)>
The polymerization average molecular weight (Mw) of the resin is a polystyrene equivalent measured using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw).

<Pigment refinement>
The fineness of the pigment was evaluated by the specific surface area of the pigment particles. The specific surface area was measured with an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the BET method of nitrogen adsorption.

<Contrast ratio (CR) of coating film>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio (CR)) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio (CR)) = (Brightness when parallel) / (Brightness when direct)
The luminance meter used was “Color Luminance Meter BM-5A” manufactured by Topcon Corporation, and the polarizing plate used was “Polarized Film LLC2-92-18” manufactured by Sanritsu. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

<Dispersed particle size of pigment dispersion>
Using a Nikkiso Microtrac UPA-EX150 employing a dynamic light scattering method (FFT power spectrum method), the particle permeability was determined as an absorption mode, the particle shape as an aspherical shape, and D50 as an average diameter.

  First, the acrylic resin solutions used in Examples and Comparative Examples, the preparation of fine pigments, and the method for producing a yellow dye dispersion will be described.

[Synthesis of acrylic resin solution]
Put 700 parts of cyclohexanone in a reaction vessel and heat to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 133 parts of n-butyl methacrylate, 46 parts of 2-hydroxyethyl methacrylate, 43 parts of methacrylic acid, paracumylphenol A mixture of 74 parts of ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) and 4.0 parts of 2,2′-azobisisobutyronitrile was dropped over 2 hours to carry out a polymerization reaction.
After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.
After cooling to room temperature, about 2 g of acrylic resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized acrylic resin solution so that the nonvolatile content was 20% by weight. Addition to obtain an acrylic resin solution 1 used in the examples. The weight average molecular weight Mw of the obtained acrylic resin was 26,000.

[Pigment]
The pigments used in Examples and Comparative Examples are shown in Table 1.

(Preparation of azo yellow pigment 2)
Azo-based yellow pigment 1 (CI Pigment Yellow 150, “E-4GN” manufactured by LANXESS) 500 parts, sodium chloride 500 parts, and diethylene glycol 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 120 The mixture was kneaded at 0 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of azo yellow pigment 2 were obtained.

(Preparation of azo yellow pigment 5)
Similar to the preparation of azo yellow pigment 2, except that azo yellow pigment 1 was changed to azo yellow pigment 4 (CI Pigment Yellow 150, “Lionol Yellow FG-1310” manufactured by Toyo Ink Co., Ltd.). An azo yellow pigment 5 was obtained.

(Preparation of yellow pigment 2 for toning)
Yellow pigment 1 for toning (CI Pigment Yellow 139, “Irgafore Yellow 2R-CF” manufactured by Ciba Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol, 1 gallon kneader made of stainless steel (Inoue Seisakusho) And kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of toning yellow pigment 2 were obtained.

(Preparation of orange pigment 2)
200 parts of diketopyrrolopyrrole-based orange pigment 1 (CI Pigment Yellow Orange 38, “Chromophthal DPP Orange TR” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) A stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) was charged and kneaded at 70 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for about 2 hours while being heated to about 80 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then at 85 ° C. overnight. Drying gave 190 parts of orange pigment 2.

[Preparation of yellow pigment dispersion]
Next, preparation of the pigment dispersion used in Examples and Comparative Examples will be described.
The mixture of the dye (a) shown in Table 2 was uniformly stirred and mixed, dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a yellow dye dispersion.
However, for the dye dispersion 3 and the dye dispersion 9, the sand mill dispersion time was changed to 12 hours.

Binder resin (b): Acrylic resin solution 1
Organic solvent (c): PGMEA (propylene glycol monomethyl ether acetate)

The structure of the dye derivative is shown below.

[Examples 1 to 13 and Comparative Examples 1 to 4]
(Preparation of yellow coloring composition for color filter)
The mixture having the composition shown in Table 3 was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain Examples 1 to 13 and Comparative Examples 1 to 4 which were alkali development type colored compositions.
However, Examples 1, 4, 8, and 9 are reference examples.

Binder resin (b): Acrylic resin solution 1
Active energy ray-curable monomer (e): Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Active energy ray polymerization initiator (d): Oxime ester photopolymerization initiator Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0- Acetyloxime) ("Irgacure OXE-02" manufactured by Ciba Japan)
Organic solvent (c): PGMEA (propylene glycol monomethyl ether acetate)

[Evaluation of coloring composition]
(Viscosity of coloring composition)
The viscosity of the coloring composition was measured at a rotation speed of 20 rpm using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. on the coloring composition adjustment day. The results are shown in Table 3.

(Preparation of colored composition coated substrate by die coater)
The obtained colored composition was applied to a 100 mm × 100 mm size glass substrate having a thickness of 0.7 mm by separating the glass substrate from the slit die by 150 μm and using a die coater at a coating speed of 100 mm / sec.
The coated film was dried by removing the solvent in an oven at 70 ° C. for 20 minutes, and then exposed to ultraviolet light with an integrated light quantity of 100 mJ / cm ² using an ultrahigh pressure mercury lamp. The coated substrate of each colored composition was obtained by heating the coated substrate at 230 ° C. for 60 minutes.

(Spectral transmittance and hue (x, y, Y) evaluation)
The spectral transmittance and hue of the obtained coated substrate were measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The light source was a C light source. The brightness Y was determined according to the following.
X: Y <77.0
Δ: 77.0 ≦ Y <80.0
○: 80.0 ≦ Y <83.0
A: 83.0 ≦ Y

(Contrast ratio evaluation)
The contrast ratio of the obtained coated substrate was measured. The contrast ratio was determined according to the following.
X: Y <8000
Δ: 8000 ≦ Y <9000
○: 9000 ≦ Y <10000
A: 10000 ≦ Y

(Color reproduction area evaluation)
The color characteristics of the color filter are as follows: the RGB chromaticity coordinates defined by the EBU standard, the square area composed of the chromaticity coordinates of Examples and Comparative Examples, and the triangular area composed of the RGB chromaticity coordinates defined by the NTSC standard The ratio (NTSC ratio) was calculated and evaluated. The light source was a C light source. NTSC ratio was determined according to the following.
X: Y <75.3
Δ: 75.3 ≦ Y <75.9
○: 75.9 ≦ Y <76.5
A: 76.5 ≦ Y
The results are shown in Table 4 below.

The yellow coating film formed from the yellow coloring composition for a color filter of the present invention had no items for which the judgment was x, and all of them had high contrast ratios, high brightness, and a wide color reproduction region. .
Comparative Examples 1 and 3 using a pigment having a specific surface area outside the range of the present invention had a low contrast ratio.
Comparative Example 2 in which the content of the toning dye (a2) is out of the range of the present invention has low brightness.
In addition, the yellow colored composition of Comparative Example 4 which does not contain the toning dye (a2), which is a feature of the present invention, was a result that the spectrum did not satisfy the scope of the present invention and the NTSC ratio was low.

(Manufacture of color filters)
The dye in the yellow dye dispersion is C.I. I. Pigment Red 254 / C.I. I. Pigment Red 177 = 60 parts / 40 parts, C.I. I. Pigment Green 36 / C.I. I. Pigment Yellow 150 = 60 parts / 40 parts, C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment Violet 23 = 90 parts / 10 parts except that the dye dispersion was prepared in the same manner as the yellow dye dispersion 2, and further, a red coloring composition for a color filter, a green coloring composition for a color filter, and a color filter A blue colored composition was obtained.
The red coloring composition was applied on a 100 mm × 100 mm glass substrate with a die coater to a thickness of about 2 μm, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Furthermore, after spray development with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, the substrate is washed with ion-exchanged water, and this substrate is heated at 230 ° C. for 30 minutes to form a red filter segment having a line width of about 50 μm. did. Next, in the same manner, the green filter segment is used with the green color composition next to the red filter segment, the blue filter segment is used with the blue color composition, and then the yellow color composition for the color filter of Example 3 is used. A yellow filter segment was used to obtain a color filter having four color filter segments on the same glass substrate.

  Since the color filter of the present invention has a high contrast ratio, high brightness, and a wide color reproduction region, a liquid crystal display device using the color filter can express a vivid and vivid color.

a Relative emission intensity of pseudo white LED backlight b Transmittance of yellow filter

Claims (6)

Yellow coloring composition for a color filter comprising a dye (a), a binder resin (b), an organic solvent (c), an active energy ray polymerization initiator (d), and an active energy ray curable monomer (e) In things,
A main coloring matter (a1) which is an azo yellow pigment having a specific surface area of 90 m ² / g or more by BET method, and a toning coloring matter (a2) which is another yellow pigment or an orange pigment; Including
The content of the toning dye (a2) is 0.07 wt% or more and less than 20 wt% in a total of 100 wt% of the dye (a),
And when a coating film was formed using the coloring composition so that the spectral transmittance at 470 nm was 1% or less, the spectral transmittance at 520 nm of the coating film was 80% or less and the spectral transmittance at 540 nm was 75% or more and the spectral transmittance at 600 nm is 90% or more,
A pigment dispersion (A1) in which a main pigment (a1) is dispersed in a binder resin (b) and an organic solvent (c), and a dispersed particle diameter D50 measured by a dynamic light scattering method is 40 nm or more and less than 200 nm. )When,
A pigment dispersion in which the toning pigment (a2) is dispersed in the binder resin (b) and the organic solvent (c), and the dispersed particle diameter D50 measured by the dynamic light scattering method is 40 nm or more and less than 200 nm A yellow coloring composition for a color filter obtained by mixing (A2).   The main pigment (a1) is C.I. I. The yellow coloring composition for a color filter according to claim 1, which is at least one selected from the group consisting of CI Pigment Yellow 13, 83, 150, 213, and 214.   Toning dye (a2) is C.I. I. Pigment yellow 139, 185, and C.I. I. The yellow coloring composition for a color filter according to claim 1 or 2, wherein the yellow coloring composition is at least one selected from the group consisting of CI Pigment Orange 38.   A color filter comprising a filter segment formed from the yellow coloring composition for a color filter according to any one of claims 1 to 3. A color filter comprising a red filter segment, a green filter segment, a blue filter segment, and a yellow filter segment, wherein the yellow filter segment is formed by the yellow coloring composition for a color filter according to any one of claims 1 to 3. Color filter that has been made. Yellow coloring composition for a color filter comprising a dye (a), a binder resin (b), an organic solvent (c), an active energy ray polymerization initiator (d), and an active energy ray curable monomer (e) In the manufacturing method of a thing,
A main coloring matter (a1) which is an azo yellow pigment having a specific surface area of 90 m ² / g or more by BET method, and a toning coloring matter (a2) which is another yellow pigment or an orange pigment; Including
Total of 100 wt% of the content of the dye (a) of該調color dye (a2), Ri der less than 0.07 wt% to 20 wt%,
Or One, when the spectral transmittance at 470nm using a colored composition to form a coating film to be less than 1%, the spectral transmittance at 520nm of the coating film is 80% or less, and the spectral transmittance in 540nm Is 75% or more and the spectral transmittance at 600 nm is 90% or more,
A pigment dispersion (A1) in which a main pigment (a1) is dispersed in a binder resin (b) and an organic solvent (c), and a dispersed particle diameter D50 measured by a dynamic light scattering method is 40 nm or more and less than 200 nm. )When,
A pigment dispersion in which the toning pigment (a2) is dispersed in the binder resin (b) and the organic solvent (c), and the dispersed particle diameter D50 measured by the dynamic light scattering method is 40 nm or more and less than 200 nm (A2) is mixed, The manufacturing method of the yellow coloring composition for color filters characterized by the above-mentioned.

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