JP2012203361A - Coloring resin composition, color filter, liquid crystal display device, and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring resin composition with which a color filter with a high viewing angle characteristic may be obtained and to provide a liquid crystal display device and an organic EL display device with high quality.SOLUTION: A coloring resin composition comprises (A) a coloring material, (B) a solvent, and (C) a binder resin. A polymer having a double bond equivalent of 550 or more is included as (C) the binder resin in a content of 30 wt.% or more based on the entire binder resin, and this polymer is obtained through polymerization using a compound having a glass transition temperature of 20°C or less as a monomer component, and the compound has a charged monomer ratio of 30 wt.% or more.

Description

  The present invention resides in a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for producing color filters used in liquid crystal display devices and the like. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.
In recent years, the trend of technological innovation has been rapid, and higher transmittance and high contrast have been required for color filters. In order to form a high-contrast color filter, it is necessary to disperse a pigment that is highly atomized and whose particle size distribution is narrowly controlled, and the technology for controlling the pigment particle size is rapidly developing.

  On the other hand, liquid crystal display devices and the like are required to further improve display characteristics such as visibility in all directions, and the influence of the color filter phase difference (retardation) on the display characteristics cannot be ignored. Since the phase difference of the color filter is relatively small compared to other members used in the liquid crystal display device, this problem has not been emphasized so far, but the phase difference of the colored display pixels is greatly different. As a leaked light, there may be a problem in viewing angle visibility.

In order to perform phase difference compensation of this liquid crystal display device or the like, a phase difference film may be used together (see Patent Document 1). As the retardation film, a film obtained by stretching a polycarbonate film or the like, or a film obtained by applying a liquid crystal material having birefringence anisotropy to a triacetyl cellulose film or the like is usually used.
However, in the above-described retardation film, the retardation amount is kept uniform in the plane, so that the optimum retardation amount is not necessarily set for each actually displayed pixel. There is no phase difference compensation. One reason for this is that the phase difference and refractive index of the liquid crystal itself have a wavelength dependency of the transmitted light, so the phase difference depends on the display pixel color of each color (actually the wavelength of the transmitted light) that makes up the color filter. The amount of retardation required for the film is also different.

In response to this, for example, as described in Patent Document 2, an attempt has been made to control the phase difference in accordance with the wavelength of transmitted light and perform phase difference compensation more optimally.
However, in reality, despite such attempts, there was a problem that when a black display with a viewing angle compensation from an oblique direction was observed, it was colored red-purple due to red and blue leakage light. .

JP-A-10-153802 JP 2005-148118 A

This invention is examined in view of the said subject, and makes it a subject to provide the colored resin composition with which the viewing angle characteristic of the obtained color filter is favorable.
Furthermore, an object of the present invention is to provide a high-quality liquid crystal display device and an organic EL display device.

As a result of intensive studies, the present inventors have found that the phase difference of the thin film is caused by the anisotropic arrangement of dipole moments possessed by resins, pigments, etc., especially when manufacturing a color filter, in the firing process of the color filter, It was speculated that the stress generated by the contraction of the thin film contributed to the anisotropic arrangement of the dipole moment.
That is, it is presumed that reducing the internal stress of the thin film during the firing process of the color filter weakens the arrangement of dipole moments such as resin and pigment, leading to a reduction in phase difference. The strength of the internal stress that occurs during the firing process, that is, during thermosetting and heating / cooling depends on the hardness and elastic modulus of the thin film, but the internal stress is particularly flexible in the main chain skeleton that forms the crosslinked structure of the binder resin. We have also found that it depends greatly on gender.

As a result of further investigation based on the above knowledge, as a binder resin, a monomer having a double bond equivalent of a specific value or higher and a monomer having a specific glass transition temperature or lower is specified as a monomer component. The inventors have found that the above problems can be solved by using a polymer containing a large amount as a resin, and have reached the present invention.
That is, the present invention is a colored resin composition containing (A) a color material, (B) a solvent, and (C) a binder resin, and (C) a polymer having a double bond equivalent of 600 or more as the binder resin. In the total binder resin, and the polymer is polymerized using a compound having a glass transition temperature of 20 ° C. or lower as a monomer component, and the charged monomer ratio of the compound is 30% by weight. The present invention resides in a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device, which are described above.

A pixel formed using the colored resin composition of the present invention can reduce the phase difference.
Therefore, a liquid crystal display device and an organic EL display device including pixels formed using the colored resin composition of the present invention have a wide viewing angle, excellent display characteristics, and high quality.

It is a cross-sectional schematic diagram which shows an example of the organic EL element containing the color filter of this invention.

Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, the “retardation” of the color filter pixel means R _th represented by the following equation.

In the above formula, _nx and _ny are refractive indexes in two in-plane orthogonal directions, _nz is a refractive index in the film thickness direction, and d is a film thickness. In the case of the pixel for a color filter, typically for an in-plane isotropy, n _x and n _y affect the value of even R _th is set to any direction of the plane it is considered that there is no.
In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ".

Further, “total solid content” means all components of the colored resin composition of the present invention other than the solvent components described later.
In the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of the base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later.

Moreover, terms such as “CI Pigment Green” mean a color index (CI).
The present invention is a colored resin composition containing (A) a color material, (B) a solvent, and (C) a binder resin, and containing a specific polymer as the binder resin.
First, (C) the binder resin will be described.

[(C) Binder resin]
{Specific polymer}
The binder resin in the present invention is obtained by polymerizing a compound having a double bond equivalent of 550 or more and a glass transition temperature of 20 ° C. or less as a monomer component, and the charged monomer ratio of the compound is 30% by weight or more. Contains a certain polymer (hereinafter sometimes referred to as “specific polymer”).

The double bond equivalent of the polymer is usually 550 or more, preferably 600 or more, more preferably 650 or more.
Moreover, since it is preferable that the binder resin used by this invention does not contain a double bond more, there is no restriction | limiting in particular about an upper limit.
Within the above range, the elastic modulus of the color filter is reduced by a necessary amount, so that the _Rth reduction effect is sufficiently exhibited, which is preferable.

Here, the double bond equivalent is the weight of the resin solid content per 1 mol of the double bond of the polymer, and can be obtained by dividing the weight of the resin solid content by the amount of the double bond of the polymer (g / Mol). In the present invention, the double bond equivalent is a theoretical value calculated from the amount of raw material charged.
(Compound having a glass transition temperature of 20 ° C. or lower)
The specific polymer of the present invention is obtained by polymerizing a compound having a glass transition temperature of 20 ° C. or lower (hereinafter sometimes referred to as “low Tg monomer”) as a monomer component, and the charged monomer ratio of the compound is 30. % By weight or more.

The glass transition temperature of the low Tg monomer is usually 20 ° C. or lower, preferably 0 ° C. or lower, more preferably −10 ° C. or lower.
Within the above range, it is preferable in that the effects of the present invention can be easily obtained.
The low Tg monomer in the present invention is preferably a (meth) acrylic compound, specifically, normal butyl (meth) acrylate, normal hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, Examples include lauryl (meth) acrylate and stearyl (meth) acrylate.

  Among these, the low Tg monomer is preferably a compound represented by the following formula (1) from the viewpoint of good compatibility with other monomers and easy copolymerization.

(In the formula (1), R ⁸⁹ represents a hydrogen atom or a methyl group,
R ⁹⁰ represents an alkyl group having 4 to 20 carbon atoms which may have a substituent. )
In the above formula, R ⁸⁹ is preferably a hydrogen atom or a methyl group in terms of providing a flexible main chain skeleton.
R ⁹⁰ represents an alkyl group having 4 to 20 carbon atoms which may have a substituent.

The alkyl group may be branched or linear, and examples thereof include 2-ethylhexyl as a branched alkyl chain, and a dodecyl group and a stearyl group as a linear one.
Examples of the substituent that the alkyl group for R ⁹⁰ may have include an unsaturated bond, halogens, a phenyl group, and a cyclohexyl group.

In addition, since a phase difference will increase when it contains a hydroxyl group, it is not preferable. This is presumed to be because the hydroxyl group reduces the affinity with the pigment.
(Low Tg monomer content)
The content of the low Tg monomer in the specific polymer is usually 30% by weight or more, preferably 50% by weight or more, and usually 100% by weight or less in terms of the charged monomer ratio.

Within the above range, it is preferable in that the effects of the present invention can be easily obtained.
In addition, the specific polymer in the present invention is preferably a polymer composed of a low Tg monomer, and the effect of the present invention is easily obtained.
The specific polymer may contain one low Tg monomer or may contain two or more different low Tg monomers.

(Specific polymer content)
The content of the binder resin (C) in the colored resin composition of the present invention is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, preferably 60% by weight in the total solid content. % Or less.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.

The content of the specific polymer in the colored resin composition of the present invention is usually 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more, and usually 100% by weight or less in the total binder resin. is there.
Within the above range, it is preferable in that the effects of the present invention can be easily obtained.
Moreover, since it is easy to obtain the effect of this invention satisfactorily that the binder resin in this invention is all a specific polymer, it is especially preferable that content of a specific polymer is 100 weight% in all the binder resins.

<Reason for effect>
The reason why the phase difference can be reduced by containing a specific polymer as the binder resin is estimated as follows.
As described above, the phase difference of the thin film is due to the fact that the dipole moment of the resin, the pigment, and the like is anisotropically arranged due to the stress generated by the shrinkage of the thin film during the firing process.

Here, since the present invention uses a specific polymer having a large double bond equivalent as the binder resin, the cross-linking density of the thin film is lowered, and the hardness and elastic modulus of the thin film are lowered.
In addition, since the monomer component of the specific polymer includes a compound having a glass transition temperature of 20 ° C. or lower, the main chain skeleton of the polymer is flexible.
From the above two points, the internal stress at the time of firing the color filter is reduced, the anisotropy of the dipole moment of the resin or pigment is reduced, and as a result, the phase difference of the obtained color filter can be reduced.

(Binder resin type)
The type of the specific polymer is not particularly limited, but since the effect of reducing the retardation of the obtained pixel is large, in the polymer having a resin skeleton described later (C-3), the double bond equivalent is within the above range, and It is preferable to contain a low Tg monomer as a monomer component.
{Other polymers}
The colored resin composition in the present invention may contain other polymers other than the specific polymer, and known resins such as JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, The polymers described in JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and the like may be contained.

Among them, the following resins (C-1) to (C-5) are preferable.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the carboxyl group-containing linear alkali-soluble resin (resin (C-2)) (hereinafter referred to as “resin (C-3)” May be referred to.)
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Among these, resin (C-3) is particularly preferable, and the resin will be described below.

Incidentally, the resins (C-1), (C-2), (C-4) and (C-5) are dissolved by an alkaline developer and have a solubility sufficient to achieve the intended development processing. As long as it has anything, it is the same as that described in JP 2009-025813 A as the same item. The preferred embodiment is also the same.
(C-3): Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion in the carboxyl group-containing linear alkali-soluble resin. The carboxyl group-containing linear alkali-soluble resin has a carboxyl group. If it does, it will not specifically limit, Usually, it obtains by superposing | polymerizing the polymerizable monomer containing a carboxyl group.

  Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl adipic acid. 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- ( (Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxybutyl Succinic acid, 2- (me ) Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; -Monomers obtained by adding lactones such as caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone; hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid, or anhydrides thereof And monomers added with acids or anhydrides. A plurality of these may be used.

Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
In addition, the carboxyl group-containing linear alkali-soluble resin may be obtained by copolymerizing the above carboxyl group-containing polymerizable monomer with another polymerizable monomer having no carboxyl group.
Examples of other polymerizable monomers include, but are not limited to, those described in JP-A-2009-52010. Of these polymerizable monomers, a copolymer resin containing benzyl (meth) acrylate is particularly preferred from the viewpoint of excellent pigment dispersibility.

Further, (C-3) resin is a resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of a carboxyl group-containing linear alkali-soluble resin.
The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.
For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- An acyclic epoxy group-containing unsaturated compound such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but an alicyclic epoxy group-containing unsaturated compound is preferred from the viewpoint of heat resistance and pigment dispersibility.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. Further, the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group, and suitable alicyclic epoxy group-containing unsaturated compounds are represented by the following formulas (3a) to (3m). The compound which is made is mentioned.

In the above formulas (3a) to (3m), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group, R ¹³ represents a divalent hydrocarbon group, and n is an integer of 1 to 10.
In the formulas (3a) to (3m), the alkylene group represented by R ¹² preferably has 1 to 10 carbon atoms.
Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and a methylene group, an ethylene group, and a propylene group are preferable.

As the hydrocarbon group R ^13, preferably has 1 to 10 carbon atoms, alkylene group, a phenylene group, and the like. These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Among these, a compound represented by the formula (3c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.

Various methods can be used to add the epoxy group-containing unsaturated compound to the carboxyl group portion. For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride A quaternary ammonium salt such as pyridine, triphenylphosphine, etc. in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours. Saturated compounds can be introduced.

In addition, when making it into a specific polymer with (C-3) resin frame | skeleton, it is preferable to contain the component described as the said low Tg monomer as another polymerizable monomer which does not have a carboxyl group, for example.
The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 mgKOH / g, preferably 20 to 150 mgKOH / g, more preferably 30 to 150 mgKOH / g. Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-100000 normally, Preferably it is 4000-50000, More preferably, it is 5000-30000.

Moreover, content of (C) binder resin is 0.1 to 80 weight% normally in a total solid, Preferably it is 1 to 60 weight%.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.
[(A) Color material]
(A) Examples of the color material include pigments and dyes, but pigments are preferably used from the viewpoint of good coloring power.
From the viewpoint of the effect of the invention, pigments of various colors such as red pigments, green pigments, yellow pigments, purple pigments, orange pigments and brown pigments can be usually used.

Examples of the chemical structure of various pigments include organic pigments such as azo, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition to these, various inorganic pigments can also be used.
Specific examples of pigments that can be used in the present invention are shown below by pigment numbers, but are not limited to these examples.

  First, as a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 242, 254, and the like.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like. Of these, C.I. I. Pigment Green 7, 3
6, 58 and so on.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 17 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203 204, 205, 206, 207, 208, and the pigments described in JP-A-2005-325350 and JP-A-2007-25687, and pigments defined by <Pigment Y> below (hereinafter referred to as “Pigment Y”) And the like.

<Pigment Y>
A compound obtained by inserting another compound into a 1: 1 complex of azobarbituric acid with nickel represented by the following structural formula or a compatible isomer thereof.

Of these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, the pigment and the pigment Y described in the above-mentioned 2 publications, and more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180, the pigment and the pigment Y described in the above-mentioned 2 publications, and the like.
Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Of these, C.I. I. Pigment violet 19, 23, etc., more preferably C.I. I. Pigment violet 23 and the like.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Of these, C.I. I. Pigment orange 38, 71 and the like.

Moreover, you may form the resin black matrix of a color filter using the colored resin composition of this invention, and a black pigment can be used in that case. In addition, a black pigment may be used independently and may mix and use pigments, such as red, green, and blue. Further, it may be an inorganic pigment or an organic pigment.
Furthermore, examples of inorganic pigments that can be used in the present invention include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.

In addition, the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, as the (A) pigment, a red pigment and a yellow pigment can be used in combination, or a green pigment and a yellow pigment can be used in combination.
The average primary particle size of the pigment in the present invention is usually 100 nm or less, preferably 80 nm or less, more preferably 20 nm or more and 70 nm or less. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, the case of containing a pigment having an average primary particle size of 20 nm to 60 nm is particularly preferable.

By keeping the average primary particle size of the pigment used in the above range, the depolarization characteristics are kept good, high contrast and transmittance are realized, dispersion stability is good, and heat resistance and light resistance are also improved. An excellent pigment dispersion and colored resin composition can be obtained.
The primary particle diameter of the pigment can be determined by the following method.
First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). However, in the case of organic pigments, the particle diameter of each pigment particle is the diameter corresponding to the area circle converted to the diameter of a circle having the same area, and the particle diameter of each of plural (usually about 200 to 300) pigment particles. Ask for. Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.

The pigment thus obtained may be used alone, but one or two or more pigments can be mixed and used within a range not impairing the effects of the present invention.
The pigment content in the present invention is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, and usually 0.1% by weight or more, preferably with respect to the total solid content. It is 0.5% by weight or more, more preferably 1% by weight or more.

By making the content of the pigment in the above range, the film thickness with respect to the color density does not become too large, without adversely affecting the gap control or the like at the time of liquid crystal cell formation, and sufficient image formability can be obtained. The dispersed state of the pigment is also maintained, and aggregation and sedimentation hardly occur, and as a result, problems such as thickening and lowering of brightness and contrast can be solved.
[(B) Solvent]
In the present invention, the solvent has a function of adjusting the viscosity by dissolving or dispersing components other than the above-described components in addition to the above components.

The solvent is not particularly limited as long as it can dissolve or disperse each component. As such a solvent, the solvent etc. which are described in international publication WO2009 / 107734 etc. are mentioned, for example.
Commercially available products corresponding to these solvents include mineral spirits, valsol # 2, Apco # 18 solvent, apco thinner, and soak solvent no. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like. These solvents may be used alone or in combination of two or more.

In addition, the content of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by weight or less, and preferably 50% by weight in consideration of viscosity suitable for coating. Above, more preferably 60% by weight or more, particularly preferably 70% by weight or more.
[(D) Dispersant]
When the colored resin composition of the present invention contains a pigment, it is preferable to further contain (D) a dispersant.

  The (D) dispersant in the present invention is not particularly limited as long as the pigment is dispersed and stable. For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. A block copolymer is particularly preferable. Among them, the block copolymer is composed of an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom, and the amine value thereof is 80 mgKOH / g or more and 150 mgKOH / g or less ( Those in terms of effective solid content) are particularly preferred. More preferably, it is 100 mgKOH / g or more and 140 mgKOH / g or less.

Within the above range, the adsorptive power to the pigment surface is sufficient and the dispersion stability is good.
As the block copolymer, a (meth) acrylic block copolymer is preferable. The acrylic block copolymer can disperse the pigment (A) very efficiently. This is presumably because the molecular arrangement is controlled, so that there are few structures that obstruct the dispersant when adsorbing to the pigment.

In the present invention, the acrylic block copolymer is preferably an AB block composed of an A block and a B block and / or an ABA block copolymer.
The B block constituting the acrylic block copolymer preferably has a primary to tertiary amino group as a functional group containing a nitrogen atom, and the amino group is preferably —NR ⁴¹ R ⁴² (provided that R ⁴¹ And R ⁴² are each independently a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. What is preferable as a partial structure containing this is represented by the following formula, for example.

^{(However, R 41} and ^{R 42} has the same meaning as above ^{R 41} and ^{R 42, R 43} is one or more alkylene groups having a carbon ^{number, R 44} represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably methyl groups, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a methyl group. Examples of such a compound include a partial structure represented by the following formula.

  Two or more kinds of the partial structure containing an amino group as described above may be contained in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing an amino group may be partially contained in the B block within a range not impairing the effects of the present invention. Examples of such a partial structure include (meth) acrylic acid esters. And a partial structure derived from a monomer.

On the other hand, in the present invention, the A block of the (D) dispersant is not particularly limited as long as it is solvophilic and is composed of a monomer that can be copolymerized with the monomer constituting the B block described above.
Examples of the A block include polymer structures obtained by copolymerizing comonomers such as styrene monomers, (meth) acrylate monomers, (meth) acrylate monomers, vinyl acetate monomers, glycidyl ether monomers, and the like. It is done.

The (D) dispersant in the present invention is an AB block or ABA block copolymeric polymer compound composed of an A block and a B block as described above. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by a living polymerization method.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.

The amine value of the dispersant (in terms of effective solid content) is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
Further, the acid value of this block copolymer is preferably lower, although it depends on the presence and type of acidic group that is the basis of the acid value, and is usually 50 mgKOH / g or less, preferably 40 or less, more preferably 30. It is as follows.

When the average primary particle size of the pigment is small, the specific surface area increases and the amount of adsorbing dispersant per unit area decreases. In this case, the dispersant made of the copolymer is preferably used because it is more effective than the other dispersants.
The dispersant in the present invention is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of pigment in the colored resin composition.

The colored resin composition of the present invention may contain other dispersants as long as the effects of the present invention are not impaired. Examples of other dispersants include those described in JP-A-2006-343648, for example.
[Dispersion aid]
When the colored resin composition of the present invention contains a pigment as the colorant (A), it may further contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

The content of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, based on the total solid content of the pigment. Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less. By controlling the addition amount within the above range, it is preferable in that the effect as a dispersion aid is exhibited and the dispersibility and dispersion stability are better.
Further, when other dispersion aids are contained, the total amount of the dispersion aids is set within the above range.

[Dispersion resin]
The colored resin composition of the present invention may contain a part or all of a resin selected from the specific polymer in the binder resin (C) or other binder resin as the following dispersion resin.
Specifically, in the dispersion treatment step to be described later, the (C) binder resin is added to the (D) dispersant by adding the (C) binder resin together with the components such as the (D) dispersant described above. A synergistic effect contributes to the dispersion stability of (A) the color material (pigment). As a result, there is a possibility that the amount of (D) dispersant added can be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of pigment in the pigment dispersion.
As the dispersion resin, various (C) binder resins described later can be used.
The acid value of the dispersion resin is preferably 0.5 mgKOH / g or more, more preferably 1 mgKOH / g or more, most preferably 5 mgKOH / g or more, more preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, and 150 mgKOH / g. The following are most preferred. By controlling the acid value within the above range, the alkali developability is improved, and the handling becomes easy in synthesis and the like.

The weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, more preferably 200000 or less, more preferably 50000 or less, and 30000 or less. Most preferred. By controlling the molecular weight within the above range, the alkali developability can be improved and the dispersion stability can be prevented from being lowered.

[(E) Photopolymerization initiation system]
The colored resin composition of the present invention contains (E) a photopolymerization initiation system. (E) The photopolymerization initiating system is usually a mixture of (E1) a photopolymerization initiator and, if necessary, (E2) a polymerization accelerator, (E3) an additive such as a sensitizing dye (photopolymerization). It is a component having a function of generating polymerization active radicals by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiation system (E1) include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; JP-A-10-300922; Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

  Specifically, for example, biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3 ′). -Methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, And (4′-methoxyphenyl) -4,5-diphenylimidazole dimer.

  Alternatively, the romethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl)- Examples thereof include s-triazine.

Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like It is.

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and the like.
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

Among these (E1) photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (E2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

Each of these (E1) photopolymerization initiator and (E2) polymerization accelerator may be used alone or in combination of two or more.
Further, (E3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(E3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content of these photopolymerization initiation systems is usually 0.1 to 40% by weight, preferably 0.2 to 30% by weight, more preferably 0.5% in the total solid content. It is in the range of ˜20% by weight. Within the above range, the sensitivity to exposure light is good, and the solubility of the unexposed portion in the developer is good, which is preferable.

[(F) polymerizable monomer]
The colored resin composition of the present invention preferably contains (F) a polymerizable monomer. (F) The polymerizable monomer is not particularly limited as long as it is a low molecular weight compound that can be polymerized, but it may be referred to as an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of the photopolymerization initiation system when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (F) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.
(F) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (F) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g.

When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored resin composition of the present invention, the content of these (F) polymerizable monomers is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. Further, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
The ratio of (F) polymerizable monomer to the total amount of all (A) coloring materials is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. In addition, it is usually 200% by weight or less, preferably 150% by weight or less, and more preferably 110% by weight or less.

Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower solubility are difficult to place. preferable.
[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, the (A) color material, (B) solvent, (C) binder resin, (E) photopolymerization initiator, ( F) It can be prepared by mixing with a polymerizable monomer and other additives.

  (A) When a pigment is included as a coloring material, the pigment is added in a solvent in the presence of (D) a dispersant and, if necessary, a dispersing aid, optionally with (C) a part of the binder resin, For example, using a paint shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like, a colored dispersion is prepared by mixing and dispersing while pulverizing. Examples of the color dispersion include (E) a photopolymerization initiator, (C) a binder resin, and, if necessary, an additive such as (F) a polymerizable monomer, and a method of preparing the mixture by mixing. it can.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. This colored resin composition is supplied onto the substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a color filter, and a liquid crystal display device (panel) and an organic EL display device using them will be described.

<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.

  First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for forming the pixel is not particularly limited as long as it is transparent and has an appropriate strength. For example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, or a thermoplastic resin is used. A sheet, an epoxy resin, a thermosetting resin, various glass, etc. are mentioned.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.

When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.
The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.

Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

  A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, further 40 ° C. or lower. Is preferred.
The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is, and is used as a part of a color display, a liquid crystal display device, or the like. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Also, a column structure (photo spacer) made of photolithography may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble according to a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device including the color filter of the present invention, for example, as shown in FIG. 1, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the following examples, “part” represents “part by weight”. [1] (C) Synthesis of Binder Resins A to H [Synthesis Example 1: (Synthesis of Binder Resin A)]
A separable flask equipped with a cooling tube was prepared as a reaction vessel, charged with 90 parts by weight of propylene glycol monomethyl ether acetate, and heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.

Meanwhile, 37.5 parts by weight of dodecyl methacrylate, 37.5 parts by weight of normal butyl methacrylate, 25 parts by weight of methacrylic acid, 0.1 part by weight of 2,2′-azobis (2-methylbutyronitrile), chained in the monomer tank Charge the transfer agent tank with 5.6 parts by weight of α-thioglycerol and 15.6 parts by weight of propylene glycol monomethyl ether acetate, and start dropping from the monomer tank and the chain transfer agent tank after the temperature of the reaction tank is stabilized at 90 ° C. Then, polymerization was started. The dropwise addition was carried out over 120 minutes while maintaining the temperature at 90 ° C., and 240 minutes after the completion of the dropwise addition, 0.1 part by weight of 2,2′-azobis (2-methylbutyronitrile), propylene glycol monomethyl ether acetate 2 .5 parts by weight were added dropwise. After completion of the additional addition, the reaction was further carried out at 90 ° C. for 2 hours, and then the temperature was raised to bring the reaction vessel to 110 ° C. Thereafter, the temperature was maintained at 110 ° C. for 2 hours, and then cooled to room temperature.

  Subsequently, 27.5 parts by weight of glycidyl methacrylate, 0.1 part by weight of α-methoxyphenol, 0.2 part by weight of 1,8-diazabicyclo [5.4.0] -7-undecene, propylene glycol monomethyl is added to the reaction vessel. 2.0 parts by weight of ether acetate was charged and reacted at 110 ° C. for 11 hours. By cooling to room temperature after the reaction, 51.1 wt% binder resin A having a weight average molecular weight of 7300, an acid value of 50.4 mg KOH / g, and a double bond equivalent of 688 was obtained.

[Synthesis Example 2: Synthesis of Binder Resin B]
In Synthesis Example 1, the same method except that 37.5 parts by weight of dodecyl methacrylate was changed to 37.5 parts by weight of 2-ethylhexyl methacrylate, weight average molecular weight 6900, acid value 62.2 mgKOH / g, double bond equivalent 688 52.8 wt% binder resin B was obtained.
[Synthesis Example 3: Synthesis of Binder Resin C]
In Synthesis Example 1, the same method except that 37.5 parts by weight of dodecyl methacrylate was changed to 37.5 parts by weight of normal hexyl methacrylate, weight average molecular weight 11600, acid value 60.8 mgKOH / g, double bond equivalent 688 55.5 wt% binder resin C was obtained. [Synthesis Example 4: Synthesis of Binder Resin D]
In Synthesis Example 1, the same method except that 37.5 parts by weight of dodecyl methacrylate was changed to 37.5 parts by weight of normal butyl methacrylate, the weight average molecular weight was 7300, the acid value was 56.7 mgKOH / g, and the double bond equivalent was 688. Obtained 5 wt% binder resin D.

[Synthesis Example 5: Synthesis of Binder Resin E]
In Synthesis Example 1, the same method except that 37.5 parts by weight of dodecyl methacrylate was changed to 37.5 parts by weight of benzyl methacrylate, and 51.51 having a weight average molecular weight of 5400, an acid value of 58.6 mgKOH / g, and a double bond equivalent of 688. A 2 wt% binder resin E polymer solution was obtained.
[Synthesis Example 6: Synthesis of Binder Resin F]
In Synthesis Example 1, the same method except that 37.5 parts by weight of dodecyl methacrylate was changed to 37.5 parts by weight of cyclohexyl methacrylate, the weight average molecular weight was 7500, the acid value was 56.8 mgKOH / g, and the double bond equivalent was 688. 62.2% by weight binder resin F was obtained.

[Synthesis Example 7: Synthesis of Binder Resin G]
In Synthesis Example 1, the same method except that 37.5 parts by weight of dodecyl methacrylate was changed to 37.5 parts by weight of methyl methacrylate, 56.56 having a weight average molecular weight of 7800, an acid value of 63.1 mgKOH / g, and a double bond equivalent of 688. A 6% by weight binder resin G was obtained.
[Synthesis Example 8: Synthesis of Binder Resin H]
In Synthesis Example 1, the same method except that 37.5 parts by weight of dodecyl methacrylate was changed to 37.5 parts by weight of tricyclodecanyl methacrylate, a weight average molecular weight of 7600, an acid value of 63.0 mgKOH / g, a double bond equivalent of 688 51.1% by weight of binder resin H was obtained.

[Synthesis Example 9: Synthesis of Binder Resin I]
In Synthesis Example 1, 37.5 parts by weight of dodecyl methacrylate is 10.7 parts by weight of normal butyl methacrylate, 25 parts by weight of methacrylic acid is 39.9 parts by weight, and 27.5 parts by weight of glycidyl methacrylate is 39.4 parts by weight. A 52.1 wt% binder I polymer solution having a weight average molecular weight of 4700, an acid value of 104.7, and a double bond equivalent of 480 was obtained in the same manner except that

[Other binder resins J to M]
Binder resin J: Random copolymer represented by the following formula (weight average molecular weight 8400, acid value 80.0 mgKOH / g, double bond equivalent 480)

(In the above structural formulas, l, m, n, and o represent integers.)
Binder resin K: Random copolymer in which the styrene portion is changed to a normal butyl group in the structural formula of the synthetic resin J (weight average molecular weight 7500, acid value 86.6 mgKOH / g, double bond equivalent 490)
Binder resin L: Random copolymer in which the tricyclodecanyl methacrylate portion is changed to a normal butyl group in the structural formula in the synthetic resin J (weight average molecular weight 7600, acid value 95.7 mgKOH / g, double bond equivalent 440)
Binder resin M: Random copolymer (weight average molecular weight 7600, acid value 95.2 mgKOH / g, double) in which the styrene portion and the tricyclodecanyl methacrylate portion are changed to normal butyl groups in the structural formula in the synthetic resin J Bond equivalent 440)
[2] (C) Synthesis of alkali-soluble resins N and O [Synthesis Example 10: (Synthesis of alkali-soluble resin N)]
114.0 g of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while performing nitrogen bubbling. 96.8 g (0.55 mol) of benzyl methacrylate, 33.3 g (0.45 mol) of methacrylic acid, and 4.925 g (0.03 mol) of 2,2′-azobis (isobutyronitrile) were added to propylene glycol 1-monomethyl. It melt | dissolved in ether 2-acetate 96.45g and it was dripped over 4 hours. After dropping, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. The obtained binder resin had a weight average molecular weight of 17000 and an acid value of 175 mgKOH / g.

[Synthesis Example 11: (Synthesis of alkali-soluble resin O)]
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Thereto, 24.1 parts by weight of methacrylic acid, 114.4 parts by weight of benzyl methacrylate and 15.4 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were dropped, and 2.2'- 6.50 parts by weight of azobis-2-methylbutyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours.
The weight average molecular weight measured by GPC of the binder resin thus obtained was about 18000.
The acid value was 100 mgKOH / g.

  The glass transition temperatures of the monomers used in the synthesis examples are shown in Table 1 below.

<Examples 1-4 and Comparative Examples 1-9>
[1] Preparation of blue pigment dispersion 78.4 parts by weight of propylene glycol monomethyl ether acetate, pigment C.I. I. Pigment Blue (P.B.) 15: 6 is 8.5 parts by weight, C.I. I. 3.5 parts by weight of Pigment Violet 23, 4.8 parts by weight of an acrylic dispersant (DB2000 manufactured by Big Chemie), and 4.0 parts by weight of the alkali-soluble resin N synthesized in the above Reference Example were mixed for 3 hours with a stirrer. A mill base having a solid content of 20% by weight was prepared by stirring. This mill base was subjected to a dispersion treatment using 600 parts by weight of 0.5 mmφ zirconia beads in a bead mill apparatus at a peripheral speed of 10 m / s and a residence time of 3 hours to obtain a blue pigment dispersion (I).

[2] Preparation of Blue Colored Resin Composition To the obtained blue pigment dispersion (I), other components are added so as to have the composition shown in Table 2 below, followed by filtration through a 5 μm membrane filter, and a blue curable resin composition A product was prepared.
The content of the blue pigment of the obtained blue curable resin composition I is 26.1% by weight with respect to the total solid content.

[3] Preparation of red pigment dispersion 78.4 parts by weight of propylene glycol monomethyl ether acetate, 12.0 parts by weight of pigment R254, 5.7 parts by weight of acrylic dispersant (Big Chemie LPN6919), synthesized in the above reference example 4.6 parts by weight of the alkali-soluble resin O thus prepared was mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid content concentration of 20% by weight. This mill base was subjected to dispersion treatment using 600 parts by weight of 0.5 mmφ zirconia beads in a bead mill apparatus at a peripheral speed of 10 m / s and a residence time of 3 hours to obtain a red pigment dispersion (I).

[4] Preparation of red colored resin composition To the obtained red pigment dispersion (I), other components were added so as to have the composition shown in Table 3 below, and the mixture was filtered through a 5 μm membrane filter. Was prepared.
The content of the red pigment in the obtained red colored resin composition is 55.7% by weight with respect to the total solid content.

[5] Manufacture of colored resin film Each of the obtained curable resin compositions is spin-coated on a transparent glass substrate for color filter (AN-100 manufactured by Asahi Glass), and pre-baked for 3 minutes on a hot plate at 80 ° C. And a dry coating film was formed. At the time of application, the rotational speed was adjusted so that the film thickness would be the color coordinate y = 0.124 after the following post-baking.

The obtained dried coating film was exposed at 60 mJ / cm ² through a mask pattern with a high-pressure mercury lamp and then post-baked in an oven at 230 ° C. for 30 minutes to form a colored resin film. The thickness of the colored resin film after drying was about 3.0 μm.
[Measurement of thickness retardation of color filter]
Using a RETS-100 manufactured by Otsuka Electronics Co., Ltd., which can measure minute phase differences up to 0.1 nm, three-dimensional refractive index measurement is performed by the rotating analyzer method, and the value obtained by a non-contact type film thickness meter is obtained. use as thickness was determined phase difference _{R th} in the thickness direction (z) at a wavelength of 420 nm. The results are shown in Table 4.

As shown in Table 4, pixels formed using the colored resin composition of the present invention have a small phase difference.
In other words, a liquid crystal display device including pixels formed using the colored resin composition of the present invention has a wide viewing angle, excellent display characteristics, and high quality.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (8)

(A) a coloring resin composition containing a coloring material, (B) a solvent, and (C) a binder resin,
(C) As a binder resin, containing a polymer having a double bond equivalent of 550 or more in a total binder resin of 30% by weight or more,
Further, the polymer is obtained by polymerizing a compound having a glass transition temperature of 20 ° C. or less as a monomer component,
A colored resin composition, wherein the charged monomer ratio of the compound is 30% by weight or more.   The colored resin composition according to claim 1, wherein the compound having a glass transition temperature of 20 ° C or lower is a (meth) acrylic compound. The colored resin composition according to claim 1, wherein the compound having a glass transition temperature of 20 ° C. or lower is a compound represented by the following formula (I).

(In the formula (1), R ⁸⁹ represents a hydrogen atom or a methyl group,
R ⁹⁰ represents an alkyl group having 4 to 20 carbon atoms which may have a substituent. )   The colored resin composition according to claim 1, further comprising (E) a photopolymerization initiation system.   Furthermore, (F) polymeric monomer is contained, The colored resin composition as described in any one of Claims 1-4 characterized by the above-mentioned.   It has a pixel formed using the colored resin composition as described in any one of Claims 1-5, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 6. An organic EL display device comprising the color filter according to claim 6.

Images