JP2009086089A - Green pigment dispersion for color filter, green-curable resin composition for color filter, color filter and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersion and a curable-resin composition having excellent pigment dispersibility, from which a color filter with high contrast can be formed. <P>SOLUTION: A green pigment dispersion for a color filter is disclosed, which contains a green pigment, a yellow or orange pigment showing a light transmittance in a specified test film, of ≥90% in a wavelength range from 560 nm to 640 nm and ≤12% in a wavelength range from 400 nm to 450 nm, a pigment dispersant and a solvent, wherein the average dispersion particle diameter of the dispersed pigment particles is from 15 to 80 nm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is used for a color pigment green pigment dispersion used for forming a colored layer such as a pixel, a green curable resin composition for a color filter, and a liquid crystal display device using the resin composition. Related to the color filter.

Liquid crystal display devices have been mainly used as monitors for personal computers, but in recent years, not only as monitors for personal computers but also for TV monitors, they have been rapidly developed. Increasing contrast is an important issue.
In general, as shown in FIG. 2A, the color liquid crystal display device (101) is provided with a gap portion 3 of about 1 to 10 μm with the color filter 1 and an electrode substrate 2 such as a TFT substrate facing each other. 3 is filled with a liquid crystal compound L, and the periphery thereof is sealed with a sealing material 4. The color filter 1 includes a light shielding layer (black matrix layer) 6 formed in a predetermined pattern on the transparent substrate 5 to shield the boundary between the colored layers, and a plurality of colors (usually normal) to form each pixel. , Red (R), green (G), and blue (B) are arranged in a predetermined order, a protective layer 8 and a transparent electrode film 9 are arranged in this order from the side close to the transparent substrate. It has a laminated structure. An alignment film 10 is provided on the inner surface side of the color filter 1 and the electrode substrate 2 facing the color filter 1. Furthermore, a spacer is provided in the gap portion 3 in order to maintain a constant and uniform cell gap between the color filter 1 and the electrode substrate 2. As the spacer, pearls 11 having a constant particle diameter are dispersed, or columnar spacers 12 having a height corresponding to the cell gap as shown in FIG. 6 is formed in a region overlapping with the position where 6 is formed. A color image is obtained by controlling the light transmittance of each colored layer colored in each color or the liquid crystal layer behind the color filter.

  At present, it is a mainstream to produce a colored layer of a color filter by a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant. However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

  In order to realize high luminance and high contrast of the color filter, it has been studied so far to make the pigment contained in the colored layer fine (for example, Patent Document 1). In Patent Document 1, in a pigment composed of an aggregate of primary particles, the number ratio of primary particles having a particle diameter of 0.1 μm or less is 95% or more of all particles, and the number ratio of primary particles having a particle diameter of more than 0.1 μm A refined pigment characterized by being less than 5% of the total number of particles is disclosed. However, the pigment particle size disclosed herein is the particle size of the produced pigment itself. Pigments whose primary particles have been made finer generally tend to aggregate, and even if finer pigments are used, the pigment particles actually dispersed in the resin composition may exist as coarse particles or fine particles. In general, it is difficult to obtain a stable coloring composition, for example, when the conversion to too much proceeds, a huge lump of pigment solid is formed. Also in Patent Document 1, in the coloring composition obtained by dispersing the above-mentioned fine pigment in a dispersion medium, the average particle diameter of the dispersed pigment particles is preferably 0.2 μm or less. Has been. In the conventional dispersed particle size distribution of the dispersed pigment as disclosed in Patent Document 1, light leaks to the OFF state, which is insufficient to improve the contrast.

  On the other hand, in order to solve the further increase in the transmittance of the color filter and the excellent color separation, Patent Document 2 proposes mixing a yellow pigment with a green pigment. However, Patent Document 2 does not describe any improvement in contrast.

JP 2003-89756 A JP 2001-249215 A

  The present invention has been accomplished in view of the above circumstances, and the object thereof is a green pigment dispersion for a color filter capable of forming a color filter having a high contrast, a green curable resin composition for a color filter, and the resin. An object of the present invention is to provide a color filter having a high contrast and a display device using the composition.

  As a result of intensive studies in view of the above problems, the present inventors have performed toning using a pigment capable of increasing parallel luminance without increasing orthogonal luminance in a wavelength range where the green pigment transmits, and dispersing When a colored layer of a color filter is formed using a green curable resin composition in which the dispersed particle diameter of the pigment is controlled, light leaks when light must be blocked (OFF state) It has been found that the transmitted light can be raised when it has to pass through (ON state) and the contrast is dramatically improved, and the present invention has been completed.

That is, the present invention includes a green pigment, a yellow or orange pigment having a light transmittance of 90% or more in the wavelength range of 560 nm to 640 nm and 12% or less in the wavelength range of 400 nm to 450 nm, A green pigment dispersion for a color filter, comprising a pigment dispersant and a solvent, wherein the dispersed pigment particles have an average dispersed particle diameter of 15 to 80 nm. I will provide a.
Further, the present invention provides a green pigment and a yellow or orange pigment having a light transmittance of 90% or more in the wavelength range of 560 nm to 640 nm and 12% or less in the wavelength range of 400 nm to 450 nm, A green curable resin composition for a color filter comprising a pigment dispersant, a curable binder system, and a solvent, wherein an average dispersed particle size of dispersed pigment particles is 15 to 80 nm. A green curable resin composition for a color filter is provided.
[Test membrane]
30 parts by weight of the yellow or orange pigment and the pigment dispersants 12 to 24 so that y = 0.450 in the chromaticity coordinates (x, y) in the XYZ color chromaticity diagram measured using a C light source A resin composition for a test film comprising 76 to 88 parts by weight of a methyl methacrylate / methacrylic acid copolymer (molar ratio 9/1) having a weight average molecular weight of 7000 to 15000 and a solvent of 520 parts by weight is obtained using an alkali-free glass. A test film is formed by applying and drying on a substrate.

  According to the present invention, the pigment dispersion is achieved by adjusting the average dispersion particle size of the pigment particles that are toned and dispersed using the yellow or orange pigment having the specific light transmittance. It is possible to obtain a green pigment dispersion for a color filter and a green curable resin composition for a color filter capable of forming a color filter having excellent properties and high contrast.

  In the pigment dispersion and the curable resin composition of the present invention, the yellow or orange pigment is 3 to 45% by weight in the total pigment, so that a specific color necessary for the green pixel of the color filter is obtained. It is preferable from the viewpoint of improving contrast while achieving it.

  In the pigment dispersion and the curable resin composition of the present invention, the green pigment is at least one selected from the group consisting of CI pigment green 36, CI pigment green 7, and CI pigment green 58. This is preferable from the viewpoint of improving the contrast while achieving a specific color necessary for the green pixel of the color filter.

  In the pigment dispersion and the curable resin composition of the present invention, the yellow or orange pigment is CI pigment yellow 150, CI pigment yellow 185, CI pigment yellow 17, CI pigment yellow 138, CI pigment yellow 139, CI pigment. A specific color necessary for the colored layer of the color filter to be at least one selected from the group consisting of yellow 173, CI pigment yellow 117, CI pigment orange 66, CI pigment orange 68, and CI pigment orange 69 From the point of improving contrast while achieving the above.

  In the pigment dispersion and the curable resin composition of the present invention, in the dispersed pigment particles, the contrast is more improved when the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm are 99% or more of the total pigment particles. It is preferable from the point.

  In the pigment dispersion and the curable resin composition of the present invention, the pigment dispersant contains a repeating unit derived from dimethylaminoethyl (meth) acrylate or a quaternary ammonium salt of dimethylaminoethyl (meth) acrylate. A polymer and / or a polyallylamine derivative is preferable from the viewpoint of high pigment dispersion performance in the combination of the solvent system and the organic pigment.

  In the pigment dispersion and the curable resin composition of the present invention, the solvent is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), and cyclohexanone. Is preferable from the viewpoints of solubility of other components and applicability.

  In the curable resin composition according to the present invention, it is preferable that the curable binder system is a photosensitive binder system because it can be cured by light in a short time and a pattern can be easily formed.

  In the curable resin composition according to the present invention, 0.450 ≦ y <0.600 in the chromaticity coordinates (x, y) in the XYZ color chromaticity diagram measured using a C light source. When the cured film of the resin composition is formed, the ratio of the luminance that is transmitted when the cured film of the resin composition is sandwiched between two polarizing plates that are orthogonal or parallel (luminance / polarized light when the polarizing plates are parallel) The luminance when the plate is orthogonal is preferably 3500 or more from the viewpoint of achieving high contrast.

The color filter according to the present invention includes a colored layer formed using the curable resin composition according to the present invention.
A display device according to the present invention includes the color filter according to the present invention.

The green pigment dispersion for a color filter and the green curable resin composition for a color filter of the present invention are a green colored layer having a high contrast due to excellent pigment dispersibility and toning that effectively uses a bright line of a backlight, In addition, there is an effect that it is possible to form a color filter including the green colored layer.
The color filter and the display device of the present invention have an effect that high contrast can be realized by using the curable resin composition according to the present invention.

  The present invention relates to a green pigment dispersion for a color filter and a method for producing the same, a green curable resin composition for a color filter, a color filter, and a display device. Hereinafter, the green pigment dispersion for color filter and the production method thereof, the green curable resin composition for color filter, the color filter, and the display device will be described in order. In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. In the present invention, (meth) acryl means either acryl or methacryl, (meth) acrylate means either acrylate or methacrylate, and (meth) acryloyl is , Meaning either acryloyl or methacryloyl.

1. Green pigment dispersion for color filter The green pigment dispersion for color filter according to the present invention has a light transmittance of 90% or more in the wavelength region of 560 nm to 640 nm and a wavelength of 400 nm to 450 nm. A green pigment dispersion for a color filter comprising a yellow or orange pigment that is 12% or less in the region, a pigment dispersant, and a solvent, wherein the dispersed pigment particles have an average dispersed particle size of 15 to 80 nm It is characterized by being.
[Test membrane]
30 parts by weight of the yellow or orange pigment and the pigment dispersants 12 to 24 so that y = 0.450 in the chromaticity coordinates (x, y) in the XYZ color chromaticity diagram measured using a C light source A resin composition for a test film comprising 76 to 88 parts by weight of a methyl methacrylate / methacrylic acid copolymer (molar ratio 9/1) having a weight average molecular weight of 7000 to 15000 and a solvent of 520 parts by weight is obtained using an alkali-free glass. A test film is formed by applying and drying on a substrate.
The pigment dispersant and solvent used for preparing the test film are the pigment dispersant and solvent used in the pigment dispersion according to the present invention. More specifically, the resin composition for test membranes, for example, mixes and disperses 30 parts by weight of a yellow or orange pigment, 12 to 24 parts by weight of a pigment dispersant, and 46 to 58 parts by weight of a solvent, The mixture is formed by mixing 76 to 88 parts by weight of a methyl methacrylate / methacrylic acid copolymer (molar ratio 9/1) having a weight average molecular weight of 7000 to 15000 and 462 to 474 parts by weight of a solvent, and mixing the two mixtures. be able to. Moreover, the residual solvent amount in the test film after drying is usually 25% or less.
In the present invention, the weight average molecular weight refers to a polystyrene equivalent value measured using gel permeation chromatography (GPC).

  Here, the dispersed particle diameter in the pigment dispersion of the present invention is a dispersed particle diameter of pigment particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. is there. For particle size measurement using a laser light scattering particle size distribution meter, the solvent used in the pigment dispersion is appropriately diluted to a concentration that can be measured with the laser light scattering particle size distribution meter (eg, 500 times). It can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is a volume average particle size.

  The pigment dispersion is a pigment composition (pigment content in the composition / total amount of the composition) that is preliminarily prepared in the pre-stage of preparing the resin composition described later. Specifically, the pigment content is 5% by weight or more. By mixing the pigment dispersion and at least the binder component, a resin composition having both the pigment dispersibility and the properties of the binder component can be prepared.

  According to the present invention, the light transmittance of the test film is toned using a yellow or orange pigment that is 90% or more in the wavelength region of 560 nm to 640 nm and 12% or less in the wavelength region of 400 nm to 450 nm. And a green pigment dispersion for a color filter capable of forming a color filter having excellent pigment dispersibility and high contrast by adjusting the average dispersed particle size of the dispersed pigment particles to 15 to 80 nm. Obtainable.

The contrast ratio is a ratio of luminance on the display device (ON state / OFF state) when light must be transmitted (ON state) and when light must be blocked (OFF state). Therefore, in order to achieve a high contrast among them, the luminance (when in an ON state) that becomes a numerator and must transmit light (hereinafter sometimes referred to as parallel luminance) is increased, while it becomes a denominator. Therefore, it is important to suppress the value of luminance (hereinafter sometimes referred to as orthogonal luminance) when light must be blocked (hereinafter, sometimes referred to as orthogonal luminance), that is, to prevent light from leaking into the OFF state. It was.
As a result of intensive studies in view of the above problems, the present inventors have determined that the average dispersed particle diameter of the dispersed pigment particles is 15 to 80 nm, and the light transmittance of the test film is 90 in the wavelength region of 560 to 640 nm. It is possible to increase the parallel luminance while keeping the orthogonal luminance small by toning the yellow or orange pigment that is not less than 12% and not more than 12% in the wavelength range of 400 nm to 450 nm in combination with the green pigment. As a result, it has been found that the contrast is dramatically improved.
When the above specific yellow or orange pigment is used in combination with a green pigment, and a green pigment dispersion composed of only a green pigment having an average dispersed particle size of 15 to 80 nm is used. Compared with, the contrast is greatly improved.
Furthermore, the contrast is dramatically improved as compared with the case of using a conventional green pigment dispersion in which the average dispersed particle size of the dispersed pigment particles is not appropriately controlled.

In the present invention, the dramatic improvement in contrast is considered to be due to the following reason.
That is, in the present invention, attention is focused on two wavelength ranges in which the transmittance of the green pigment is not so high, 560 nm to 640 nm and 400 nm to 450 nm, among the wavelength ranges where the green pigment of the bright line of the backlight transmits. For bright lines in the wavelength range of 560 nm to 640 nm, since the transmittance in the wavelength region is not so high with the green pigment alone, the parallel luminance is considerably lower than the parallel luminance in the case of air. On the other hand, in the present invention, a yellow or orange pigment having a transmittance of 90% or more in the wavelength region of 560 nm to 640 nm under a specific condition is also used, so that it is parallel to the emission line in the wavelength range of 560 nm to 640 nm. The brightness is remarkably improved. Furthermore, among the yellow or orange pigments having a transmittance of 90% or more in the wavelength range of 560 nm to 640 nm, a pigment having a transmittance of 12% or less in the wavelength range of 400 nm to 450 nm is selected and used. The toning can prevent the transmittance in the range of 400 nm to 450 nm from becoming larger than that of the green pigment, and can prevent the orthogonal luminance with respect to the bright line in the range of 400 nm to 450 nm from increasing. Further, among yellow or orange pigments having a transmittance of 90% or more in the wavelength region of 560 nm to 640 nm and a transmittance of 12% or less in the wavelength region of 400 nm to 450 nm, the average dispersed particle size of the dispersed pigment particles By selecting and using a pigment having a thickness of 15 to 80 nm, a large number of regions where the light scattering of visible light is unaffected by the My scattering, the influence of the particle size is reduced, and it leaks to the OFF state Light can be effectively reduced and the orthogonal luminance can be prevented from increasing.

On the other hand, among the yellow or orange pigments having a transmittance of 90% or more in the wavelength range of 560 nm to 640 nm, when using a pigment having a high transmittance in the wavelength range of 400 nm to 450 nm, bright lines in the range of 400 nm to 450 nm The orthogonal luminance with respect to increases. An increase in the value of the orthogonal luminance of the denominator in the contrast ratio has a greater effect than an increase in the value of the numerator, so that even if the parallel luminance is greatly increased, the contrast is not greatly improved.
Further, pigment particles dispersed in a dispersion medium even in the case of a yellow or orange pigment having a transmittance of 90% or more in the wavelength region of 560 nm to 640 nm and a transmittance of 12% or less in the wavelength region of 400 nm to 450 nm If the average dispersed particle size of the particles is not properly controlled, for example, if a large number of particles having a dispersed particle size of 100 nm or more are included, the particles having a dispersed particle size of 100 nm or more have the property of diffracting scattered light depending on the size. The amount of light increases, the amount of light that leaks to the OFF state increases, the orthogonal luminance increases in each bright line of the backlight, and the contrast decreases. Even if a finer pigment is used as the pigment, it is often aggregated in the dispersion medium, and the average dispersed particle diameter of the pigment particles actually dispersed in the dispersion medium becomes large as in Patent Document 1. There is a case.

  As described above, in the present invention, as a result of performing appropriate color matching with the dispersed particle diameter of the pigment particles, the parallel luminance can be improved, while the increase in the orthogonal luminance can be suppressed, the contrast ( It is estimated that the ON state (parallel luminance) / OFF state (orthogonal luminance)) can be remarkably improved.

The green pigment dispersion for a color filter of the present invention contains at least a pigment, a pigment dispersant, and a solvent, and may contain other compounds as necessary.
Hereinafter, each configuration of the pigment dispersion of the present invention will be described in detail in order.

<Pigment>
As a pigment used in the present invention, a green pigment and a yellow or orange color whose light transmittance of the test film is 90% or more in a wavelength region of 560 nm to 640 nm and 12% or less in a wavelength region of 400 nm to 450 nm. At least a pigment. The green pigment and the yellow or orange pigment are appropriately selected depending on the use and specifications of the color filter. The green pigment and the yellow or orange pigment are used by mixing one or more of inorganic pigments and organic pigments. Moreover, unless the chromaticity required for the use and specification in a color filter can be achieved and the effect of this invention is not impaired, the other pigment may be further contained.
As organic pigments, for example, compounds classified as Pigment in the Color Index (CI; published by The Society of Dyers and Colorists), specifically, the following Color Index (CI) numbers are attached. You can list what you have.

  Examples of the green pigment include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, and Green Pigment containing a compound whose central metal is a metal other than Cu such as Zn in C.I. Pigment Green 36. C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 58 are preferable from the viewpoint of improving contrast while achieving a specific color required for the green pixel of the color filter. Among these, C.I. Pigment Green 58 is a high-brightness pigment, and is therefore preferably used because it has high brightness when the polarizing plate is parallel when measuring contrast and the contrast is easily improved.

  The yellow or orange pigment used in combination with the green pigment preferably has a higher transmittance in the wavelength region of 560 nm to 640 nm, and the lower the transmittance in the wavelength region of 400 nm to 450 nm, the parallel luminance can be improved. On the other hand, since an increase in orthogonal luminance can be suppressed, it is preferable from the viewpoint that contrast (ON state (parallel luminance) / OFF state (orthogonal luminance)) can be improved. Above all, the yellow or orange pigment preferably has a light transmittance of 93% or more in the wavelength range of 560 nm to 640 nm. The light transmittance of the test film is preferably 8% or less in the wavelength region of 400 nm to 450 nm.

Examples of yellow or orange pigments capable of achieving a light transmittance of 90% or more in the wavelength range of 560 nm to 640 nm and 12% or less in the wavelength range of 400 nm to 450 nm of the test film include CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Yellow 17, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 173, CI Pigment Yellow 117, CI Pigment Orange 66, CI Pigment Orange 68, CI Pigment Orange 69, and the like.
Among these, CI pigment yellow 150, CI pigment yellow 185, CI pigment yellow 17, CI pigment yellow 138, CI pigment yellow 139, CI pigment yellow 173, and CI pigment yellow 117 are preferably used.

Even if the pigment has the pigment number, if the average dispersed particle size of the pigment particles is too large or the average dispersed particle size is small, but there are coarse particles, the light transmittance of the test film is low. In some cases, 90% or more in the wavelength region of 560 nm to 640 nm and 12% or less in the wavelength region of 400 nm to 450 nm cannot be achieved.
From this point, the yellow or orange pigment used in combination is preferably a material having a primary particle size distribution in the range of 5 to 100 nm, and the average dispersed particle size of dispersed pigment particles is 15 to 80 nm. Is preferred.

  The specific yellow or orange pigment is preferably 3 to 45% by weight in the total pigment from the viewpoint of improving the contrast while achieving the green chromaticity required for the specification of the color filter, Furthermore, it is preferable that it is 3 to 40 weight% in all the pigments.

  The method of refining the pigment used is not particularly limited as long as the dispersion particle size distribution as specified in the present invention is obtained when the pigment is dispersed in the dispersion medium. For example, a method of mechanically pulverizing pigment particles as typified by the solvent salt milling method, a method of returning the pigment particles to a molecular state once by dissolution, etc., and precipitating in a fine particle state using a temperature change or a poor solvent, Examples thereof include a method of directly producing fine particle pigments during pigment synthesis by controlling reaction conditions.

  The pigment is preferably blended in a proportion of 3 to 20% by weight, more preferably 5 to 15% by weight, based on the total amount of the green pigment dispersion for color filters.

<Pigment dispersant>
The pigment dispersant is further blended in the pigment dispersion to disperse the above-mentioned pigment satisfactorily. Examples of the pigment dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable. A pigment derivative that dissolves in a small amount in a solvent may be used as a pigment dispersant.

  The pigment dispersant is appropriately selected and used in order to favorably disperse the pigment used. Specific examples include amide compounds such as nonanamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide, diethylamine, diheptylamine, Amine compounds such as dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethyl) Polyoxyethylene) -1,2-diaminoethane, 1 , 4-bis (2-hydroxyethyl) piperazine and amines having a hydroxy group such as 1- (2-hydroxyethyl) piperazine, and the like, and other compounds such as nipecotamide, isonipecotamide, and nicotinamide are listed. be able to.

  Further, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid ( Partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphorus Acid salts; amides obtained by the reaction of poly (lower alkyleneimine) and free carboxyl group-containing polyester, salts thereof, and the like can be mentioned.

  Examples of the pigment dispersant used in the present invention include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid , (Partial) ammonium salts and (partial) alkylamine salts; hydroxyl group-containing unsaturated carboxylic acid ester (co) polymers such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; Siloxanes; Long-chain polyaminoamide phosphates; Amides obtained by the reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters and their salts are effective for dispersion in non-aqueous systems (solvent systems) It is preferable because it is a dispersant that can utilize steric hindrance and acid-base adsorption.

  Among these, as the pigment dispersant used in the present invention, a polymer containing a repeating unit derived from dimethylaminoethyl (meth) acrylate or a quaternary ammonium salt of dimethylaminoethyl (meth) acrylate is preferable. Examples of the polymer include methyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and γ-butyrolactone modified product of (meth) acrylic acid. Copolymers with other (meth) acrylic acid esters are preferably used. Among them, (meth) acrylic acid methyl and (meth) acrylic acid dimethylaminoethyl or (meth) acrylic acid dimethylaminoethyl quaternary ammonium salts A copolymer containing a repeating unit derived from is preferably used, and in particular, a block copolymer containing poly (meth) acrylate methyl and polyblock (meth) acrylate dimethylaminoethyl or a quaternary ammonium salt thereof. Are preferably used.

  The pigment dispersant used in the present invention is preferably a polyallylamine derivative. The polyallylamine derivative preferably used as a pigment dispersant in the present invention is, for example, a polyester or polyamide having a side chain amino group and a free carboxyl group, or a co-condensate of polyester and amide (polyesteramide). A polyallylamine derivative represented by the following general formula (I) is obtained by reacting with one or more compounds selected from three kinds of compounds.

（式中、ＸおよびＹは、それぞれ独立に水素、重合開始剤残基又は連鎖移動触媒残基のいずれかを、Ｒ¹ は遊離のアミノ基、下記一般式（II）又は(III）で示される基を、ｎは２〜１，０００の整数を表す。但しｎ個のＲ¹中、少なくとも１個は一般式（III）で示される基を表す。

(Wherein X and Y are each independently hydrogen, a polymerization initiator residue or a chain transfer catalyst residue, R ¹ is a free amino group, represented by the following general formula (II) or (III) N represents an integer of 2 to 1,000, provided that at least one of n R ^{1 s} represents a group represented by formula (III).

式中、Ｒ²は遊離のカルボン酸を有するポリエステル、遊離のカルボン酸を有するポリアミド、または遊離のカルボン酸を有するポリエステルアミドのいずれかからカルボキシル基を除いた残基を表す。）

In the formula, R ² represents a residue obtained by removing a carboxyl group from any of a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid. )

  This polyallylamine derivative is, for example, a polyallylamine having a polymerization degree of 2 to 1,000, a polyester having a free carboxyl group, represented by the following general formula (IV) or (V), and the following general formula (VI) or One kind of polyamide represented by (VII) can be prepared as a raw material alone or in combination of two or more kinds.

（式中Ｒ³ は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基を、そしてａは２〜１００の整数を示す。）

(In the formula, R ³ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and a represents an integer of 2 to 100.)

（式中Ｒ⁴ は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基、Ｃ₆ Ｈ₄ またはＣＨ＝ＣＨを、Ｒ⁵ は炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基、ポリアルキレングリコールから２つの水酸基を除いた残基を、そしてｂは２〜１００の整数を示す。また、前期鎖中にエーテル結合を有することもある。）

Wherein R ⁴ is a linear or branched alkylene group having 2 to 20 carbon atoms, C ₆ H ₄ or CH═CH, and R ⁵ is a linear or branched alkylene having 2 to 20 carbon atoms. A group, a residue obtained by removing two hydroxyl groups from polyalkylene glycol, and b represents an integer of 2 to 100. In addition, an ether bond may be present in the primary chain.)

（式中Ｒ⁶ は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基を、そしてｃは２〜１００の整数を示す。）

(In the formula, R ⁶ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and c represents an integer of 2 to 100.)

（式中Ｒ⁴ は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基、Ｃ₆ Ｈ₄ またはＣＨ＝ＣＨを、Ｒ⁷ は炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基を、そしてｄは２〜１００の整数を示す。）

(Wherein R ⁴ is a linear or branched alkylene group having 2 to 20 carbon atoms, C ₆ H ₄ or CH═CH, and R ⁷ is a linear or branched alkylene having 2 to 20 carbon atoms. A group, and d represents an integer of 2 to 100.)

  In addition, the polyallylamine derivative suitably used as a pigment dispersant in the present invention is a polyester in which repeating components of general formula (IV) and general formula (V) are randomly polymerized to polyallylamine, general formula (VI) and general A polyamide in which the repeating component of the formula (VII) is randomly polymerized, and further a polyesteramide in which the repeating components of the general formula (IV) and / or (V) and the general formula (VI) and / or (VII) are randomly polymerized. It can also be produced by reacting.

  Commercially available dispersants include Disperbyk-101, -116, -130, -140, -160, -161, -162, -163, -164, -166, and -167. -168, -170, -171, -174, -182, -182, -2000, -2001, and -2050 (above, manufactured by Big Chemie Japan Co., Ltd.), EFKA-4046, and- 4047 (manufactured by EFAK CHEMICALS), Solsperse 12000, 13240, 13940, 17000, 20000, 24000GR, 24000SC, 27000, 28000, 32000, 33500, 33500, 35200, 37500 (above, manufactured by Nippon Lubrizol Co., Ltd.), Addispar PB711, 82 , The 822,823,824 (or more, Ajinomoto Fine manufactured by Techno Co., Ltd.), and the like. Moreover, it is more preferable to use what refine | purified them in order to improve the reliability of a color filter.

  The pigment dispersant is preferably blended at a ratio of 20 to 80 parts by weight, and further 20 to 60 parts by weight with respect to 100 parts by weight of the pigment.

<Solvent>
The green pigment dispersion for color filter according to the present invention contains a solvent for dispersing the pigment.
Examples of the solvent used in the pigment dispersion of the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; Carbitol solvents such as ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone and cyclohexanone; methoxyethyl acetate Cellosolve acetate solvents such as methoxypropyl acetate, methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; methoxyethoxyethyl Carbitol acetate solvents such as cetate and ethoxyethoxyethyl acetate; ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Aprotic amide solvents; lactone solvents such as γ-butyrolactone; unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane And organic solvents such as Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA); Ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol diethyl ether; ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate are preferably used. Among them, the solvent used in the present invention is selected from the group consisting of propylene glycol monomethyl ether acetate (CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), propylene glycol monomethyl ether, butyl carbitol acetate (BCA), and cyclohexanone. It is preferable that it is 1 or more types from the point of the solubility of another component, and the applicability | paintability.

These solvents may be used alone or in combination of two or more.
The pigment dispersion according to the present invention is prepared by using the above solvent in a proportion of usually 60 to 85% by weight with respect to the total amount of the pigment dispersion containing the solvent. When the amount of the solvent is too small, the viscosity is increased, and the pigment dispersibility and the pigment dispersion stability with time are likely to be lowered. Moreover, when there are too many solvents, a pigment density | concentration will fall and it may be difficult to achieve the chromaticity coordinate which makes a resin composition the target after preparation.

<Other ingredients>
If necessary, the pigment dispersion according to the present invention may further contain a pigment dispersion auxiliary resin and other components.
Examples of the pigment dispersion auxiliary resin include a binder resin described below.

<Physical properties of pigment dispersion>
The pigment dispersion according to the present invention has an average dispersed particle diameter of 15 to 80 nm as measured with a laser light scattering particle size distribution meter. Among these, the average dispersed particle diameter of the pigment measured by a laser light scattering particle size distribution meter is preferably 15 to 70 nm, and more preferably 15 to 60 nm.

  In the pigment dispersion according to the present invention, among the dispersed pigment particles, the pigment particles having a dispersed particle size of 5 nm or more and less than 100 nm have 99% or more of the total pigment particles and have a similar average dispersed particle size. Even in this case, it is preferable in that the light leaking into the OFF state can be greatly reduced and the contrast can be drastically improved. If the dispersed pigment particles contain particles with a dispersed particle size of 100 nm or more, the particles with a dispersed particle size of 100 nm or more have a property of diffracting the scattered light depending on the size, so that the scattered light of polarized light increases, and the OFF state Light that leaks into the screen will be generated. When particles having a dispersed particle diameter of 100 nm or more are not included, even if the average dispersed particle diameter is the same, it is presumed that the influence of the particle size is almost eliminated and light leaking into the OFF state can be effectively reduced. In addition, among the dispersed pigment particles, it is preferable that the pigment particle having a dispersed particle size of 5 nm or more and less than 100 nm is 99.5% or more, more preferably 99.9% or more of the total pigment particles. In addition, 99% or more of the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm means 99% by volume or more.

  Among them, in the pigment dispersion according to the present invention, particles having a dispersed particle diameter of 1/5 or more of the absorption wavelength of the contained pigment are less than 1%, further less than 0.5%, particularly less than 0.1%. Preferably there is.

The dispersion particle size distribution of the pigment in the pigment dispersion is, among other things, 5 to 30% by volume of the pigment particles having a dispersion particle size of 5 nm or more and less than 30 nm in the dispersed pigment particles. It is preferable that 30 to 90% by volume of pigment particles of 30 nm or more and less than 61 nm, and 0 to 50% by volume of pigment particles of 61 nm or more and less than 100 nm. In particular, pigment particles having a dispersed particle size of 5 nm or more and less than 30 nm are It is preferable that 10 to 50% by volume, 50 to 90% by volume of pigment particles having a dispersed particle diameter of 30 to 61 nm, and 0 to 20% by volume of pigment particles having 61 to 100 nm.
Furthermore, it is preferable that the particle size when the cumulative particle size distribution is 50% by volume in all pigment particles is 65 nm or less.

  Further, after storing the pigment dispersion at 40 ° C. for 1 week, it was measured again at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution analyzer, and the average dispersed particle size before and after storage was measured. The dispersion stability can be examined on the basis of whether or not is increased by 10 nm. When the dispersion stability is high, the average dispersed particle diameter does not change and is less than 10 nm within the error range.

  In the present invention, after the dispersion of the pigment molecules proceeds, coarse particles having a specific size such as 100 nm or more in the dispersed pigment molecules or a primary particle size of less than 5 nm, for example, by centrifugation as described later. Fine particles can be stably dispersed by removing particles that cannot be present in a stable dispersion state, or particles that are in an unstable dispersion state that has been agglomerated because the surface treatment is not complete even at 5 nm or more. From the viewpoint of obtaining a dispersion liquid. Thus, when the unstable particles aggregated from the dispersion are removed, the remaining fine pigment particles are difficult to aggregate and can exist stably. Further, even in a resin composition prepared using this pigment dispersion, fine pigment particles hardly aggregate and exist stably as fine particles in the resin composition.

<Method for producing pigment dispersion>
The pigment dispersion of the present invention is prepared by mixing the above-mentioned pigment, the pigment dispersant, and if necessary, other components in the above-mentioned solvent in an arbitrary order and dispersing them using a known disperser. Can do.
Since the pigment dispersion liquid of the present invention contains a green pigment and a specific yellow or orange pigment, two or more kinds of pigments are included. For each type of pigment, one pigment dispersion liquid is prepared. Then, they may be mixed to obtain the green pigment dispersion of the present invention, or a green pigment dispersion may be obtained by dispersing two or more kinds of pigments at a time.
Among them, the dispersion time varies up to the dispersion limit for each pigment, and the dispersion often exceeds the dispersion time. Therefore, the average dispersion particle size of the pigment particles specified in the present invention is obtained. It is preferable to prepare one pigment dispersion for each pigment and then mix them to obtain the green pigment dispersion of the present invention. In this case, if different dispersants are used for the respective pigments, they may be aggregated. Therefore, it is preferable that the types of the pigment dispersants used for dispersing the respective pigments are the same.

When a photosensitive resin composition is produced later, an alkali-soluble resin may be added to the dispersion in advance after confirming that the dispersibility by the dispersant is not inhibited. In this case, the pigment particles are less likely to come into contact with each other due to the steric hindrance of the alkali-soluble resin, and the effect of reducing the dispersant due to the dispersion stabilization and the dispersion stabilization effect can also be expected.
Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.10 to 1.0 mm.

  When dispersing the pigment, it is preferable to add zirconia beads or the like as appropriate and perform dispersion for about 1 to 5 hours using a paint shaker (manufactured by Asada Steel Corporation) or the like. Specifically, it is possible to disperse with 2 mm zirconia beads having a relatively large bead diameter for 1 hour and further with 0.1 mm zirconia beads having a relatively small bead diameter for 2 to 10 hours. Moreover, it is preferable to filter with a membrane filter of 0.5 to 0.1 μm after dispersion.

  In particular, in the case of dispersed pigment particles, when the pigment particle having a dispersed particle size of 5 nm or more and less than 100 nm is 99% or more of the total pigment particles, as described later, it is centrifuged for a short time at a high rotational speed of a specific value or more. It is preferable to further use a method of removing pigment particles having a dispersed particle diameter of 100 nm or more from pigment particles that are separated and classified and dispersed.

A method for producing a green pigment dispersion for a color filter in which pigment particles having a dispersion particle size of 5 nm or more and less than 100 nm are 99% or more of the total pigment particles is obtained by using the pigment dispersion obtained above as a pre-prepared pigment dispersion. The preliminarily prepared pigment dispersion is centrifuged at a maximum centrifugal force of 137,000 × g or more for 1 to 60 minutes to have a coarse particle removal step of separating and removing pigment particles having a dispersed particle diameter of 100 nm or more. .
By centrifuging the preliminarily prepared pigment dispersion for 1 to 60 minutes at a maximum centrifugal force of 137,000 × g or more, pigment particles having a dispersed particle diameter of 100 nm or more can be selectively separated and removed from the dispersed pigment particles. It becomes possible. Under conditions such as centrifugation for 1 hour at a maximum centrifugal force of about 35000 × g, the entire pigment tends to settle, and pigment particles having a dispersed particle size of 100 nm or more cannot be selectively separated and removed. There wasn't. The pigment particles having a dispersed particle diameter of 100 nm or more are obtained by performing the centrifugal separation under the conditions of a high rotational speed that generates a maximum centrifugal force of 137,000 × g or more as shown in the present invention and a short time. It became possible to selectively separate and remove.
The method for producing such a pigment dispersion has a coarse particle removal step of separating and removing pigment particles having a dispersion particle size of 100 nm or more, so that the average dispersion particle size of dispersed pigment particles is 15 to 80 nm. In addition, in the dispersed pigment particles, it is possible to achieve a pigment dispersion in which the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm are 99% or more of the total pigment particles, and have excellent pigment dispersibility, contrast A green pigment dispersion for color filters and a green curable resin composition for color filters capable of forming a high color filter can be obtained.

  The centrifuge used in the above step is not particularly limited as long as it can be centrifuged for 5 to 60 minutes with a maximum centrifugal force of 137000 × g or more. For example, the ultracentrifuge XL-100K manufactured by Beckman Coulter can be exemplified by setting Type 90Ti as a rotor and 13.5 ml quick-seal polyallomer tube as a centrifuge tube. Further, as the conditions for centrifugal separation, pigment particles having a dispersed particle diameter of 100 nm or more are selectively separated and removed most efficiently at a maximum centrifugal force of 137,000 × g or more and for 1 to 60 minutes. The conditions may be appropriately selected and used. That is, after selectively classifying pigment particles having a dispersed particle size of 100 nm or more, conditions are selected as appropriate so that particles having a dispersed particle size of less than 100 nm are not included in the fraction of pigment particles having a dispersed particle size of 100 nm or more. It is preferable to do.

  When the pigment particles having a dispersed particle diameter of 100 nm or more are classified by the centrifugal separator, the pigment particles having the dispersed particle diameter of 100 nm or more are selectively removed from the preliminarily prepared pigment dispersion in the dispersed pigment particles. As a method for selective removal, for example, the centrifuged sample that has entered the centrifuge tube is arbitrarily divided into several parts (generally 4 to 10 parts) from the supernatant and gently taken out in order from the top so as not to mix. Each separated sample is measured for particle size by a method using a laser light scattering particle size distribution meter, which will be described later, and by removing the lower sample from the portion of the sample containing pigment particles having a dispersed particle size of 100 nm or more, particles of 100 nm or more exist. Can be obtained.

  In this way, the pigment dispersion according to the present invention is obtained. This pigment dispersion is used as a preliminary preparation for preparing a green curable resin composition for a color filter having excellent pigment dispersibility.

2. Green curable resin composition for color filter The green curable resin composition for a color filter according to the present invention has a light transmittance of 90% or more and 400 nm in a wavelength range of 560 nm to 640 nm for a green pigment and the following test film. A green curable resin composition for a color filter, comprising a yellow or orange pigment having a wavelength of ˜450 nm of 12% or less, a pigment dispersant, a curable binder system, and a solvent. The average dispersed particle size of the pigment particles is 15 to 80 nm.
30 parts by weight of the yellow or orange pigment and the pigment dispersants 12 to 24 so that y = 0.450 in the chromaticity coordinates (x, y) in the XYZ color chromaticity diagram measured using a C light source A resin composition for a test film comprising 76 to 88 parts by weight of a methyl methacrylate / methacrylic acid copolymer (molar ratio 9/1) having a weight average molecular weight of 7000 to 15000 and a solvent of 520 parts by weight is obtained using an alkali-free glass. A test film is formed by applying and drying on a substrate.

  Here, the dispersed particle diameter of the pigment particles in the green curable resin composition for color filters of the present invention is the dispersed particle diameter of the pigment particles dispersed in the curable resin composition, and is a laser light scattering particle size distribution meter. It is measured by. The particle size can be measured with a laser light scattering particle size distribution meter using the solvent used in the green curable resin composition for color filters, and the green curable resin composition for color filters can be measured with a laser light scattering particle size distribution meter. Diluted to a suitable concentration (for example, 500 times) and measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nikkiso Nanotrac particle size distribution analyzer UPA-EX150). can do. The average dispersed particle size here is a volume average particle size.

  The green curable resin composition for a color filter according to the present invention performs toning using a pigment capable of increasing parallel luminance without increasing orthogonal luminance in a wavelength region where the green pigment transmits, and By controlling the dispersed particle size of the dispersed pigment, the same effect as described in the above pigment dispersion, the excellent dispersibility of the pigment, and the toning that effectively uses the bright line of the backlight, the contrast It is presumed that a green curable resin composition for a color filter capable of forming a high color filter can be obtained.

The green curable resin composition for a color filter according to the present invention contains at least a pigment, a pigment dispersant, a curable binder system, and a solvent, and may contain other compounds as necessary. is there.
As the pigment, the pigment dispersant, and the solvent, the same pigments as those described in the section of the green pigment dispersion for color filter can be used, and the description thereof is omitted here.

<Curable binder system>
In the present invention, from the point of imparting sufficient strength, durability, and adhesion to the coating film, after forming a pattern on the substrate by coating or transfer, the coating film can be cured by a polymerization reaction. A curable binder system is used. Examples of such a curable binder system include a photosensitive binder system that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a heat that can be polymerized and cured by heating. Examples include curable binder systems such as curable binder systems. As the curable binder system used in the present invention, a photosensitive binder system, a thermosetting binder system, and a system including both a photosensitive binder system and a thermosetting binder system can be used. Further, in preparing the resin composition according to the present invention using the pigment dispersion according to the present invention having excellent pigment dispersibility and pigment dispersion temporal stability, the excellent pigment dispersibility and pigment dispersion temporal stability It is necessary to select a curable binder system as appropriate so as not to hinder.

(1) Photosensitive binder system The photosensitive binder system contains a photocurable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams, and by curing the exposed area and dissolving and removing the unexposed area. Examples thereof include a negative photosensitive binder system that makes it possible to create a coating film pattern only in the exposed area.
In the green curable resin composition for a color filter according to the present invention, the curable binder system is a negative photosensitive binder system, so that a pattern can be easily formed using an existing process by a photolithography method. It is preferable from the point.

  A negative photosensitive binder system containing a photocurable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams comprises (i) an alkali-soluble resin, (ii) a polyfunctional monomer, and (iii) a photopolymerization initiator. And a sensitizer and the like.

(I) Alkali-soluble resin The alkali-soluble resin in the present invention has a carboxyl group in the side chain, acts as the binder resin, and is preferably soluble in an alkali developer, especially used for pattern formation. As long as it is, it can be appropriately selected and used.
The preferred alkali-soluble resin in the present invention is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the curable resin composition.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group functions as a component that suppresses alkali solubility of the photocurable resin composition.

  Moreover, as said acrylic copolymer containing a photopolymerizable functional group, glycidyl (meth) acrylate, 3,4-epoxy cyclohexylmethyl (meth) with respect to some carboxyl groups of the said acrylic copolymer. React the epoxy group of a compound having an epoxy group and an ethylenically unsaturated group in one molecule such as acrylate, 4- (2,3-epoxypropyl) butyl (meth) acrylate, allyl glycidyl ether, etc. The side chain obtained by reacting an isocyanate group of a compound having an isocyanate group and an ethylenically unsaturated group in one molecule such as 2-methacryloyloxyethyl isocyanate with respect to a part or all of the hydroxyl groups of the coalescence is not ethylenic. An acrylic copolymer having a saturated group can also be used.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by weight, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by weight, there is a tendency that the formed pattern is easily detached from the substrate or the pattern surface is roughened during development with an alkali developer.

  The preferred molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 500,000, pattern formation may be difficult during development with an alkaline developer.

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
Although it does not specifically limit as an epoxy compound, A bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, an aliphatic epoxy compound, or Examples thereof include epoxy compounds such as bisphenolfluorene type epoxy compounds. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, (meth) acryloyloxyethyl hexahydrophthalic acid, (Meth) acrylic acid dimer, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like. Also, half-ester compounds that are reaction products of hydroxyl group-containing acrylates with saturated or unsaturated dibasic acid anhydrides, reaction products of unsaturated group-containing monoglycidyl ethers with saturated or unsaturated dibasic acid anhydrides. A half ester compound is also mentioned. These unsaturated group-containing monocarboxylic acids may be used alone or in combination of two or more.

Examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Dibasic acid anhydrides such as methylenetetrahydrophthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl Aromatic polycarboxylic anhydrides such as ether tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, endobicyclo- [2 , 2,1] -Hept-5-ene-2,3-dica Polycarboxylic anhydride derivatives such as carbon anhydride, and the like. These may be used alone or in combination of two or more.
The molecular weight of the epoxy (meth) acrylate compound having a carboxyl group thus obtained is not particularly limited, but is preferably 1000 to 40000, more preferably 2000 to 5000.

(Ii) Polyfunctional monomer Examples of the polyfunctional monomer in the present invention include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; di (meth) acrylate of polyalkylene glycol such as polyethylene glycol and polypropylene glycol. ) Acrylates; poly (meth) acrylates of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. and their dicarboxylic acid modified products; polyesters, epoxy resins, urethane resins, alkyd resins , Oligo (meth) acrylates such as silicone resins and spirane resins; both ends such as hydroxypoly-1,3-butadiene at both ends, hydroxypolyisoprene at both ends, and hydroxypolycaprolactone at both ends Di hydroxylated polymer (meth) acrylates; tris (2- (meth) acryloyloxyethyl) phosphate and the like.

  Of these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. Succinic acid modified products of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable. The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of alkali-soluble resin, Preferably it is 20-300 weight part. In this case, when the amount of the polyfunctional monomer used is less than 5 parts by weight, the pattern strength and the smoothness of the pattern surface tend to be reduced. On the other hand, when it exceeds 500 parts by weight, for example, alkali developability is reduced, There is a tendency that stains and film residues are likely to occur in regions other than the portion where the pattern is formed.

  In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer. Examples of such monofunctional monomers include carboxyl group-containing unsaturated monomers or other unsaturated monomers constituting alkali-soluble resins, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl. A methacrylate etc. can be mentioned. Among these monofunctional monomers, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, methoxy Triethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate and the like are preferable. The monofunctional monomers can be used alone or in admixture of two or more. The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total amount of the polyfunctional monomer and the monofunctional monomer.

(Iii) Photopolymerization initiator and sensitizer The negative photosensitive binder system is usually blended with a photopolymerization initiator having activity with respect to the wavelength of the light source used. The photopolymerization initiator is appropriately selected in consideration of the difference in the reaction format of the polymer having photopolymerization and the photopolymerization monomer (for example, radical polymerization and cationic polymerization) and the kind of each material, and is not particularly limited.

  Examples of photopolymerization initiators are compounds that generate free radicals by the energy of ultraviolet rays, and include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, and polynuclear quinone compounds. , Xanthone compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, etc. . These can be used alone or in combination.

  Moreover, in this invention, 1 or more types chosen from the group of a sensitizer and a hardening accelerator can also be further used together with the said photoinitiator as needed. Specific examples of the sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4- Dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Etc. Specific examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4, Examples include chain transfer agents such as 6-dimethylaminopyridine, 1-phenyl-5-mercapto-1H-tetrazole, and 3-mercapto-4-methyl-4H-1,2,4-triazole.

(2) Thermosetting binder system Examples of thermosetting systems include ring-opening addition reaction systems such as epoxy groups and active hydrogen, cyclic urea groups and hydroxyl groups, and polyimide precursors that heat-close imidize polyamic acid. A system or the like can be used.
As the thermosetting binder system, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is preferably used, and a catalyst capable of promoting a thermosetting reaction may be added. An epoxy group is preferably used as the thermosetting functional group. In addition, a polymer having no polymerization reactivity as described above may be further used.

  As a compound having two or more thermosetting functional groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule is usually used. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included). The epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, etc. Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). These can be used widely.

  Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , Fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, water Bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Shi resin, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin. More specifically, bisphenol A type novolak epoxy resins such as trade name Epicoat 157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) and cresol novolac type epoxy resins such as trade name YDCN-701 (manufactured by Tohto Kasei Co., Ltd.) can be mentioned. .

  As an epoxy compound, a polymer having a relatively high molecular weight that is usually used as a binder component in order to impart adhesion, heat resistance, and alkali resistance to a cured film (hereinafter sometimes referred to as “binder epoxy compound”), In order to increase the crosslinking density of the cured film or to adjust the viscosity of the composition, the compound having a molecular weight smaller than that of the binder epoxy compound and having two or more epoxy groups in one molecule (hereinafter referred to as “polyfunctional epoxy compound”). May be used in combination.

  The average molecular weight of the binder epoxy compound is preferably 1,000 to 100,000, and particularly preferably 2,000 to 50,000, when expressed in terms of polystyrene-equivalent weight average molecular weight. If the molecular weight of the binder epoxy compound is too smaller than 1,000, physical properties such as strength and solvent resistance required for a cured resin layer as details of a color filter are likely to be insufficient, while the molecular weight is 100, If it is larger than 000, the viscosity is likely to increase, the uniformity during coating on the substrate is impaired, and a large distribution tends to occur in the film thickness.

On the other hand, the weight average molecular weight in terms of polystyrene of the polyfunctional epoxy compound is preferably 4,000 or less, particularly preferably 3,000 or less, on condition that it is smaller than the binder epoxy compound combined therewith. In addition, a weight average molecular weight means the value calculated | required by polystyrene conversion using the gel permeation chromatography (For example, HLC-8029, Tosoh Corporation make) which used tetrahydrofuran as the developing liquid.
The binder epoxy compound has a limit in the amount of epoxy that can be introduced into the copolymer molecule. When a polyfunctional epoxy compound having a relatively small molecular weight is added to the resin composition, the epoxy group is replenished in the composition, the reaction point concentration of the epoxy is increased, and the crosslinking density can be increased. The polyfunctional epoxy compound can be appropriately selected from the polyvalent epoxy compounds described above.

Moreover, as a hardening | curing agent, polyhydric carboxylic acid anhydride or polyhydric carboxylic acid is used, for example. The polyvalent carboxylic acid anhydride and the polyvalent carboxylic acid can be used singly or in combination of two or more.
When the thermosetting functional group is an epoxy group, the amount of the curing agent used in the present invention is usually in the range of 1 to 100 parts by weight per 100 parts by weight of the epoxy group-containing components (monomer and resin). The amount is preferably 5 to 50 parts by weight. When the blending amount of the curing agent is less than 1 part by weight, curing becomes insufficient and a tough coating film cannot be formed. Moreover, when the compounding quantity of a hardening | curing agent exceeds 100 weight part, the adhesiveness with respect to the board | substrate of a coating film will be inferior, and a uniform and smooth coating film cannot be formed.

In order to improve the hardness and heat resistance of the cured resin layer, a catalyst capable of promoting a thermosetting reaction such as between acid and epoxy may be added to the thermosetting binder system of the present invention. As such a catalyst, a thermal latent catalyst that exhibits activity during heat curing can be used.
The heat-latent catalyst exhibits catalytic activity when heated, accelerates the curing reaction and gives good properties to the cured product, and is added as necessary. The thermal latent catalyst is preferably one that exhibits acid catalytic activity at a temperature of 60 ° C. or higher. As such, a compound obtained by neutralizing a protonic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, Lewis Examples thereof include a mixture of an acid and a trialkyl phosphate, sulfonic acid esters, onium compounds and the like, and various compounds as described in JP-A-4-218561 can be used.

<Other ingredients>
If necessary, the green curable resin composition for a color filter according to the present invention may further contain a surfactant, an adhesion promoter, an ultraviolet absorber, a surface conditioner (leveling agent), or other components. May be.

(Surfactant)
Furthermore, when various surfactants are used in combination, the dispersion stability can be improved. Examples of the surfactant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. For example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether Examples include alkylphenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; and polyethyleneimines.
The product names of the surfactants are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (Dainippon Ink Chemical Co., Ltd.) )), Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), and the like.

(Adhesion promoter)
Examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.

(UV absorber)
For example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like can be given.
(Leveling agent)
Examples thereof include commercially available silicon-based, polyoxyalkylene-based, fatty acid ester-based, and special acrylic polymers.

<Combination ratio of each component in the resin composition>
A pigment is mix | blended in the ratio of 10 to 40 weight% with respect to the solid content whole quantity of curable resin composition, More preferably, it is 15 to 35 weight%. If the amount of the pigment is too small, the transmission density when the curable resin composition is applied to a predetermined film thickness (usually 1.0 to 4.0 μm) may not be sufficient. There is a possibility that the properties as a coating film such as adhesion to the substrate when the resin composition is applied and cured on the substrate, surface roughness of the cured film, and coating film hardness may be insufficient, and its curability. Since the ratio of the amount of the dispersant used for dispersing the pigment in the resin composition increases, characteristics such as developability and heat resistance may be insufficient.
Here, the solid content for specifying the blending ratio includes all components except the solvent, and liquid polymerizable monomers and the like are also included in the solid content.
The pigment dispersant content is preferably 20 to 80 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the total amount of pigment.
The total amount of the curable binder system is preferably 15 to 95% by weight, preferably 25 to 80% by weight, based on the total solid content of the curable resin composition.

In the green curable resin composition for a color filter in the present invention, the weight ratio (P / V) of the whole pigment (P) and the solid content (V) other than the pigment is 0.1 to 5.0. It is preferable that it is 0.3-3.0.
In the present invention, the solid content concentration of the green curable resin composition for a color filter is adjusted to 5 to 70% by weight using a solvent.

<Method for producing green curable resin composition for color filter>
The green curable resin composition for a color filter of the present invention is mixed with a pigment and a curable binder system together with other blending components as necessary, into a single solvent or a solvent that is a mixed solvent, and mixed. It can also be produced by dissolving or dispersing solid components by a method.
However, in the above method, a large amount of the pigment cannot be sufficiently dispersed in the solvent, and as a result, the dispersed particle size distribution of the pigment of the present invention may not be achieved. Therefore, it is preferable to prepare the pigment dispersion according to the present invention in advance and prepare a binder liquid in which other components such as a binder system are mixed, dispersed or dissolved with a solvent. And the green curable resin for color filters which was excellent in pigment dispersibility and pigment dispersion temporal stability by mixing the obtained pigment dispersion liquid and binder liquid concerning this invention, and performing a dispersion process as needed. A composition is easily obtained.

  If the pigment dispersion is not prepared in advance, first add the pigment and the pigment dispersant to the solvent, mix well, stir to disperse the pigment, and after passing through the coarse particle removal step using centrifugation as appropriate It is preferable to manufacture by adding and mixing the remaining components including the binder system. By blending a binder system or the like after pigment dispersion, not only the pigment dispersibility is not inhibited by the binder component and other blending components in the pigment dispersion step, but also the pigment dispersion stability is excellent.

<Physical properties of green curable resin composition for color filter>
In the curable resin composition according to the present invention, the dispersed pigment particles have an average dispersed particle size of 15 to 80 nm. Among these, the average dispersed particle diameter of the pigment measured by a laser light scattering particle size distribution meter is preferably 15 to 70 nm, and more preferably 15 to 60 nm.

  In the curable resin composition according to the present invention, among the dispersed pigment particles, it is preferable that the pigment particles having a dispersed particle size of 5 nm or more and less than 100 nm are 99% or more of the total pigment particles. Even if it has, it is preferable at the point which can reduce the light which leaks into an OFF state significantly, and can improve contrast drastically. If the dispersed pigment particles contain particles with a dispersed particle size of 100 nm or more, the particles with a dispersed particle size of 100 nm or more have a property of diffracting the scattered light depending on the size, so that the scattered light of polarized light increases, and the OFF state Light that leaks into the screen will be generated. When particles having a dispersed particle diameter of 100 nm or more are not included, even if the average dispersed particle diameter is the same, it is presumed that the influence of the particle size is almost eliminated and light leaking into the OFF state can be effectively reduced. In addition, among the dispersed pigment particles, it is preferable that the pigment particle having a dispersed particle size of 5 nm or more and less than 100 nm is 99.5% or more, more preferably 99.9% or more of the total pigment particles. In addition, 99% or more of the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm means 99% by volume or more.

  Among them, in the curable resin composition according to the present invention, particles having a dispersed particle diameter of 1/5 or more of the absorption wavelength of the contained pigment are less than 1%, further less than 0.5%, particularly 0.1%. It is preferable that it is less than.

The dispersion particle size distribution of the pigment in the curable resin composition is, among other things, in the dispersed pigment particles, the pigment particles having a dispersion particle size of 5 nm or more and less than 30 nm are dispersed in an amount of 5 to 30% by volume of the total pigment particles. The pigment particles having a particle size of 30 nm or more and less than 61 nm are preferably 30 to 90% by volume, and the pigment particles having a particle size of 61 nm or more and less than 100 nm are preferably 0 to 50% by volume. It is preferable that 10 to 50% by volume of the particles, 50 to 90% by volume of the pigment particles having a dispersed particle diameter of 30 nm to less than 61 nm, and 0 to 20% by volume of the pigment particles having a diameter of 61 nm to less than 100 nm.
Furthermore, it is preferable that the particle size when the cumulative particle size distribution is 50% by volume in all pigment particles is 65 nm or less.

  In addition, after storing the resin composition at 40 ° C. for 1 week, the dispersion particle size of the pigment particles is measured again in the same manner, and the dispersion stability is determined based on whether the average dispersion particle size before and after storage is 10 nm larger. Sex can be examined. When the dispersion stability is high, the average dispersed particle diameter does not change and is less than 10 nm within the error range.

<Curing film for color filter>
When the green curable resin composition for a color filter thus obtained is a photosensitive resin composition and has alkali developability, the composition is applied to a support to form a coating film, After drying, the coating film is irradiated with light in a predetermined pattern to selectively cure a part of the coating film. By developing with a liquid, a cured film having a predetermined pattern is obtained.
Further, when the obtained green curable resin composition for a color filter is a thermosetting resin composition or does not have alkali developability, the composition is printed on a predetermined region of the support, thermal transfer, etc. After selectively attaching by the above, a cured film having a predetermined pattern is obtained by curing by heating or light irradiation.

As a light beam used for the curing reaction, a light beam having a wavelength that causes a reaction of the photosensitive binder system is appropriately selected and used from radiation such as ultraviolet rays and ionizing radiation or visible light. Irradiation energy required for curing is typically, 10 to 500 mJ / m ² approximately. In the exposure step, a predetermined position of the coating film can be selectively exposed and cured by irradiating the surface of the coating film with laser light or irradiating light through a mask.
Moreover, although the conditions of heat-curing differ with binder systems, normally, it dries at 50-200 degreeC using a vacuum dryer, oven, a hotplate, or another apparatus to which heat is given, and then 120-400 degreeC. Heat cure at a moderate temperature.

The cured film for a color filter formed using the curable resin composition according to the present invention can achieve high contrast while achieving a specific color necessary for the colored layer of the color filter.
A transmission electron microscope is used to confirm whether the dispersion average particle diameter in the cured film or whether particles of 100 nm or more are present in the cured film. For example, a cured film for a color filter is thinned in a cross-sectional direction by a FIB (focused ion beam apparatus) (for example, FB-2000A manufactured by Hitachi), and a cross-sectional TEM sample thereof is transmitted through a transmission electron microscope (for example, JEM-200CX manufactured by JEOL Ltd. Observation is performed at a voltage of 100 kV and 10,000 to 500,000 times, and the major axis of each particle is measured. The average can be obtained from the major axis of all pigment particles in the observation sample, and the particle size distribution can be obtained by measuring the total number of pigment particles in the observation sample and the number of pigment particles of less than 5 nm and 100 nm or more. it can. Therefore, in the dispersed pigment particles, the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm are 99% or more of all pigment particles. The pigment particles having a particle diameter of 5 nm or more and less than 100 nm after dispersion are 99% of all pigment particles. That means that.

Ratio of transmitted luminance when the cured film of the curable resin composition according to the present invention is sandwiched by combining two polarizing plates so as to be orthogonal or parallel ((luminance when polarizing plate is parallel / polarizing plate orthogonal) Brightness), also simply referred to as “contrast” in the present invention, is preferably 3500 or more, and more preferably 4000 or more.
More specifically, as the green curable resin composition, when a cured film having a y-coordinate of 0.450 ≦ y <0.600 in the XYZ color system of CIE when measured with a C light source is formed, The contrast is preferably 3500 or more.

In addition, the said contrast in this invention is a value at the time of measuring as follows more specifically.
The brightness is measured using a contrast measuring device CT-1 manufactured by Aisaka Electric Co., Ltd. (light source: F10 lamp between cold cathodes, luminance meter: LS-100 manufactured by Konica Minolta, spectral luminance meter: CS-1000T manufactured by Konica Minolta). The contrast can be derived from the following formula using the measured luminance value.
Contrast = parallel luminance (cd / m ² ) / orthogonal luminance (cd / m ² )

3. Color filter The color filter according to the present invention includes a colored layer formed using the green curable resin composition for a color filter according to the present invention.
The color filter according to the present invention includes a colored layer formed using the green curable resin composition for a color filter according to the present invention, thereby realizing a high contrast while realizing a spectral spectrum necessary for the color filter. Is feasible.

FIG. 1 is a longitudinal sectional view showing an example (color filter 103) of a color filter for a display device belonging to the color filter according to the present invention.
The color filter 103 covers the light shielding layer 6 formed in a predetermined pattern on the transparent substrate 5, the colored layer 7 (7R, 7G, 7B) formed in a predetermined pattern on the light shielding layer, and the colored layer. The protective film 8 formed in this way is provided. A transparent electrode 9 for driving liquid crystal may be formed on the protective film as necessary. An alignment film 10 is formed on the innermost surface of the color filter 103, in this case on the transparent electrode.

  The columnar spacer 12 has a shape of a convex spacer, and is formed at a plurality of predetermined positions on the transparent electrode 9 in accordance with the region (non-display region) where the light shielding layer 6 is formed. The columnar spacer 12 is formed on the transparent electrode 9, the colored layer 7, or the protective film 8. In the color filter 103, columnar spacers are formed in a sea island shape on the protective film 8 via the transparent electrode 9, but the protective film 8 and the columnar spacer 12 are integrally formed and transparent so as to cover it. An electrode layer may be formed.

  The transparent substrate 5 of the color filter 101 is a transparent rigid material having no flexibility such as quartz glass, Pyrex (registered trademark) glass, or synthetic quartz plate, or a flexibility such as a transparent resin film or an optical resin plate. The transparent flexible material which has can be used. Among them, Corning 1737 glass is a material having a small coefficient of thermal expansion, excellent in dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the glass. Suitable for filters.

The light shielding layer 6 is provided so as to surround between the colored layers 7R, 7G, and 7B and the outside of the colored layer forming region in order to improve the contrast of the display image. In the present invention, the light shielding layer 6 is preferably formed using a resin composition containing light shielding particles. For example, when the resin composition for forming a light shielding layer has alkali developability, first, the resin composition for forming a light shielding layer is applied onto the transparent substrate 5 and dried as necessary to form a photosensitive coating film. The light-shielding layer 6 can be formed by forming, exposing and developing the coating film through a photomask for the light-shielding layer, and performing heat treatment as necessary. On the other hand, when the light shielding layer forming resin composition is a thermosetting resin composition or has no alkali developability, the light shielding layer forming resin composition is printed on a predetermined region on the transparent substrate 5, After selectively attaching by thermal transfer or the like, the light shielding layer 6 can be formed by curing by heating or light irradiation.
The thickness of the light shielding layer varies depending on the color filter to be applied, and is about 0.5 to 2.5 μm.

  The colored layer 7 includes a red pattern, a green pattern, and a blue pattern arranged in a desired form such as a mosaic type, a stripe type, a triangle type, and a four colored layer arrangement type, thereby forming a display region. In the present invention, a colored layer is formed using the curable resin composition according to the present invention. Among these, it is preferable to use a resin composition containing a photosensitive binder system because fine patterning is possible. This case will be described below as an example.

In addition to the green curable resin composition according to the present invention, red and blue curable resin compositions are prepared. Next, a certain color, for example, a green curable resin composition is applied on the transparent substrate 5 so as to cover the light shielding layer 6 by a known method such as spin coating to form a photosensitive green resin layer. The green colored layer 7G is formed by performing exposure through a photomask for use, and after alkali development and heat curing in a clean oven or the like. Thereafter, the red and blue curable resin compositions are sequentially used to pattern each color in the same manner to form the red colored layer 7R and the blue colored layer 7B.
The thickness of the colored layer is usually about 0.5 to 2.5 μm.

The protective film 8 is provided to flatten the surface of the color filter and prevent the components contained in the colored layer 7 from eluting into the liquid crystal layer. The protective film 8 covers the light-shielding layer 6 and the colored layer 7 with a known negative photocurable transparent resin composition or thermosetting transparent resin composition by a method such as spin coater, roll coater, spraying, printing, or the like. And can be formed by curing with light or heat.
When forming the protective film, the thickness of the protective film is set in consideration of the light transmittance of the resin composition, the surface state of the color filter, and the like, and is, for example, about 0.1 to 2.0 μm. When using a spin coater, the number of revolutions is set within a range of 500 to 1500 revolutions / minute.

  The transparent electrode film 9 on the protective film is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and alloys thereof, such as sputtering, vacuum deposition, CVD, etc. It is formed by a general method, and is formed into a predetermined pattern by etching using a photoresist or using a jig as necessary. The thickness of the transparent electrode can be about 20 to 500 nm, preferably about 100 to 300 nm.

  A plurality of convex spacers are provided in a non-display area on the substrate in order to maintain a cell gap when the color filter 103 is bonded to a liquid crystal driving side substrate such as a TFT array substrate. The shape and size of the convex spacer are not particularly limited as long as it can be selectively provided in a non-display region on the substrate and can maintain a predetermined cell gap over the entire substrate. When the columnar spacer 12 as shown in the figure is formed as the convex spacer, it has a certain height in the range of about 2 to 10 μm, and the protruding height (pattern thickness) is required for the liquid crystal layer. It can set suitably from thickness etc. Moreover, the thickness of the columnar spacer 12 can be appropriately set within a range of about 5 to 20 μm. Further, the formation density (density) of the columnar spacers 12 can be appropriately set in consideration of the thickness unevenness of the liquid crystal layer, the aperture ratio, the shape and material of the columnar spacers, for example, red, green and blue Necessary and sufficient spacer function is expressed at a ratio of one for each colored layer. The shape of such a columnar spacer may be a columnar shape, and may be, for example, a columnar shape, a prismatic shape, a truncated cone shape, or the like.

  The convex spacer can be formed using a curable resin composition. That is, first, the coating liquid of the curable resin composition is applied directly on a transparent substrate by a method such as spin coater, roll coater, spray, printing, or through another layer such as a transparent electrode, and then dried. Then, a photocurable resin layer is formed. The rotational speed of the spin coater may be set within a range of 500 to 1500 revolutions / minute, as in the case of forming the protective film. Next, this resin layer is exposed through a photomask for convex spacers, and developed with a developer such as an alkaline solution to form a predetermined convex pattern. A convex spacer is formed by heat treatment (post-bake) or the like.

The convex spacer can be provided directly on the color filter or indirectly through another layer. For example, a transparent electrode such as ITO or a protective film may be formed on the color filter, and a convex spacer may be formed thereon, or a protective film and a transparent electrode may be formed in this order on the color filter, and the transparent electrode A convex spacer may be formed on the top.
The alignment film 10 is provided on the inner surface side of the color filter so as to cover the display portion including the colored layer 7 and the non-display portion including the light shielding layer 6 and the columnar spacer 12. The alignment film can be formed by applying a coating solution containing a resin such as a polyimide resin by a known method such as spin coating, drying, curing with heat or light as necessary, and then rubbing.

  When the color filter 103 (display side substrate) thus obtained and the TFT array substrate (liquid crystal drive side substrate) are opposed to each other, and the inner peripheral side peripheral portions of both the substrates are bonded with a sealant, the both substrates are separated by a predetermined distance. Bonding is performed with the cell gap maintained. An active matrix color liquid crystal display device belonging to the liquid crystal panel can be obtained by filling the liquid crystal in the gap between the substrates and sealing the liquid crystal.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

<Selection of yellow or orange pigment>
(1) Preparation of test film 10 parts by weight of yellow or orange pigment, 8 parts by weight of pigment dispersant, and 82 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed to prepare a yellow or orange pigment dispersion. . On the other hand, the copolymer reaction solution obtained in the following Production Example 1 as a methyl methacrylate / methacrylic acid copolymer (molar ratio 9/1) having a weight average molecular weight of 7000 to 15000 is a copolymer solution having a solid content of 40%. As above, 29.2 parts by weight were weighed and mixed with 24.6 parts by weight of propylene glycol monomethyl ether acetate to prepare a copolymer dilution. Each of the two mixtures obtained above was mixed with 46.1 parts by weight of a yellow or orange pigment dispersion and 53.9 parts by weight of a copolymer diluent. The two mixtures obtained above were mixed to prepare a test film forming resin composition.
The test film-forming resin composition was applied onto a 0.7 mm thick glass substrate (NH Techno Glass Co., Ltd., NA35) by spin coating. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. The film thickness after drying was adjusted so that y = 0.450 in the chromaticity coordinates (x, y) in the XYZ color chromaticity diagram measured using a C light source. In addition, when it is difficult to apply the resin composition on the glass, the coating suitability can be improved by adding a small amount of a surfactant such as MegaFac (Dainippon Ink Chemical Co., Ltd.).

(2) Light transmittance measurement Using Olympus microspectrophotometer OSP-SP200, the light transmittance value of the same glass substrate as the glass substrate on which the test film forming resin composition is applied is obtained as 100%. The transmission spectrum of a C light source on the test film was measured, and the light transmittance was calculated.

<Production Example 1>
150 parts by weight of PGMEA was placed in a four-necked flask equipped with a stirrer and a nitrogen introduction tube, and heated to 100 ° C. with a mantle heater. Then, 90 parts by weight of methyl methacrylate (MMA), 10 parts by weight of methacrylic acid (MAA), 4.0 parts by weight of n-dodecyl mercaptan and 1.60 parts by weight of AIBN were added from the dropping funnel over 1.5 hours. And dripped. During dropping, the temperature in the flask was set to 100 ± 1 ° C. After completion of dropping, 0.3 part by weight of AIBN was added and reacted at 100 ° C. for 2 hours to obtain a colorless and transparent MMA / MAA copolymer solution. After completion of the reaction, the reaction mixture was cooled and the molecular weight was confirmed by GPC measurement using polystyrene as a standard. The resulting polymer had a weight average molecular weight of 7,000. Moreover, when solid content was measured by heating in 150 degreeC oven for 2 hours, it was 40.0%.

<Example 1>
In the selection of the yellow or orange pigment, the light transmittance of the test film was 95% or more in the wavelength region of 560 nm to 640 nm and 5% or less in the wavelength region of 400 nm to 450 nm. I. A green pigment dispersion and a green curable resin composition were prepared using a pigment yellow 150 refined pigment (primary particles 10 to 50 nm).

(1) Preparation of green pigment dispersion for color filter From 10 parts by weight of refined pigment (CI pigment green 36 (PG36) primary particles 10 to 70 nm), from quaternary ammonium salt of dimethylaminoethyl (meth) acrylate 10 parts by weight of a pigment dispersant (BYK2000, manufactured by BYK Chemie, solid content 40% by weight), which is a polymer containing derived repeating units, and an alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer) (Molar ratio 30/40/10/20, acid value: 70 mg KOH / g, molecular weight 6000)) 4 parts by weight and 76 parts by weight of solvent propylene glycol monomethyl ether acetate are mixed, and 1 mm with 2 mm zirconia beads in a paint shaker. Time, further 0.1mm zirconia beads 2.5 hours and dispersed, to obtain a pre-prepared pigment dispersion A. The bead filling rate in the vessel during dispersion was 70%. The dispersed particle diameter of the pigment particles is measured at 23 ° C. by a dynamic light scattering method using a Nanotrac particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd. after diluting the pigment dispersion with propylene glycol monomethyl ether acetate 1000 times. did. The preliminarily prepared pigment dispersion A had a volume average particle size of 62 nm.
A pigment which is a polymer containing a repeating unit derived from a quaternary ammonium salt of dimethylaminoethyl (meth) acrylate with respect to 10 parts by weight of a finer pigment (CI Pigment Yellow 150 (PY150) primary particles 10 to 50 nm) 10 parts by weight of a dispersant (BYK2000, manufactured by Big Chemie, solid content 40% by weight) and an alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer (molar ratio 30/40/10/20, acid) (Value: 70 mg KOH / g, molecular weight 6000)) 4 parts by weight and 76 parts by weight of solvent propylene glycol monomethyl ether acetate are mixed and dispersed in a paint shaker for 1 hour with 2 mm zirconia beads and further for 4 hours with 0.1 mm zirconia beads To obtain a pre-prepared pigment dispersion B . The bead filling rate in the vessel during dispersion was 70%. When the dispersion particle diameter of the pigment particles was measured in the same manner as in the above-prepared pigment dispersion liquid A, the volume average particle diameter of the above-prepared pigment dispersion liquid B was 78 nm.
The preliminarily prepared pigment dispersion A and the preliminarily prepared pigment dispersion B were mixed at a ratio of 80 parts by weight and 20 parts by weight, respectively, to prepare a green pigment dispersion (pigment dispersion C) according to the present invention. When the dispersed particle diameter of the pigment particles was measured in the same manner as the above-prepared pigment dispersion liquid A, the volume average particle diameter of the green pigment dispersion liquid (pigment dispersion liquid C) according to the present invention was 69 nm. .
In addition, the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm were 95% by volume of the total pigment particles. Furthermore, pigment particles of 5 nm or more and less than 30 nm were 1% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 44% by volume, and pigment particles of 61 nm or more and less than 100 nm were 50% by volume. Further, the particle size when the cumulative particle size distribution was 50% by volume in all particles was 62 nm.

(2) Preparation of green curable resin composition for color filter In 46 parts by weight of the green pigment dispersion (pigment dispersion C) obtained in Example 1 above, 23 parts by weight of the following binder composition and propylene glycol monomethyl ether acetate 31 parts by weight was added and pressure filtration was performed to obtain a green curable resin composition for a color filter of Example 1, respectively.
<Binder composition>
Alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer (molar ratio 30/40/10/20, acid value: 70 mg KOH / g, molecular weight 6000)): 14 parts by weight Acrylate monomer (KAYARAD DPHA, manufactured by Nippon Kayaku): 18 parts by weight. Photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907) Ciba Specialty Chemicals)): 6 parts by weight Photosensitizer (4,4'-dimethylaminobenzophenone): 2 parts by weight Solvent (propylene glycol monomethyl ether acetate): 40 parts by weight

(3) Evaluation of green curable resin composition for color filter (i) Particle size distribution The dispersed particle size of pigment particles was obtained by diluting the green curable resin composition for color filter 1000 times with propylene glycol monomethyl ether acetate. The measurement was performed at 23 ° C. by a dynamic light scattering method using a Nanotrac particle size distribution analyzer UPA-EX150 manufactured by the company.
The dispersed particle size of the curable resin composition of Example 1 was 70 nm in volume average particle size.
Moreover, the pigment particles of 5 nm or more and less than 100 nm were 93% by volume of the total pigment particles. Further, pigment particles of 5 nm or more and less than 30 nm were 1% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 42% by volume, and pigment particles of 61 nm or more and less than 100 nm were 50% by volume. Further, the particle size when the cumulative particle size distribution was 50% by volume in all particles was 64 nm.

(Ii) Contrast The curable resin composition for a color filter was applied onto a glass substrate having a thickness of 0.7 mm (NA Techno Glass Co., Ltd., NA35) by spin coating.
Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (colored layer) was obtained by exposure (60 mJ) using a small aligner. The film thickness after drying and curing was adjusted so that the target chromaticity y = 0.450.

Luminance was measured using a contrast measuring device CT-1 manufactured by Aisaka Electric Co., Ltd. (light source: F10 lamp between cold cathodes, luminance meter: LS-100 manufactured by Konica Minolta, spectral luminance meter: CS-1000T manufactured by Konica Minolta). . The contrast can be derived from the following formula using the measured luminance value.
Contrast = parallel luminance (cd / m ² ) / orthogonal luminance (cd / m ² )
As a result, in Example 1, the parallel luminance in the bright line of the cold cathode tube in the wavelength range of 560 nm to 640 nm is improved without increasing the orthogonal luminance to the bright line of the cold cathode tube in the wavelength range of 400 nm to 450 nm. I was able to confirm. As a result, the contrast was 7780.

<Example 2>
(1) Preparation of Green Pigment Dispersion for Color Filter The preliminarily prepared pigment dispersion A and the preliminarily prepared pigment dispersion B are mixed at a ratio of 90 parts by weight and 10 parts by weight, respectively. (Pigment dispersion D) was prepared. When the dispersed particle diameter of the pigment particles was measured in the same manner as in the above-prepared pigment dispersion liquid A, the volume average particle diameter of the green pigment dispersion liquid (pigment dispersion liquid D) according to the present invention was 67 nm. .
In addition, the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm were 95% by volume of the total pigment particles. Furthermore, pigment particles having a particle size of 5 nm or more and less than 30 nm were 2% by volume of all pigment particles, pigment particles having a particle size of 30 to 61 nm were 54% by volume, and pigment particles having a particle size of 61 to 100 nm were 39% by volume. Furthermore, the particle size was 60 nm when the cumulative particle size distribution was 50% by volume of all particles.

(2) Preparation of green curable resin composition for color filter Instead of using the green pigment dispersion (pigment dispersion C) of Example 1 in the preparation of the green curable resin composition for color filter of Example 1, the above A green curable resin composition for a color filter of Example 2 was obtained in the same manner as in Example 1, except that the green pigment dispersion liquid (Pigment dispersion liquid D) obtained in Example 2 was used.

(3) Evaluation of green curable resin composition for color filter In the same manner as in Example 1, particle size distribution and contrast were evaluated.
(I) Particle size distribution The dispersed particle size of the curable resin composition of Example 2 was 68 nm in volume average particle size.
Moreover, the pigment particles of 5 nm or more and less than 100 nm were 95% by volume of the total pigment particles. Further, the pigment particles of 5 nm or more and less than 30 nm were 2% by volume of the total pigment particles, the pigment particles of 30 nm or more and less than 61 nm were 51% by volume, and the pigment particles of 61 nm or more and less than 100 nm were 42% by volume. Further, the particle size when the cumulative particle size distribution was 50% by volume in all particles was 61 nm.

(Ii) Contrast The contrast value of the cured film adjusted to a film thickness of y = 0.450 using the green curable resin composition for a color filter of Example 2 was 7780.

<Comparative Example 1>
Only the preliminarily prepared pigment dispersion A (CI Pigment Green 36) was used as the green pigment dispersion.
Using the green pigment dispersion, a green curable resin composition for a color filter was prepared in the same manner as in Example 1.
About the obtained green curable resin composition for color filters, the particle size distribution and the contrast were evaluated in the same manner as in Example 1.

(I) Particle size distribution The dispersed particle size of the curable resin composition of Comparative Example 1 had a volume average particle size of 62 nm.
Moreover, the pigment particles of 5 nm or more and less than 100 nm were 95% by volume of the total pigment particles. Further, pigment particles of 5 nm or more and less than 30 nm were 6% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 50% by volume, and pigment particles of 61 nm or more and less than 100 nm were 39% by volume. Furthermore, the particle size was 58 nm when the cumulative particle size distribution was 50% by volume of all particles.

(Ii) Contrast Using the green curable resin composition for color filter of Comparative Example 1 to measure the contrast with a cured film adjusted to a film thickness such that y = 0.450, 560 nm to 640 nm when the polarizing plate was parallel. It was confirmed that the luminance at the bright line of the cold cathode fluorescent lamp in the wavelength region of lower than that of Example 1 was 6, and the contrast value was 6440.

<Comparative example 2>
(1) Preparation of green pigment dispersion for color filter From 10 parts by weight of fine pigment (CI Pigment Yellow 150 (PY150) primary particles 10 to 50 nm), from quaternary ammonium salt of dimethylaminoethyl (meth) acrylate 10 parts by weight of a pigment dispersant (BYK2000, manufactured by BYK Chemie, solid content 40% by weight), which is a polymer containing a derived repeating unit, and an alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer) 4 parts by weight (acid value: 70 mg KOH / g), molecular weight 6000) and 76 parts by weight of solvent propylene glycol monomethyl ether acetate are mixed, and 1 hour with 2 mm zirconia beads in a paint shaker, and further 7 with 0.1 mm zirconia beads. Time-dispersed and pre-prepared face To obtain a dispersion E. The bead filling rate in the vessel during dispersion was 70%. When the dispersed particle diameter of the pigment particles was measured in the same manner as in the above-prepared pigment dispersion A, the dispersed-particle diameter of the above-prepared pigment dispersion E was 133 nm in volume average particle diameter due to aggregation due to overdispersion.
The preliminarily prepared pigment dispersion A and the preliminarily prepared pigment dispersion E were mixed at a ratio of 80 parts by weight and 20 parts by weight, respectively, to prepare a green pigment dispersion (pigment dispersion F) of Comparative Example 2. When the dispersed particle diameter of the pigment particles was measured in the same manner as the above-prepared pigment dispersion liquid A, the volume average particle diameter of the green pigment dispersion liquid (pigment dispersion liquid F) of Comparative Example 2 was 136 nm. .
The pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm were 47% by volume of the total pigment particles. Further, pigment particles of 5 nm or more and less than 30 nm were 0% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 20% by volume, and pigment particles of 61 nm or more and less than 100 nm were 27% by volume. Furthermore, the particle size when the cumulative particle size distribution was 50% by volume in all particles was 112 nm.

(2) Preparation of green curable resin composition for color filter Instead of using the green pigment dispersion (pigment dispersion C) of Example 1 in the preparation of the green curable resin composition for color filter of Example 1, the above A green curable resin composition for a color filter of Comparative Example 2 was obtained in the same manner as in Example 1 except that the green pigment dispersion liquid (Pigment Dispersion Liquid F) of Comparative Example 2 obtained in 1 was used.

(3) Evaluation of green curable resin composition for color filter In the same manner as in Example 1, particle size distribution and contrast were evaluated.
(I) Particle Size Distribution The dispersed particle size of the curable resin composition of Comparative Example 2 was a volume average particle size of 136 nm.
Moreover, the pigment particles of 5 nm or more and less than 100 nm were 42% by volume of the total pigment particles. Further, pigment particles of 5 nm or more and less than 30 nm were 0% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 18% by volume, and pigment particles of 61 nm or more and less than 100 nm were 24% by volume. Furthermore, the particle size was 118 nm when the cumulative particle size distribution was 50% by volume of all particles.

(Ii) Contrast Using the green curable resin composition for color filter of Comparative Example 2 and measuring the contrast of the cured film adjusted to a film thickness such that y = 0.450, the contrast was measured in the wavelength range of 560 nm to 640 nm. Although the parallel luminance in the bright line of a certain cold cathode tube was improved almost the same as in Example 1, the orthogonal luminance when orthogonal to the polarizing plate was increased over the entire wavelength region due to scattering by coarse particles. It could be confirmed. As a result, the contrast value was 3200.

<Result>
FIG. 3 shows the spectral luminance (parallel luminance) when the polarizing plates of Example 1 of the present invention and Comparative Example 1 are parallel. FIG. 4 shows the spectral luminance (orthogonal luminance) when the polarizing plates of Example 1 and Comparative Example 1 of the present invention are orthogonal. From FIG. 3 and FIG. 4, in Example 1 in which the specific yellow pigment was added so that the average dispersed particle diameter was in the specific range of the present invention, the parallel luminance of the bright line in the wavelength region of 560 to 640 nm was particularly high. On the other hand, since it was possible to suppress the increase in orthogonal luminance including the wavelength range of 400 nm to 450 nm, it was revealed that the contrast was dramatically improved.
In FIG. 5, the spectral luminance at the time of the polarizing plate parallel of Example 1 of this invention and Comparative Example 2 is shown. In FIG. 6, the spectral luminance at the time of the polarizing plate orthogonal of Example 1 of this invention and Comparative Example 2 is shown. 5 and 6, even when the same yellow pigment (Y150) as in Example 1 is used, when a pigment dispersion having an average dispersed particle size outside the specific range of the present invention is used, 560 is used. It has been clarified that since the orthogonal luminance of the bright line as a whole has increased, including the wavelength range of ˜640 nm, the contrast is lowered even if the parallel luminance of the bright line in the wavelength range of 560 to 640 nm is improved. .

<Example 3>
In the selection of the yellow or orange pigment, the light transmittance of the test film was 90% or more in the wavelength region of 560 nm to 640 nm and 8% or less in the wavelength region of 400 nm to 450 nm. I. A green pigment dispersion and a green curable resin composition were prepared using a pigment yellow 185 finer pigment (primary particles 10 to 50 nm).

(1) Preparation of green pigment dispersion for color filter From 10 parts by weight of refined pigment (CI pigment yellow 185 (PY185) primary particle 10-50 nm), from quaternary ammonium salt of dimethylaminoethyl (meth) acrylate 10 parts by weight of a pigment dispersant (BYK2000, manufactured by BYK Chemie, solid content 40% by weight), which is a polymer containing derived repeating units, and an alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer) 4 parts by weight (acid value: 70 mg KOH / g), molecular weight 6000) and 76 parts by weight of solvent propylene glycol monomethyl ether acetate are mixed with a paint shaker for 1 hour with 2 mm zirconia beads, and further with 4 with 0.1 mm zirconia beads. Time-dispersed and pre-prepared face To obtain a dispersion G. The bead filling rate in the vessel during dispersion was 70%. When the dispersed particle diameter of the pigment particles was measured in the same manner as in the above-prepared pigment dispersion liquid A, the volume average particle diameter of the dispersed particle diameter of the above-prepared pigment dispersion liquid G was 72 nm.
The preliminarily prepared pigment dispersion A and the preliminarily prepared pigment dispersion G were mixed at a ratio of 80 parts by weight and 20 parts by weight, respectively, to prepare a green pigment dispersion (pigment dispersion H) according to the present invention. When the dispersed particle diameter of the pigment particles was measured in the same manner as the above-prepared pigment dispersion liquid A, the dispersed particle diameter of the green pigment dispersion liquid (pigment dispersion liquid H) according to the present invention was 68 nm in volume average particle diameter. .
Further, the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm were 98% by volume of the total pigment particles. Furthermore, pigment particles of 5 nm or more and less than 30 nm were 1% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 44% by volume, and pigment particles of 61 nm or more and less than 100 nm were 53% by volume. Further, the particle size when the cumulative particle size distribution was 50% by volume in all particles was 64 nm.

(2) Preparation of green curable resin composition for color filter Instead of using the green pigment dispersion (pigment dispersion C) of Example 1 in the preparation of the green curable resin composition for color filter of Example 1, the above A green curable resin composition for a color filter of Example 3 was obtained in the same manner as in Example 1 except that the green pigment dispersion liquid (pigment dispersion liquid H) obtained in Example 3 was used.

(3) Evaluation of green curable resin composition for color filter In the same manner as in Example 1, particle size distribution and contrast were evaluated.
(I) Particle size distribution The volume average particle size of the dispersed particle size of the curable resin composition of Example 3 was 69 nm.
In addition, pigment particles of 5 nm or more and less than 100 nm were 97% by volume of the total pigment particles. In addition, pigment particles of 5 nm or more and less than 30 nm were 1% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 42% by volume, and pigment particles of 61 nm or more and less than 100 nm were 54% by volume. Further, the particle size when the cumulative particle size distribution was 50% by volume in all particles was 65 nm.

(Ii) Contrast The contrast value of the cured film adjusted to a film thickness of y = 0.450 using the green curable resin composition for a color filter of Example 3 was 6860.

<Example 4>
CI pigment green 58 (PG58) as the green pigment and C.I. I. A green pigment dispersion and a green curable resin composition were prepared using a pigment yellow 150 refined pigment (primary particles 10 to 50 nm).

(1) Preparation of green pigment dispersion for color filter From 10 parts by weight of finer pigment (CI Pigment Green 58 (PG58) primary particles 10 to 50 nm), from quaternary ammonium salt of dimethylaminoethyl (meth) acrylate 20 parts by weight of a pigment dispersant (BYK2000, manufactured by BYK Chemie, solid content of 40% by weight), which is a polymer containing a repeating unit to be derived, and 76 parts by weight of a solvent propylene glycol monomethyl ether acetate are mixed and 2 mm by a paint shaker. Dispersion with zirconia beads for 1 hour and further with 0.1 mm zirconia beads for 2 hours gave Preliminary Preparation Pigment Dispersion Liquid I. The bead filling rate in the vessel during dispersion was 70%. When the dispersed particle diameter of the pigment particles was measured in the same manner as in the above-prepared pigment dispersion liquid A, the volume average particle diameter of the dispersed particle diameter of the above-prepared pigment dispersion liquid I was 48 nm.
The pre-prepared pigment dispersion I and the pre-prepared pigment dispersion B obtained in Example 1 were mixed at a ratio of 80 parts by weight and 20 parts by weight, respectively, and the green pigment dispersion (pigment dispersion J ) Was prepared. When the dispersed particle diameter of the pigment particles was measured in the same manner as the above-prepared pigment dispersion liquid A, the volume average particle diameter of the green pigment dispersion liquid (pigment dispersion liquid J) according to the present invention was 52 nm. .
Further, the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm were 98% by volume of the total pigment particles. Further, pigment particles of 5 nm or more and less than 30 nm were 12% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 52% by volume, and pigment particles of 61 nm or more and less than 100 nm were 34% by volume. Further, the particle size was 55 nm when the cumulative particle size distribution was 50% by volume in all particles.

(2) Preparation of green curable resin composition for color filter Instead of using the green pigment dispersion (pigment dispersion C) of Example 1 in the preparation of the green curable resin composition for color filter of Example 1, the above A green curable resin composition for a color filter of Example 4 was obtained in the same manner as in Example 1 except that the green pigment dispersion liquid (Pigment dispersion liquid J) obtained in Example 4 was used.

(3) Evaluation of green curable resin composition for color filter In the same manner as in Example 1, particle size distribution and contrast were evaluated.
(I) Particle size distribution The volume average particle size of the dispersed particle size of the curable resin composition of Example 4 was 57 nm.
In addition, pigment particles of 5 nm or more and less than 100 nm accounted for 98% by volume of the total pigment particles. Further, the pigment particles of 5 nm or more and less than 30 nm were 10% by volume of the total pigment particles, the pigment particles of 30 nm or more and less than 61 nm were 53% by volume, and the pigment particles of 61 nm or more and less than 100 nm were 35% by volume. Further, the particle size was 57 nm when the cumulative particle size distribution was 50% by volume in all particles.

(Ii) Contrast The contrast value of the cured film adjusted to a film thickness of y = 0.450 using the green curable resin composition for a color filter of Example 4 was 7800.

<Comparative Example 3>
Only the pre-prepared pigment dispersion I (CI Pigment Green 58) prepared in Example 4 was used as the green pigment dispersion.
Using the green pigment dispersion, a green curable resin composition for a color filter was prepared in the same manner as in Example 1.
About the obtained green curable resin composition for color filters, the particle size distribution and the contrast were evaluated in the same manner as in Example 1.

(I) Particle size distribution The dispersed particle size of the curable resin composition of Comparative Example 3 had a volume average particle size of 48 nm.
In addition, pigment particles of 5 nm or more and less than 100 nm accounted for 98% by volume of the total pigment particles. Further, the pigment particles of 5 nm or more and less than 30 nm were 12% by volume of the total pigment particles, the pigment particles of 30 nm or more and less than 61 nm were 57% by volume, and the pigment particles of 61 nm or more and less than 100 nm were 29% by volume. Furthermore, the particle size when the cumulative particle size distribution was 50% by volume in all particles was 52 nm.

(Ii) Contrast The contrast value of the cured film adjusted to a film thickness of y = 0.500 using the green curable resin composition for a color filter of Comparative Example 3 was 7530.

<Comparative example 4>
In selecting the yellow or orange pigment, the light transmittance of the test film is 90% or more in the wavelength range of 560 nm to 640 nm, and the maximum transmittance is 15.4% (450 nm) in the wavelength range of 400 nm to 450 nm. C. I. A green pigment dispersion and a green curable resin composition were prepared using a pigment yellow 17 refined pigment (primary particles 10 to 80 nm).

(1) Preparation of green pigment dispersion for color filter From 10 parts by weight of fine pigment (CI Pigment Yellow 17 (PY17) primary particles 10 to 80 nm), from quaternary ammonium salt of dimethylaminoethyl (meth) acrylate 10 parts by weight of a pigment dispersant (BYK2000, manufactured by BYK Chemie, solid content 40% by weight), which is a polymer containing derived repeating units, and an alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer) 4 parts by weight (acid value: 70 mg KOH / g), molecular weight 6000) and 76 parts by weight of solvent propylene glycol monomethyl ether acetate are mixed with a paint shaker for 1 hour with 2 mm zirconia beads, and further with 4 with 0.1 mm zirconia beads. .5 hours dispersion, pre-prepared face To obtain a dispersion K. The bead filling rate in the vessel during dispersion was 70%. When the dispersion particle diameter of the pigment particles was measured in the same manner as in the above-prepared pigment dispersion liquid A, the dispersion-average particle diameter of the above-prepared pigment dispersion liquid K was 76 nm.
The preliminarily prepared pigment dispersion A and the preliminarily prepared pigment dispersion K were mixed at a ratio of 80 parts by weight and 20 parts by weight, respectively, to prepare a green pigment dispersion (pigment dispersion L) according to the present invention. When the dispersed particle diameter of the pigment particles was measured in the same manner as in the above-prepared pigment dispersion liquid A, the dispersed particle diameter of the green pigment dispersion liquid (pigment dispersion liquid L) according to the present invention was 72 nm in volume average particle diameter. .
Further, the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm were 94% by volume of the total pigment particles. Furthermore, pigment particles of 5 nm or more and less than 30 nm were 2% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 35% by volume, and pigment particles of 61 nm or more and less than 100 nm were 57% by volume. Further, the particle size was 67 nm when the cumulative particle size distribution was 50% by volume of all particles.

(2) Preparation of green curable resin composition for color filter Instead of using the green pigment dispersion (pigment dispersion C) of Example 1 in the preparation of the green curable resin composition for color filter of Example 1, the above A green curable resin composition for a color filter according to Comparative Example 4 was obtained in the same manner as in Example 1 except that the green pigment dispersion liquid (Pigment Dispersion Liquid L) obtained in Comparative Example 4 was used.

(3) Evaluation of green curable resin composition for color filter In the same manner as in Example 1, particle size distribution and contrast were evaluated.
(I) Particle size distribution The dispersed average particle size of the curable resin composition of Comparative Example 4 was 74 nm in volume average particle size.
Moreover, the pigment particles of 5 nm or more and less than 100 nm were 95% by volume of the total pigment particles. Further, pigment particles of 5 nm or more and less than 30 nm were 1% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 36% by volume, and pigment particles of 61 nm or more and less than 100 nm were 58% by volume. Further, the particle size when the cumulative particle size distribution was 50% by volume in all particles was 71 nm.

(Ii) Contrast The contrast value of the cured film adjusted to a film thickness of y = 0.450 using the green curable resin composition for color filter of Comparative Example 4 was 5830. Although the parallel luminance of the bright line in the wavelength range of 560 to 640 nm was improved, on the other hand, the orthogonal luminance in the wavelength range of 400 nm to 450 nm was also increased, so the contrast was lowered.

<Comparative Example 5>
In the selection of the yellow or orange pigment, the light transmittance of the test film was 90% or more in the wavelength region of 560 nm to 640 nm, and the maximum transmittance was 25% (450 nm) in the wavelength region of 400 nm to 450 nm. . I. A green pigment dispersion and a green curable resin composition were prepared using a pigment yellow 139 fine pigment (primary particles 10 to 60 nm).

(1) Preparation of green pigment dispersion for color filter From 10 parts by weight of refined pigment (CI pigment yellow 139 (PY139) primary particles 10-60 nm), from quaternary ammonium salt of dimethylaminoethyl (meth) acrylate 10 parts by weight of a pigment dispersant (BYK2000, manufactured by BYK Chemie, solid content 40% by weight), which is a polymer containing a derived repeating unit, and an alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer) (Acid value: 70 mg KOH / g), molecular weight 6000) 4 parts by weight and solvent propylene glycol monomethyl ether acetate 76 parts by weight are mixed, and 2 mm zirconia beads for 1 hour in a paint shaker, and further 0.1 mm zirconia beads 2 .5 hours dispersion, preparatory To obtain a pigment dispersion M. The bead filling rate in the vessel during dispersion was 70%. When the dispersed particle diameter of the pigment particles was measured in the same manner as in the above-prepared pigment dispersion liquid A, the volume average particle diameter of the pre-prepared pigment dispersion liquid M was 78 nm.
The preliminarily prepared pigment dispersion A and the preliminarily prepared pigment dispersion M were mixed at a ratio of 80 parts by weight and 20 parts by weight, respectively, to prepare a green pigment dispersion (pigment dispersion N) according to the present invention. When the dispersed particle diameter of the pigment particles was measured in the same manner as the above-prepared pigment dispersion liquid A, the dispersed particle diameter of the green pigment dispersion liquid (pigment dispersion liquid N) according to the present invention was 82 nm in volume average particle diameter. .
Further, pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm were 90% by volume of all pigment particles. Furthermore, pigment particles of 5 nm or more and less than 30 nm were 2% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 40% by volume, and pigment particles of 61 nm or more and less than 100 nm were 48% by volume. Further, the particle size when the cumulative particle size distribution was 50% by volume in all particles was 79 nm.

(2) Preparation of green curable resin composition for color filter Instead of using the green pigment dispersion (pigment dispersion C) of Example 1 in the preparation of the green curable resin composition for color filter of Example 1, the above A green curable resin composition for a color filter according to Comparative Example 5 was obtained in the same manner as in Example 1 except that the green pigment dispersion liquid (Pigment Dispersion Liquid L) obtained in Comparative Example 5 was used.

(3) Evaluation of green curable resin composition for color filter In the same manner as in Example 1, particle size distribution and contrast were evaluated.
(I) Particle size distribution The dispersed average particle size of the curable resin composition of Comparative Example 5 was 81 nm in volume average particle size.
Moreover, the pigment particles of 5 nm or more and less than 100 nm were 88% by volume of the total pigment particles. Further, the pigment particles of 5 nm or more and less than 30 nm were 2% by volume of the total pigment particles, the pigment particles of 30 nm or more and less than 61 nm were 40% by volume, and the pigment particles of 61 nm or more and less than 100 nm were 46% by volume. Further, the particle size when the cumulative particle size distribution was 50% by volume in all particles was 81 nm.

(Ii) Contrast Using the green curable resin composition for a color filter of Comparative Example 5, the contrast value of the cured film adjusted to a film thickness such that y = 0.500 was 5720. Although the parallel luminance of the bright line in the wavelength range of 560 to 640 nm was improved, on the other hand, the orthogonal luminance in the wavelength range of 400 nm to 450 nm was also increased, so the contrast was lowered.

<Example 5>
(1) Preparation of Green Pigment Dispersion for Color Filter Dispersion A in which coarse particles were removed from the above-prepared pigment dispersion A and the above-prepared pigment dispersion B using an ultracentrifuge at 40,000 rpm for 10 minutes. Made with 'and B'. Each was mixed at a ratio of 90 parts by weight and 10 parts by weight to prepare a green pigment dispersion (pigment dispersion C ′) according to the present invention. When the dispersed particle diameter of the pigment particles was measured in the same manner as the above-prepared pigment dispersion liquid A, the dispersed particle diameter of the green pigment dispersion liquid (pigment dispersion liquid C ′) according to the present invention was 42 nm in volume average particle diameter. It was.
Further, the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm were 99% by volume of the total pigment particles. Furthermore, pigment particles of 5 nm or more and less than 30 nm were 12% by volume of all pigment particles, pigment particles of 30 nm or more and less than 61 nm were 64% by volume, and pigment particles of 61 nm or more and less than 100 nm were 23% by volume. Further, the particle size was 43 nm when the cumulative particle size distribution was 50% by volume of all particles.

(2) Preparation of green curable resin composition for color filter Instead of using the green pigment dispersion (pigment dispersion C) of Example 1 in the preparation of the green curable resin composition for color filter of Example 1, the above A green curable resin composition for a color filter of Example 5 was obtained in the same manner as in Example 1 except that the green pigment dispersion (pigment dispersion C ′) obtained in 1 was used.

(3) Evaluation of green curable resin composition for color filter In the same manner as in Example 1, particle size distribution and contrast were evaluated.
(I) Particle size distribution The dispersed particle size of the curable resin composition of Example 5 was 44 nm in volume average particle size.
Moreover, the pigment particles of 5 nm or more and less than 100 nm were 99% by volume of the total pigment particles. Further, the pigment particles of 5 nm or more and less than 30 nm were 11% by volume of the total pigment particles, the pigment particles of 30 nm or more and less than 61 nm were 64% by volume, and the pigment particles of 61 nm or more and less than 100 nm were 24% by volume. Furthermore, the particle size was 45 nm when the cumulative particle size distribution was 50% by volume in all particles.

(Ii) Contrast The contrast value of the cured film adjusted to a film thickness of y = 0.450 using the green curable resin composition for a color filter of Example 2 was 8200. In addition, particles having a size of 100 nm or more were not observed in a field of view of 100000 times by cross-sectional TEM observation.

It is a typical longitudinal section showing an example of a color filter concerning the present invention. It is typical sectional drawing about an example of a liquid crystal panel. It is typical sectional drawing about another example of a liquid crystal panel. It is a figure which shows the spectral luminance at the time of the polarizing plate of Example 1 and Comparative Example 1 of this invention parallel. It is a figure which shows the spectral luminance at the time of the polarizing plate orthogonal of Example 1 and Comparative Example 1 of this invention. It is a figure which shows the spectral luminance at the time of the polarizing plate of Example 1 of this invention and the comparative example 2 parallel. It is a figure which shows the spectral luminance at the time of the polarizing plate orthogonal of Example 1 and Comparative Example 2 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Color filter 2 Electrode substrate 3 Gap part 4 Sealing material 5 Transparent substrate 6 Black matrix layer 7 (7R, 7G, 7B) Colored layer 8 Protective film 9 Transparent electrode film 10 Orientation film 11 Pearl 12 Columnar spacer 101, 102 Color liquid crystal display Device 103 Color filter

Claims (19)

A green pigment, a yellow or orange pigment having a light transmittance of 90% or more in the wavelength region of 560 nm to 640 nm and 12% or less in the wavelength region of 400 nm to 450 nm, a pigment dispersant, and a solvent. A green pigment dispersion for color filters, wherein the dispersed pigment particles have an average dispersed particle size of 15 to 80 nm.
[Test membrane]
30 parts by weight of the yellow or orange pigment and the pigment dispersants 12 to 24 so that y = 0.450 in the chromaticity coordinates (x, y) in the XYZ color chromaticity diagram measured using a C light source A resin composition for a test film comprising 76 to 88 parts by weight of a methyl methacrylate / methacrylic acid copolymer (molar ratio 9/1) having a weight average molecular weight of 7000 to 15000 and a solvent of 520 parts by weight is obtained using an alkali-free glass. A test film is formed by applying and drying on a substrate.   The green pigment dispersion for a color filter according to claim 1, wherein the yellow or orange pigment is 3 to 45 wt% in the total pigment.   The green color for a color filter according to claim 1 or 2, wherein the green pigment is at least one selected from the group consisting of CI Pigment Green 36, CI Pigment Green 7, and CI Pigment Green 58. Pigment dispersion.   The yellow or orange pigment is CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Yellow 17, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 173, CI Pigment Yellow 117, CI Pigment Orange 66, CI Pigment The green pigment dispersion for a color filter according to any one of claims 1 to 3, wherein the dispersion is one or more selected from the group consisting of orange 68 and CI pigment orange 69.   The green pigment for a color filter according to any one of claims 1 to 4, wherein in the dispersed pigment particles, the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm are 99% or more of the total pigment particles. Dispersion.   Further, a polymer containing a pigment dispersant, the polymer containing a repeating unit derived from dimethylaminoethyl (meth) acrylate or a quaternary ammonium salt of dimethylaminoethyl (meth) acrylate, and / or poly The green pigment dispersion for a color filter according to any one of claims 1 to 5, which is an allylamine derivative.   7. The solvent according to claim 1, wherein the solvent is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate, and cyclohexanone. Green pigment dispersion for color filters. A green pigment, a yellow or orange pigment having a light transmittance of 90% or more in the wavelength range of 560 nm to 640 nm and 12% or less in the wavelength range of 400 nm to 450 nm, a pigment dispersant, and a curing A green curable resin composition for a color filter, comprising an adhesive binder system and a solvent, wherein the dispersed pigment particles have an average dispersed particle diameter of 15 to 80 nm. Resin composition.
[Test membrane]
30 parts by weight of the yellow or orange pigment and the pigment dispersants 12 to 24 so that y = 0.450 in the chromaticity coordinates (x, y) in the XYZ color chromaticity diagram measured using a C light source A resin composition for a test film comprising 76 to 88 parts by weight of a methyl methacrylate / methacrylic acid copolymer (molar ratio 9/1) having a weight average molecular weight of 7000 to 15000 and a solvent of 520 parts by weight is obtained using an alkali-free glass. A test film is formed by applying and drying on a substrate.   The green curable resin composition for a color filter according to claim 8, wherein the yellow or orange pigment is 3 to 45% by weight in the total pigment.   The green color for a color filter according to claim 8 or 9, wherein the green pigment is at least one selected from the group consisting of CI pigment green 36, CI pigment green 7, and CI pigment green 58. Curable resin composition.   The yellow or orange pigment is CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Yellow 17, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 173, CI Pigment Yellow 117, CI Pigment Orange 66, CI Pigment The green curable resin composition for a color filter according to any one of claims 8 to 10, wherein the composition is one or more selected from the group consisting of orange 68 and CI pigment orange 69.   The green cured color filter according to any one of claims 8 to 11, wherein in the dispersed pigment particles, the pigment particles having a dispersed particle diameter of 5 nm or more and less than 100 nm are 99% or more of the total pigment particles. Resin composition.   Further, a polymer containing a pigment dispersant, the polymer containing a repeating unit derived from dimethylaminoethyl (meth) acrylate or a quaternary ammonium salt of dimethylaminoethyl (meth) acrylate, and / or poly The green curable resin composition for a color filter according to any one of claims 8 to 12, which is an allylamine derivative.   14. The solvent according to claim 8, wherein the solvent is one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate, and cyclohexanone. Green curable resin composition for color filters.   The green curable resin composition for a color filter according to any one of claims 8 to 14, wherein the curable binder system is a photosensitive binder system.   When a cured film of a resin composition in which 0.450 ≦ y <0.600 is formed in chromaticity coordinates (x, y) in an XYZ color chromaticity diagram measured using a C light source, the resin composition The ratio of the luminance that is transmitted when a cured film of a product is sandwiched between two polarizing plates that are orthogonal or parallel (luminance when the polarizing plates are parallel / luminance when the polarizing plates are orthogonal) is 3500 or more. The green curable resin composition for a color filter according to any one of claims 8 to 15, wherein   A color filter comprising a colored layer formed using the green curable resin composition for a color filter according to any one of claims 8 to 16.   The ratio of the luminance that is transmitted when the color filter is sandwiched between two polarizing plates that are orthogonal or parallel (luminance when the polarizing plates are parallel / luminance when the polarizing plates are orthogonal) is 3500 or more. The color filter according to claim 17, wherein:   A display device comprising the color filter according to claim 17 or 18.

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