JP2012098599A - Colored resin composition, color filter, liquid crystal display device and organic el display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition capable of effectively increasing retardation without lowering the transmittance of pixels, while keeping compatibility between contrast ratio control and hue control.SOLUTION: There are provided a colored resin composition that contains (A) a pigment and (B) a polymerizable monomer in which (B) the polymerizable monomer is a compound having a specific structure, and the uses of the colored resin composition.

Description

  The present invention relates to a colored resin composition (hereinafter sometimes referred to as “resist”), a color filter, a liquid crystal display device, and an organic EL display.

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 improve display characteristics such as visibility in all directions, and the retardation (optical anisotropy) of the color filter in the thickness direction also affects the display characteristics. It cannot be ignored. This problem has not been emphasized so far because the retardation of the color filter was relatively small compared to other members used in liquid crystal display devices. For example, optical design is usually centered on green. For this reason, if the retardations of the red and blue colored display pixels and the green colored display pixels are significantly different, there may be a problem in visibility of the viewing angle as leakage light.

  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. Therefore, the optimum retardation amount is not always set for each actually displayed pixel, and the optimum retardation compensation is not necessarily performed. Is not done. 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 that the phase difference depends on the display pixel 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.

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

Another reason is that when each colored display pixel constituting the color filter itself has retardation, a phase difference occurs in the transmitted light, so that the viewing angle dependency of the liquid crystal display device increases and the display characteristics deteriorate. Is mentioned. For example, as described in Patent Documents 3 to 5, for example, a colored polymer thin film corresponding to a pixel of a color filter contains a polymer having a planar structure group in a side chain or is colored. There has been proposed an attempt to reduce the amount of retardation of a color filter by incorporating into a polymer thin film birefringence reducing particles having a birefringence opposite to that of the polymer. However, such a method has a problem that the solubility in the colored resin composition is insufficient and a necessary amount cannot be added, and there is a problem that the transmittance of the pixel is lowered due to coloration due to the addition.

  In addition, in order to provide a color filter with controlled retardation in each of red, green, and blue color display pixels, as described in Patent Documents 6 and 7, selection of pigment types and respective atomization are performed. A method of controlling the thickness direction retardation value of each color display pixel by controlling the degree (primary particle diameter of the pigment) has been proposed. However, such a method has a problem that it is difficult to achieve both contrast ratio control and hue control.

  On the other hand, in order to balance the retardation of each specific color, it may be intended to intentionally increase the retardation. However, in the above known technique, the direction of changing the retardation is reduced (ie, , Eliminate the phase difference). Further, according to the verification by the present inventors, a compound that increases retardation as described in Patent Document 8 has an adverse effect on development solubility and pixel forming ability, and the adverse effect becomes stronger as the addition amount increases. There was a problem.

JP-A-10-153802 JP 2005-148118 A JP 2000-136253 A JP 2000-187114 A JP 2003-344655 A JP 2008-152140 A JP 2007-293061 A JP 2008-185986 A

The present invention has been made in view of the above-mentioned problems, and its object is as follows.
(1) To provide a colored resin composition that is excellent in development solubility and pixel forming ability, and that can adjust retardation in an increasing direction while maintaining compatibility with pixel contrast ratio control and hue control.
(2) By using such a colored resin composition, it is possible to produce a color filter with high transmittance, high contrast, and low film thickness as a result.
(3) By providing such a color filter, a liquid crystal display device and an organic EL display having good visibility without coloring even when observed from an oblique direction are provided.

As a result of intensive studies to solve the above problems, the present inventors have found that the retardation can be increased in the color filter pixel by containing a compound having a specific structure in the polymerizable monomer. Invented.
That is, the gist of the present invention is as follows.
(1) A colored resin composition comprising (A) a pigment and (B) a polymerizable monomer, wherein (B) the polymerizable monomer is a compound represented by the following general formula (i).

(In the general formula (i), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted phenyl. Or a group having an ethylenic double bond, provided that at least one of R ^{1 to} R ⁴ is a group having an ethylenic double bond.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an arbitrary substituent. )
(2) The colored resin composition as described in (1) above, wherein the double bond equivalent of the compound represented by the general formula (i) is 120 or more and 300 or less.
(3) In the above (1) or (2), the content of the compound represented by the general formula (i) is 15% by weight or more and 100% by weight or less based on the total amount of the polymerizable monomers. The colored resin composition as described.
(4) The colored resin composition according to any one of (1) to (3), further comprising (C) a dispersant.
(5) The colored resin composition according to any one of (1) to (4), further comprising (D) a binder resin.
(6) The colored resin composition according to any one of (1) to (5), further comprising (E) a photopolymerization initiator and / or a thermal polymerization initiator.
(7) A color filter having a pixel produced using the colored resin composition according to any one of (1) to (6).
(8) A liquid crystal display device comprising the color filter according to (7).
(9) An organic EL display comprising the color filter according to (7).

  By using the colored resin composition of the present invention, the retardation can be adjusted in the increasing direction while maintaining both the contrast ratio control and the hue control of the pixel. In addition, by using such a colored resin composition, a color filter having high transmittance, high contrast, and low film thickness can be produced as a result, and there is no coloration even in observation from an oblique direction. A liquid crystal display device and an organic EL display with good characteristics can be provided.

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

The constituent requirements and embodiments of the present invention will be described in detail below, but these are examples of the embodiments of the present invention, and the present invention is not limited to these contents.
“(Meth) acryl” and the like mean “at least one of acryl and methacryl” and “(meth) acrylate” and the like mean “at least one of acrylate and methacrylate”. “Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

Further, “total solid content” means all components other than the solvent components described later, which are contained in the pigment dispersion or the colored resin composition.
In the present invention, unless otherwise specified, the weight average molecular weight refers to a polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography). “C.I.” means a color index (C.I.).

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 amount of KOH per 1 g of the solid content of the dispersant. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
Furthermore, in the present invention, “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.
<Colored resin composition>
Each component of the colored resin composition of this invention is demonstrated below. The colored resin composition according to the present invention contains (A) a pigment and (B) a polymerizable monomer as essential components, and may further contain additives other than the above components if necessary.

<(A) Pigment>
The colored resin composition of the present invention comprises (A) a pigment as an essential component. For example, when forming a color filter pixel or the like, a red pigment, a blue pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, brown Various color pigments such as pigments can be used.
Examples of the chemical structure include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition to these, various inorganic pigments can also be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

Examples of red pigments include 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 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 20
8,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253, 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 blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 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. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60, etc., more preferably C.I. I. Pigment Blue 15: 6 or 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, 36, 58, and the like.
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, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 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 pigments described in JP-A-2005-325350 and JP-A-2007-25687. Of these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and the pigments described in the above-mentioned 2 publications, and more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180, and the pigments described in the above-mentioned 2 publications.

  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, it is preferable that the (A) pigment used for the colored resin composition of this invention contains what has a phthalocyanine skeleton. Among these, it is particularly preferable to use brominated zinc phthalocyanine.
Ordinary zinc phthalocyanine has 16 hydrogen atoms in one molecule, and these bromine atoms substituted with bromine or chlorine atoms are brominated zinc phthalocyanine pigments particularly preferably used in the present invention. is there. Of these, brominated zinc phthalocyanine having an average of 13 or more bromine atoms in one molecule is particularly preferable because it exhibits extremely high transmittance and is suitable for forming a pixel of a color filter. Furthermore, brominated zinc phthalocyanine having 13 to 16 bromine atoms in one molecule and not containing chlorine or having an average of 3 or less in one molecule is preferable, and in particular, an average of 14 bromine atoms in one molecule is 14 Brominated zinc phthalocyanine having ˜16 and containing no chlorine atom in one molecule or having an average of 2 or less is preferred.

  Examples of such brominated zinc phthalocyanine pigments include phthalocyanine green pigments having a specific hue as described in JP-A-2004-70342 and JP-A-2004-70343. Especially, C.I. I. Pigment Green 58 is preferable. Such brominated zinc phthalocyanine pigments can be produced by a known production method disclosed in JP-A-50-130816.

  In addition, when brominated zinc phthalocyanine is used as the pigment (A) used in the colored resin composition of the present invention, it may be used alone, but brominated zinc phthalocyanine having a different bromination rate or chlorination rate, As long as the effect of the present invention is not impaired, it can be used by mixing with brominated phthalocyanine or the like in which the central metal is substituted with another metal. By changing the chlorination rate and bromination rate, or by changing the central metal, it is expected that the color tone of the pigment will change and that variations in the reproducible hue will increase.

On the other hand, examples of inorganic pigments that can be used in the colored resin composition of the present invention include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, and chromium oxide.
The above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

When forming the resin black matrix of a color filter using the colored resin composition of this invention, a black pigment can be used. A black pigment may be used alone, or pigments such as red, green, and blue may be mixed and used. Further, it may be an inorganic pigment or an organic pigment.
Examples of black pigments that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.

The average primary particle size of the pigment (A) according to the present invention is usually 100 nm or less, preferably 40 nm or less, more preferably 10 nm or more and 30 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 10 nm to 30 nm is particularly preferable.
By making the average primary particle size of the pigment (A) used within the above range, the depolarization characteristics are kept good, high contrast and transmittance are realized, dispersion stability is good, heat resistance and light resistance A colored resin composition for a color filter having excellent properties 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). In the case of organic pigments and titanium black pigments, a plurality of (usually about 200 to 300) pigment particles are obtained with the diameter of each pigment particle being equivalent to an area circle diameter converted to the diameter of a circle having the same area. The particle diameter is determined for each of. 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 (A) thus obtained may be used alone, but may be used alone or in combination of two or more types within a range not impairing the effects of the present invention.
The content of the pigment (A) in the colored resin composition of the present invention is usually 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less based on the total solid content, and usually 0%. .1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more. (A) If the amount of the pigment is too large, the dispersion state of the pigment is difficult to be maintained, and aggregation and sedimentation may occur. As a result, problems such as thickening, luminance, and decrease in contrast may occur. The problem is that the color density is thin and the color filter does not function sufficiently.

In addition, it is also preferable to adjust the pigment content in the colored resin composition that forms each pixel of the color filter to be described later to an optimum range.
<(B) Polymerizable monomer>
In the present invention, it is essential to contain a polymerizable monomer (B) represented by the following general formula (i). When the colored resin composition of the present invention contains the polymerizable monomer (B), the retardation of the color filter pixel formed using the colored resin composition can be adjusted in the increasing direction. Become.

(In the general formula (i), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted phenyl. Or a group having an ethylenic double bond, provided that at least one of R ^{1 to} R ⁴ is a group having an ethylenic double bond.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an arbitrary substituent. )
In the general formula (i), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent. Or a group having an ethylenic double bond. However, at least one of R ^{1 to} R ⁴ is a group having an ethylenic double bond. Moreover, it is more preferable that at least one of R ^{1 to} R ⁴ is a hydrogen atom.

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ each independently represent a hydrogen atom or an arbitrary substituent.
As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group , A heptyl group, an octyl group, a 2-ethylhexyl group and the like, and an alkyl group having 1 to 12 carbon atoms such as an ethyl group, a propyl group, and a neopentyl group are preferable.

Examples of the group having an ethylenic double bond include partial (meth) acrylates of polyhydric alcohols such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Etc.
Examples of the substituent further possessed by the alkyl group include a vinyl group, a (meth) acryl group, and a (meth) acryloxy group. Among them, a (meth) acryl group and a (meth) acryloxy group are preferable.

Examples of the substituent that the phenyl group further has include, for example, the alkyl group having 1 to 12 carbon atoms; an alkoxy group having 1 to 8 carbon atoms described later; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Etc.
As for R ^{5 to} R ¹⁰ , any group may be used as long as the effects of the present invention are not impaired. For example hydrogen atom;
Methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, An alkyl group having 1 to 12 carbon atoms such as 2-ethylhexyl group;
An alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;
A cyano group etc. are mentioned.

These groups may further have other optional substituents. Other optional substituents include, for example, the alkyl group. Further, adjacent R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , or R ⁹ R ¹⁰ may be bonded to form a ring structure. In the present invention, from the viewpoint of improving developability, it is preferable that R ^{5 to} R ¹⁰ are all hydrogen atoms.
In the present invention, the double bond equivalent of the compound represented by the general formula (i) is usually 120 or more and 300 or less, preferably 130 or more and 280 or less.

Further, the content of the compound represented by the general formula (i) is usually 15% by weight or more and 100% by weight or less, preferably 20% by weight or more and 100% by weight or less, based on the total amount of the polymerizable monomers. More preferably, it is 25 weight% or more and 100 weight% or less.
<Polymerizable monomer other than (B ′) and (B)>
The colored resin composition of the present invention may further contain a polymerizable monomer other than the above (B) (hereinafter sometimes referred to as “(B ′) component”) as necessary.

Examples of the component (B ′) include those described in International Publication WO2009 / 107734 and the like.
These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.

  A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be inferior. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  More preferred polyfunctional monomers having acid groups are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentaacrylate succinic acid ester, which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

  The blending ratio of the component (B ′) is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 80% by weight in the total solid content of the colored resin composition of the present invention. Hereinafter, it is preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The ratio to (A) pigment is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably 100%. % By weight or less, more preferably 80% by weight or less.

<Solvent>
In the colored resin composition of the present invention, the solvent has a function of adjusting viscosity by dissolving or dispersing components (A) and (B) other than these polymerizable monomers in addition to the polymerizable monomer.
There is no restriction | limiting in particular as a solvent, What is necessary is just a thing which can melt | dissolve or disperse | distribute each component.

Examples of such a solvent include the solvents described in International Publication WO2009 / 107734 and the like.
Commercially available products corresponding to these solvents include mineral spirit, Valsol # 2, Apco # 18 solvent, Apco thinner, Soal 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.

  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. If the solvent exceeds 99% by weight, the amount of (A) pigment, (B) polymerizable monomer, etc. will be too small to form a coating film. On the other hand, the lower limit of the solvent content is usually 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more in consideration of viscosity suitable for coating.

<(C) Dispersant>
The colored resin composition of the present invention can further contain (C) a dispersant in combination with the above components within a range not impairing the effects of the present invention.
The type of the (C) dispersant is not particularly limited as long as the effects of the present invention are not impaired, but (C-1) a graft copolymer containing a nitrogen atom (hereinafter referred to as (C-1) dispersant. And / or (C-2) an acrylic block copolymer containing a nitrogen atom (hereinafter, sometimes referred to as (C-2) dispersant). .

  In any of these (C-1) and (C-2) dispersants, the nitrogen atom contained in the dispersant structure has an affinity for the pigment surface, and the portion other than the nitrogen atom has an affinity for the medium. By increasing it, it is estimated that it contributes to the improvement of dispersion stability as a whole. In addition, the performance of (C) the dispersant is greatly influenced by the adsorption behavior to the solid surface. Regarding the relationship between the molecular architecture and the adsorption behavior, it is known that when the same unit is used, the adsorption behavior is excellent in the order of random copolymerization <graft copolymer <block copolymer (for example, Jones and Richards, “Polymers at Surfaces and Interfaces” p. 281).

<(C-1) Graft copolymer containing nitrogen atom>
Examples of the (C-1) dispersant include those described in paragraphs 0048 to 0061 of JP-A-2008-248255.
When the colored resin composition of the present invention contains (C-1) a dispersant, the content of the (C-1) dispersant is usually 10 to 300 weights with respect to the pigment component in the colored resin composition. %. Preferably it is 20-100 weight%, Most preferably, it is 30-80 weight%.

<(C-2) Acrylic Block Copolymer Containing Nitrogen Atom>
(C-2) Acrylic block copolymers containing nitrogen atoms are preferred in that (A) pigments can be dispersed very efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed on the pigment. The acrylic block copolymer is particularly preferably a block copolymer comprising an A block having a solvophilic group and a B block having a nitrogen atom-containing functional group.

Specific examples of the B block having a nitrogen atom-containing functional group include a unit structure having a quaternary ammonium base and / or an amino group in the side chain, while quaternary ammonium is used as a solvophilic A lock. Examples include a unit structure having no base or amino group.
The B block constituting the acrylic block copolymer has a unit structure having a quaternary ammonium base and / or an amino group, and has a pigment adsorption function.

  Further, when the B block has a quaternary ammonium base, the quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Good. Moreover, as such a quaternary ammonium base, what contains the partial structure represented with the following general formula (VI) especially is preferable.

In the above general formula (VI), R ³⁴ represents a hydrogen atom or a methyl group.
X ¹ represents a divalent linking group.
R ³¹ , R ³² and R ³³ are each independently an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 15 carbon atoms, or an optionally substituted carbon. An aralkyl group of several 7 to 20 is preferable.

Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, methyl, ethyl, propyl, butyl, benzyl and the like are preferable.
In the general formula (VI), examples of the divalent linking group X ¹ include an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ³⁵ —, —COO—R ³⁶ — (provided that R ³⁵ and R ³⁶ are each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ³⁷ —O—R ³⁸ —: R ³⁷ and R ³⁸ are Each independently represents an alkylene group.), Etc., and is preferably —COO—R ³⁶ —.

Examples of the counter anion Z ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .
Moreover, the partial structure containing the said specific quaternary ammonium base may be contained 2 or more types in one B block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. Furthermore, the partial structure which does not contain the quaternary ammonium base may be contained in the B block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later, etc. Is mentioned. The content of the partial structure containing no quaternary ammonium base in the B block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. It is most preferable that it is not contained in.

In addition, the B block of the acrylic block copolymer described above may have some tertiary amino groups. This remains when the quaternization reaction of the tertiary amino group is not completely completed, and its amine value is usually about 10 mgKOH / g or less.
On the other hand, when the B block constituting the acrylic block copolymer includes a primary to tertiary amino group, the content ratio of the monomer having the primary to tertiary amino group constitutes the copolymer. In the monomer composition, it is preferably 20 mol% or more, more preferably 50 mol% or more.

The primary to tertiary amino group is preferably —NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² each independently represents 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 is preferable. As a partial structure including this (repeating unit), preferred examples thereof include A structure represented by the general formula can be given.

(However, R ⁴¹ and R ⁴² have the same meanings as R ⁴¹ and R ⁴² described above, R ⁴³ represents an alkylene group having 1 or more carbon atoms, and R ⁴⁴ represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably a methyl group, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following general formula is particularly preferably used.

(In the above general formula, R ⁴⁴ has the same meaning as described above.)
Furthermore, the partial structure containing the said amino group may be contained 2 or more types 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. Moreover, a partial structure not containing an amino group may be partially contained in the B block, and examples of such a partial structure include a partial structure derived from a (meth) acrylate monomer. . The content of such a partial structure not containing an amino group in the B block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably it is not included.

  In addition, the solvophilic A block constituting the block copolymer of the (C-2) dispersant does not have a nitrogen atom-containing functional group such as an amino group as described above, and is a monomer constituting the B block as described above. There is no particular limitation as long as it is composed of a monomer that can be copolymerized with. The A block is a solvophilic site that does not have a nitrogen atom-containing functional group that serves as a pigment adsorbing group, and has an affinity for the solvent, and thus has a function of stabilizing the pigment adsorbed on the dispersant in the solvent. .

  Examples of the solvophilic A block include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol ( (Meth) acrylate monomers such as (meth) acrylate and polypropylene glycol (meth) acrylate; polyalkylene glycols such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate Vinyl acetate monomers; (meth) (meth) acrylate monomers such as acrylic acid chloride allyl glycidyl ether, polymer structure in which the comonomer is copolymerized, such as glycidyl ether monomers such as crotonic acid glycidyl ether.

  Among these, as the A block, those containing a (meth) acrylic acid ester monomer as a copolymerization component are preferable. Also preferred are those containing polyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate as copolymerization components (that is, containing a partial structure derived from polyalkylene glycol (meth) acrylate). . Furthermore, when the dispersing agent used for the colored resin composition of the present invention is a (meth) acrylic copolymer, an A block having a partial structure represented by the following general formula (VIII) is particularly preferable.

(In the general formula (VIII), n represents an integer of 1 to 5, but when there are a plurality of the units, that is, the general formula (VIII) in one molecule, n may be the same or different.
R ₁ represents a hydrogen atom or a methyl group,
V represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. V is particularly preferably an ethyl group. )
The partial structure represented by the general formula (VIII) is preferably contained in an amount of 3 to 20 mol% in terms of monomers constituting the (meth) acrylic copolymer. It is most preferable that 10 mol% is contained.

Although the detailed mechanism of action is unclear, by having a partial structure derived from polyalkylene glycol (meth) acrylate, particularly a partial structure represented by the above general formula, it is possible to improve hydrogen bonding properties and disperse It is considered that the affinity with the solvent is improved and the stability of the dispersion system is increased.
Two or more partial structures represented by the general formula (VIII) may be contained in one A block. Of course, the A block may further contain a partial structure other than these. When partial structures derived from two or more types of monomers are present in the A block, each partial structure may be contained in the A block in any form of random copolymerization or block copolymerization.

The dispersant (C-2) that can be used in the colored resin composition of 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, the method described in JP-A-2007-270147 and the like can be mentioned.

The amine value of 1 g of the above (C-2) dispersant is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferred range is not the case where the B block has a quaternary ammonium base. It depends on the case.
That is, when the B block of the AB block copolymer and ABA block copolymer of the (C-2) dispersant has a quaternary ammonium base, the amount of the quaternary ammonium base in 1 g of the copolymer is 0. It is preferable that it is 1-10 mmol. Outside this range, it may not be possible to combine good heat resistance and dispersibility. In such a block copolymer, an amino group generated in the production process may be contained, and its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 50 mgKOH per 1 g of the copolymer. / G, more preferably 1 to 30 mg KOH / g.

  When the quaternary ammonium base is not included in the B block, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more and 150 mgKOH. / G or less, more preferably 90 to 150 mgKOH / g, and most preferably 100 to 140 mgKOH / g.

If the number of functional groups containing nitrogen atoms is too small, the adsorptive power of the dispersant molecules on the pigment surface may be insufficient, and it may be difficult to obtain sufficient dispersion stability. On the other hand, if the amine value is too high, the molecular weight of the A block becomes relatively small, and the dispersion stability may be insufficient.
The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably lower, usually 100 mgKOH / g or less, preferably 50 mgKOH / g or less. , More preferably 40 mgKOH / g or less, most preferably 30 mgKOH / g or less. The molecular weight is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-equivalent weight average molecular weight (Mw) measured by GPC.
In the present invention, a commercially available (meth) acrylic block copolymer having the same structure as that described above can also be used.

<Other dispersants>
(C) The dispersant may contain a dispersant other than the above (C-1) and (C-2) dispersant (hereinafter also referred to as (C-3) dispersant). Good.
(C-3) Examples of the dispersant include a urethane-based dispersant, a polyallylamine-based dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether-based dispersant, and a polyoxyethylene diester-based dispersant. Examples thereof include a dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

  Specific examples of these dispersants include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical) ), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.), etc.

In addition, (C-1) dispersing agent-(C-3) dispersing agent mentioned above may be used individually by 1 type, and may use 2 or more types together.
In the present invention, when the colored resin composition further contains (C) a dispersant, the content ratio of the (C) dispersant is preferably about 0 to 200% by weight based on the pigment (A). It is more preferable to use about 10 to 100% by weight. (C) By controlling the content ratio of the dispersant within this range, a sufficient amount of the dispersant adheres to the pigment surface, so that aggregation is effectively prevented without reducing the coloring power of the colored resin composition. In addition, since high viscosity or gelation can be avoided, high dispersion stability can be ensured.

<Dispersing aid>
The colored resin composition of the present invention may further contain a dispersion aid. As the dispersion aid (pigment derivative), for example, various compounds described in JP-A-2007-113000 and the like can be used.
<Dispersed resin>
The colored resin composition of the present invention may contain a part or all of a resin selected from (D) a binder resin described later. Specifically, in the dispersion treatment step to be described later, the (D) binder resin is added to the (C) dispersant by adding the (D) binder resin together with the components such as the (C) dispersant described above. It contributes to the dispersion stability of the pigment (A) by a synergistic effect. As a result, there is a possibility that the amount of (C) dispersant added may be reduced, which is preferable.

As described above, the (D) 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 (D) binder resins described later can be used, and (D-1) resin and (D-4) resin are particularly preferable.

  The acid value of the dispersion resin is preferably 0 mgKOH / g or more, more preferably 1 mgKOH / g or more, most preferably 5 mgKOH / g or more, preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, and 150 mgKOH / g or less. Is 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.

  Further, the polystyrene-reduced weight average molecular weight measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, preferably 200000 or less, more preferably 50000 or less, and 30000 or less. Is 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.

<(D) Binder resin>
The (D) binder resin used in the colored resin composition of the present invention can be used without particular limitation as long as it can be used for pixel formation of a color filter. For example, a thermosetting resin composition used in a so-called lift-off color filter manufacturing process described in JP-A-60-184202 or the like, or an inkjet-type color filter manufacturing process described in JP-A-2004-220036 or the like. The resin contained in the thermosetting resin composition etc. used for this, or the photopolymerizable resin mentioned later etc. are mentioned.

Examples of such binder resins include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, and JP-A-2000-56118. Various polymer compounds described in JP-A-2003-233179, JP-A-2007-270147, and the like can be used.
(D-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 part of the epoxy group of the copolymer. A resin obtained by addition, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction,
(D-2): a linear alkali-soluble resin containing a carboxyl group in the main chain,
(D-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the carboxyl group-containing resin,
(D-4): (Meth) acrylic resin and the like.

Among these, (D-1) resin and (D-4) resin are particularly preferable.
Hereinafter, each of these resins will be described.
<(D-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 obtained by addition or resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction>
Among the (D) binder resins used in the colored resin composition of the present invention, one of the particularly preferred (D) binder resins is “copolymerization of an epoxy group-containing (meth) acrylate with another radical polymerizable monomer. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the copolymer or a polybasic acid anhydride is added to at least a part of the hydroxyl group generated by the addition reaction. Resin obtained ”(hereinafter referred to as (D-1) resin).

  More specifically, “an epoxy group contained in the copolymer with respect to a copolymer of 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radical polymerizable monomer. A resin obtained by adding a polybasic acid anhydride to a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the above, or 10 to 100 mol% of a hydroxyl group generated by the addition reaction " Can be mentioned.

  (D-1) Examples of the “epoxy group-containing (meth) acrylate” constituting the resin include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl ( Examples include meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is preferably a mono (meth) acrylate having a structure represented by the following general formula (1).

In the general formula (1), R ^{81 to} R ⁸⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁸⁶ and R ⁸⁸ are connected to each other to form a ring. May be.
In general formula (1), the ring formed by linking R ⁸⁶ and R ⁸⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and has 5 to 6 carbon atoms. Is preferred.

Especially, as a structure represented by General formula (1), the structure represented by following Structural formula (1a), (1b), or (1c) is preferable.
(D) By introducing these structures into the binder resin, when the colored resin composition of the present invention is used for a color filter or a liquid crystal display element, the heat resistance of the composition is improved, or the composition is It is possible to increase the intensity of the pixels formed by use.

  In addition, the mono (meth) acrylate which has a structure represented by General formula (1) may be used individually by 1 type, and may use 2 or more types together.

  Various mono (meth) acrylates having the structure represented by the general formula (1) can be used as long as they have the structure, and those represented by the following general formula (2) are particularly preferable.

In the general formula (2), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the general formula (1).
In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (1) is: Among repeating units derived from “other radical polymerizable monomers”, those containing 5 to 90 mol% are preferable, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable. preferable.

The “other radical polymerizable monomer” other than the mono (meth) acrylate having the structure represented by the general formula (1) is not particularly limited.
Specifically, for example, vinyl aromatics such as styrene, derivatives in which α-, o-, m-, or p-positions of styrene are substituted with alkyl groups, nitro groups, cyano groups, amide groups, ester groups, and the like. Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso -Propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) Isoamyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) Dodecyl crylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, Promethyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate , (Meth) acrylic acid furyl, (meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl , (Meta) 1,1,1-trifluoroethyl laurate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, (meth) Triphenylmethyl acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate (Meth) acrylic acid esters such as propyl; (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N- Dipropylamide, (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenylamide, etc. T) Acrylic acid amides; (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl compounds such as N-vinylpyrrolidone, vinylpyridine, vinyl acetate Unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide, etc. Monomaleimides of N- (meth) acryloylphthalimide and the like.

  Among these “other radically polymerizable monomers”, at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is used to impart excellent heat resistance and strength to the colored resin composition. It is effective to use In particular, in the repeating unit derived from “another radical polymerizable monomer”, the content of the repeating unit derived from at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 70 mol. % Is preferable, and 3 to 50 mol% is more preferable.

Various solution polymerization methods are applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can do.

  When (D-1) resin is contained in the colored resin composition of the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, epoxy group-containing (meta ) A repeating unit derived from 5 to 90 mol% derived from acrylate and a repeating unit derived from 10 to 95 mol% derived from another radical polymerizable monomer is preferred. The former 20 to 80 mol% and the latter 80 What consists of -20 mol% is still more preferable, and what consists of the former 30-70 mol% and the latter 70-30 mol% is especially preferable.

When there are too few epoxy group containing (meth) acrylates, the addition amount of the polymeric component mentioned later and a polybasic acid anhydride may become inadequate, on the other hand, there are too many epoxy group containing (meth) acrylates and others. If the amount of the radically polymerizable monomer is too small, the heat resistance and strength may be insufficient.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride are added to the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radical polymerizable monomer. React.

Various “unsaturated monobasic acids” to be added to the epoxy group can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, or p-vinylbenzoic acid, the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These 1 type may be used independently and may use 2 or more types together.

By adding such components, polymerizability can be imparted to the (D) binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of unsaturated monobasic acid is too small, there is a concern about the adverse effects of the remaining epoxy groups on the temporal stability of the colored resin composition. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, various things can be used as "polybasic acid anhydride" added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of the copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the (D) binder resin.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol%. More preferably, it is added to 30 to 80 mol%. Adjustment of the addition ratio in this range is considered to be effective for controlling the wettability of the composition. If the addition ratio is too large, the remaining film ratio at the time of development may decrease, and if it is too small, the solubility may be insufficient. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

  Furthermore, when the colored resin composition of the present invention is a photopolymerizable composition, in order to improve the sensitivity to light, after adding the above-mentioned polybasic acid anhydride, one of the generated carboxyl groups is added. Glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to the part. Moreover, in order to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group to some produced | generated carboxyl groups. Both of these may be added.

  Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. As commercial products, for example, trade names “Denacol EX-111”, “Denacol EX-121”, “Denacol EX-141”, “Denacol EX-145”, “Denacol EX-146”, “Denacol EX-146” manufactured by Nagase Chemical Industries, Ltd. Denacol EX-171 "," Denacol EX-192 "and the like.

Such a resin structure is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.
3000-100000 are preferable and, as for the weight average molecular weight (Mw) of polystyrene conversion measured by GPC of the resin mentioned above, 5000-50000 are especially preferable. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 2.0-5.
0 is preferred.

The acid value of the resin (D-1) used in the colored resin composition of the present invention is usually 0 to 200 mgKOH / g, preferably 0 to 150 mgKOH / g, more preferably 0 to 100 mgKOH / g. By controlling the acid value within these ranges, it is possible to prevent the solubility in the developer from decreasing or the film from being roughened.
<(D-2) A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as (D-2) resin)>
(D-2) The linear alkali-soluble resin containing a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group, and usually obtained by polymerizing a polymerizable monomer containing a carboxyl group. It is done.

  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.
Moreover, (D-2) resin may copolymerize the other polymerizable monomer which does not have a carboxyl group with said carboxyl group-containing polymerizable monomer.
Other polymerizable monomers are not particularly limited, and examples thereof include 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.

Moreover, the acid value of (D-2) resin used for the colored resin composition of this invention is 30-500 mgKOH / g normally, Preferably it is 40-350 mgKOH / g, More preferably, it is 50-300 mgKOH / g. By controlling the acid value within these ranges, it is possible to prevent the solubility in the developer from decreasing or the film from being roughened.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-20000 normally, Preferably it is 3000-50000, More preferably, it is 4000-30000.

<Resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (D-3) (D-2) (hereinafter sometimes referred to as (D-3) resin)>
A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the (D-2) linear alkali-soluble resin containing a carboxyl group in the main chain is also particularly preferable.
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 general formulas (3a) to (3m). And the compounds represented.

In the general 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 represents an integer of 1 to 10. is there.
In the general 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 general 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 of the resin (D-2). 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.

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. By controlling the acid value within these ranges, it is possible to prevent the solubility in the developer from decreasing or the film from being roughened.
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.

<(D-4) (Meth) acrylic resin (hereinafter sometimes referred to as (D-4) resin)>
Examples of the (meth) acrylic resin include a resin (D-4) obtained by polymerizing a monomer component essentially including a compound represented by the following general formula (4).

In the general formula (4), R ^1a and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
Hereinafter, the compound of General formula (4) is explained in full detail.
In the ether dimer represented by the general formula (4), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1a and R ^2a is not particularly limited. A linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; an aryl group such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ^1a and R ^2a may be the same type of substituent or different substituents.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like.

  Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.

These ether dimers may be used alone or in combination of two or more.
The proportion of the ether dimer in the monomer component in obtaining the (D-4) resin is not particularly limited, but is usually 2 to 60% by weight, preferably 5 to 55% by weight, more preferably in all monomer components. Is 5 to 50% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight product during polymerization, or it may be easily gelled. The coating film performance may be insufficient.

  (D-4) The resin preferably has an acid group. By having an acid group, the resulting colored resin composition is cured by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter sometimes referred to as “acid-epoxy curing”). A possible colored resin composition, or a composition in which an uncured part can be developed with an alkaline developer. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups contained in one molecule of the resin may be only one kind or two or more kinds.

  (D-4) In order to introduce an acid group into the resin, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter referred to as “monomer for introducing an acid group”) May be used as a monomer component. In addition, when using "monomer which can provide an acid group after superposition | polymerization" as a monomer component, the process for providing an acid group as mentioned later is required after superposition | polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.

Only one type of monomer for introducing these acid groups may be used, or two or more types may be used.
(D-4) When the monomer component for obtaining the resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited, but is usually 5 to 70% by weight in the total monomer component, preferably Is from 10 to 60% by weight. By adjusting the amount of the monomer for introducing the acid group within this range, good electrical characteristics and developability can be obtained.

Moreover, (D-4) resin may have a radically polymerizable double bond.
In order to introduce a radical polymerizable double bond into the resin (D-4), for example, “a monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter referred to as “introducing a radical polymerizable double bond”). May be referred to as a “monomer”.) After polymerization as a monomer component, a treatment for imparting a radical polymerizable double bond as described later may be performed.

  Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomers: Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzylglycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

  (D-4) When the monomer component for obtaining the resin also includes a monomer for introducing the radical polymerizable double bond, the content ratio is not particularly limited, but usually 5 to 70 in all the monomer components. % By weight, preferably 10 to 60% by weight. By adjusting the amount of the monomer for introducing the radical polymerizable double bond within this range, good plate making characteristics can be obtained, and a pixel having a desired taper angle with little chipping can be obtained.

(D-4) The resin preferably also has an epoxy group. In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter sometimes referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component.
Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types.

  (D-4) When the monomer component for obtaining the resin also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but is usually 5 to 70% by weight in the total monomer component, preferably Is preferably 10 to 60% by weight. By adjusting the amount of the monomer for introducing the epoxy group within this range, the heat resistance and the like can be improved without deteriorating exposure sensitivity and color characteristics.

(D-4) The monomer component for obtaining the resin may contain other copolymerizable monomers as required in addition to the essential monomer component.
Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as: aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene; Substituted butadiene compounds; ethylene, propylene, vinyl chloride Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like.

Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.
When the monomer component for obtaining the (D-4) (meth) acrylic resin also contains the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by weight or less, 85 More preferably, it is less than wt%. When there is too much content rate, developability may deteriorate.

(D-4) The weight average molecular weight of the resin is not particularly limited, but the polystyrene equivalent weight average molecular weight measured by GPC is preferably 2,000 to 200,000, more preferably 4,000 to 100,000.
(D-4) When resin has an acid group, a preferable acid value is 5-500 mgKOH / g, More preferably, it is 10-400 mgKOH / g.

Incidentally, (D-4) resins, that is, copolymers having a compound represented by the general formula (4) as an essential monomer component are disclosed in, for example, JP-A-2004-300203 and JP-A-2004-300204. Examples include compounds described in publications and the like.
Furthermore, as the (D) binder resin according to the present invention, for example, an acrylic resin described in JP-A-2005-154708 can be used.

In addition, the colored resin composition of the present invention may contain a binder resin other than the above-mentioned (D-1) to (D-4) resins as long as the effects of the present invention are not impaired.
As the (D) binder resin used in the colored resin composition of the present invention, one of the various resins described above may be used alone, or two or more may be used in combination.
Furthermore, the content ratio of the total amount of (D) binder resin is usually 0% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, preferably 60% by weight or less in the total solid content. .

<(E) Photopolymerization initiators and / or thermal polymerization initiators>
The colored resin composition of the present invention preferably further contains (E) a photopolymerization initiator and / or a thermal polymerization initiator for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In the present invention, the (E) photopolymerization initiators are a photopolymerization initiator (hereinafter also referred to as (E-1) component) and a polymerization accelerator (hereinafter referred to as (E-2) component). And an additive such as a sensitizing dye (hereinafter sometimes referred to as component (E-3)).

  (E) Component (E-1) constituting the photopolymerization initiator includes, for example, titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; Hexaarylbiimidazole derivatives described in JP-A No.-300922, JP-A-11-174224, JP-A-2000-56118, and the like; halomethylated oxadiazole derivatives described in JP-A-10-39503, Radical activators such as halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-amino Alkylphenone derivatives; oxime ester derivatives described in JP-A No. 2000-80068 and the like.

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-difluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  As biimidazole derivatives, 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole 2 amount 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.

  The halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl). Vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2- And trichloromethyl-5-furyl-1,3,4-oxadiazole.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl). ) -S-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s -Triazine etc. are mentioned.

Examples of the 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 The

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 such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- ( acetophenone derivatives such as p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
And anthrone derivatives such as benzanthrone.

Among these (E-1) components, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.
Moreover, the coloring resin composition of this invention can mix | blend (E-2) a polymerization accelerator further as needed, especially when (E) photoinitiators are included. (E-2) Examples of the polymerization accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

These (E-1) component and (E-2) polymerization accelerator may be used individually by 1 type, respectively, and may use 2 or more types together.
In the colored resin composition of the present invention, a sensitizing dye (E-3) may be used in the photopolymerization initiators (E-3) for the purpose of increasing the sensitivity. (E-3) As the sensitizing dye, an appropriate dye is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc. A coumarin dye having a heterocyclic ring described in JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin described in JP-A-3-239703, JP-A-5-289335, etc. 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 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP No. 5-107761, JP-A-5-210240, it may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

Among these (E-3) sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. (E-3) Particularly preferred as the sensitizing dye is, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone. Benzophenone compounds such as 3,3′-diaminobenzophenone and 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethyl) Aminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazo 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1 , 3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, P-dialkylaminophenyl group-containing compounds such as (p-diethylaminophenyl) pyrimidine. Among these, 4,4′-dimethylaminobenzophenone and 4,4′-dialkylaminobenzophenone such as 4,4′-diethylaminobenzophenone are most preferable.
(E-3) 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 ratio of these (E) photopolymerization initiators ((E-1) photopolymerization initiator, (E-2) polymerization accelerator and (E-3) sensitizing dye). The total solid content is usually 0% by weight or more, preferably 0.1% by weight or more, and usually 40% by weight or less, preferably 30% by weight or less.
<Thermal polymerization initiators>
Specific examples of the thermal polymerization initiators that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used.

Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-carbonitrile), 2, 2′-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2-azobis {2 -Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2 '-Azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2'-azobis [N-butyl-2-methylpropionamide], 2,2'-azobis (N-cyclo Xyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionate), 2,2′-azobis (2 , 4,4-trimethylpentene) and the like. Among these, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like are preferable. .

  Examples of the organic peroxide include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like. Specifically, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di (2-ethoxyethyl) peroxy Dicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t -Butyl peroxypivale Di (3,5,5-trimethylhexanoyl) peroxide, di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (T-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) Cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t- Butyl peroxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) Hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2,2-di (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-di (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyltrimethylsilyl peroxide, 2, 3-dimethyl-2,3-diphenylbutane, di (3-methylbenzoyl) peroxy Mixtures of benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide may be mentioned.

In addition, some of the above-described (E-1) photopolymerization initiators also function as thermal polymerization initiators such as α-aminoalkylphenone derivatives. Therefore, you may use the compound selected from the examples given as an example of (E-1) photoinitiator as a thermal-polymerization initiator.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together. In the present invention, when the thermal polymerization initiators are further contained, the content ratio may be 0 to 30% by weight, particularly 0 to 20% by weight, based on the total solid content of the colored resin composition of the present invention. preferable.

<Surfactant>
The colored resin composition of the present invention may further contain a surfactant. Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but they may adversely affect various properties such as voltage holding ratio and compatibility with organic solvents. It is preferable to use a nonionic surfactant in terms of low properties.

Examples of the surfactant include those described in JP-A-2009-25813.
The content of these surfactants is usually 0% by weight or more, preferably 0.001% by weight or more, more preferably 0.005% by weight or more in the total solid content of the colored resin composition of the present invention. Moreover, it is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less. By controlling the surfactant content within this range, there is no possibility that the overcoat will be repelled when the overcoat is applied in the actual line, and the coating film may be cracked after curing. , Less wrinkling film.

<Preparation method of colored resin composition>
The colored resin composition of the present invention may be prepared by mixing the components constituting the composition at once or sequentially. However, as described below, a pigment dispersion is prepared in advance, B) It is preferable to mix a polymerizable monomer and other components.
Hereinafter, although an example of the method of preparing the colored resin composition of this invention is demonstrated, there is no restriction | limiting in particular in a preparation method, It is not necessarily limited to the method described below.

The colored resin composition of the present invention is preferably used as a pixel forming material for a color filter. The colored resin composition of the present invention may be photocurable (photopolymerizable) or thermopolymerizable depending on the production process of the color filter to be applied.
The colored resin composition of the present invention first prepares a pigment dispersion containing at least (A) a pigment, and optionally (C) a dispersant, a dispersion aid, a dispersion resin, a solvent, and the like. It is preferable to prepare by mixing other components such as (B) a polymerizable monomer, (D) a binder resin, (E) a photopolymerization initiator, and / or a thermal polymerization initiator.

First, (A) the pigment, and optionally (C) the dispersant, the dispersion resin, and the like are weighed in predetermined amounts, and in the dispersion treatment step, (A) the pigment is dispersed to obtain an ink-like liquid (pigment dispersion). In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used.
By carrying out this dispersion treatment, the pigment is made fine, so that the coating characteristics of the colored resin composition are improved and the transmittance of the product color filter substrate and the like is improved. (A) When dispersing the pigment, as described above, it is preferable to use a dispersion aid or the like as appropriate.

  When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the ink-like liquid and the size of the sand grinder apparatus.

(B) a polymerizable monomer, and optionally used (B ′) polymerizable monomer other than (B), (D) a binder resin, and (E) a photopolymerization initiator. And / or other components such as thermal polymerization initiators and surfactants are mixed to obtain a uniform dispersion solution to obtain a colored resin composition.
In addition, in each process of a dispersion | distribution process and a mixing process, since fine refuse may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.

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

<Manufacture of color filter substrates>
Next, the color filter of the present invention (hereinafter sometimes referred to as “color filter substrate”) will be described.
The color filter of the present invention is characterized by having pixels formed on the substrate using the above-described colored resin composition.

<Transparent substrate (support)>
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, or various glasses. Among these, glass or heat resistant resin is preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, for improvement of surface properties such as adhesion, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, etc. May be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, Usually, 10 micrometers or less, Preferably it is the range of 5 micrometers or less.

<Black Matrix>
The color filter according to the present invention can be manufactured by providing a black matrix on the above-described transparent substrate and further forming pixel images of red, green and blue colors. The colored resin composition of the present invention is usually used as a coating liquid for forming pixels which are red, green and blue.

The black matrix is formed on the transparent substrate using a light shielding metal thin film or a coating liquid for forming a black matrix (which may be the colored resin composition of the present invention). As the light shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate, perchloric acid, and / or nitric acid are added to chromium. Other materials are etched using an etching solution according to the material, and finally a positive photoresist is stripped with a special stripping agent to form a black matrix. be able to. In this case, first, a thin film of these metals or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the colored resin composition on the thin film, the coating film is exposed and developed using a photomask having a repeated pattern such as stripes, mosaics, and triangles to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  When using a black matrix forming coating solution, a black matrix is formed using a colored resin composition containing a black pigment. For example, by black pigments such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black alone or in combination, or a mixture of red, green, blue and the like appropriately selected from inorganic or organic pigments and dyes Using a colored resin composition containing a black pigment, a black matrix can be formed in the same manner as in the following method for forming red, green, and blue pixel images.

  In the case of producing a color filter (pixels) by an ink jet method, first, a partition pattern (black matrix) is provided on a substrate, and pixels are included in the pattern (hereinafter sometimes referred to as “pixel bank”). A forming filter (colored resin composition) is directly applied to produce a color filter. Since ink droplets can be drawn at a desired position, high productivity and cost reduction of the color filter can be achieved.

  The black matrix of the color filter by the ink jet method not only functions as a light blocking function that is conventionally required, but also functions as a partition to prevent the RGB ink driven into the pixel bank from being mixed. The film thickness is thicker than that of the color filter according to (1). Usually, the film thickness is 1.5 μm or more, preferably about 1.8 to 2.5 μm, more preferably about 2.0 to 2.3 μm. ). In addition, in order to prevent color mixing of RGB ink, liquid repellent treatment is often applied to the upper surface of the black matrix.

Therefore, it was formed using a photosensitive material including a black color material from a conventionally used chromium compound such as chromium, chromium oxide and chromium nitride, and a black matrix made of a light-shielding metal material such as nickel and tungsten alloy. A resin black matrix is preferred.
When the color filter of the present invention is produced by the inkjet method, the resin black matrix may be formed by a general photolithography method using the photosensitive coloring resin composition for black matrix as described above. Subsequently, the surface of the transparent substrate is made hydrophilic and the black matrix pattern is made liquid repellent by chemical treatment or physical treatment, respectively.

<Formation of pixels>
The method for forming the pixel varies depending on the type of the colored resin composition to be used. First, a case where a photopolymerizable composition is used as the colored resin composition and pixels are formed by photolithography will be described as an example.
On a transparent substrate provided with a black matrix, a colored resin composition of one of red, green, and blue is applied and dried, and then a photomask is overlaid on the coating film, and image exposure is performed through this photomask. A pixel image is formed by development and, if necessary, thermal curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

  The colored resin composition can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, and there is no influence of mist and the like adhering when using the spin coating method. It is preferable from a viewpoint.

If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if it is too small, it is difficult to increase the pigment concentration. Color expression may be impossible. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, as the thickness after drying.
Moreover, it is 20 micrometers or less normally, Preferably it is 10 micrometers or less, More preferably, it is the range of 5 micrometers or less.

Next, a case where pixels are formed by an inkjet method will be described.
In the pixel bank on the substrate provided with the resin black matrix, the colored resin composition of the present invention is used to draw by an inkjet apparatus, and the composition is completely cured by drying, photocuring and / or heat curing, A color filter is obtained by forming pixels. As the colored resin composition for pixel formation, three colors of R (red), G (green), and B (blue) are often used, but are not limited thereto.

<Drying of coating film>
Drying of the coating film formed by applying the colored resin composition to the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried.
The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

  The temperature condition for the reheating drying is preferably higher than the pre-drying temperature. Specifically, it is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130 ° C. It is the range below ℃. The drying time is preferably in the range of usually 10 seconds or more, especially 15 seconds or more, and usually 10 minutes or less, especially 5 minutes, although it depends on the heating temperature. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the polymer may be decomposed to induce thermal polymerization and cause poor development. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a reduced pressure chamber, without raising temperature. Preferred drying conditions are 0.1 to 1 Torr, and the drying time is in the range of 10 seconds to 60 minutes.

Moreover, when the colored resin composition of this invention is photopolymerizable, an exposure process is performed following this drying process.
<Exposure process>
Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating an ultraviolet or visible light source through the mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen.

  The light source used for the image exposure is not particularly limited. As the light source, 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, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples thereof include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

When the color filter of the present invention is produced by photolithography, the process further proceeds to a development process.
<Development process>
The color filter of the present invention is developed using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after image exposure to the coating film using the colored resin composition of the present invention with the light source. By performing the above, an image can be formed on the substrate and manufactured. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Examples of the alkaline compound 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, phosphorus Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- Or trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline Organic alkali compound may be mentioned.

These alkaline compounds may be a mixture of two or more.
Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
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, more preferably 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.

<Heat curing (firing) treatment>
The color filter after development is preferably subjected to thermosetting treatment. In this case, the thermosetting treatment conditions are such that the temperature is usually 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 250 ° C. or lower, and the time is 5 minutes or longer and 60 minutes or shorter. Selected by range. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. The order of patterning the four colors is not limited to the above order.

In the case of producing a color filter by an ink jet method, if the colored resin composition of the present invention is photopolymerizable, after the exposure step, if it is thermosetting, after the coating step by the ink jet method, thermosetting Process. Preferred conditions for the thermosetting treatment are the same as described above.
In addition to the manufacturing method described above, the color filter of the present invention applies (1) the colored resin composition of the present invention containing a polyimide resin as a binder resin to a substrate and forms a pixel image by an etching method. It can also be produced by a method. Also, (2) a method of directly forming a pixel image on a transparent substrate by a printing press using the colored resin composition of the present invention as a colored ink, and (3) using the colored resin composition of the present invention as an electrodeposition liquid. And a method of depositing a colored film on the ITO electrode having a predetermined pattern by immersing the substrate in this electrodeposition solution, and (4) a film coated with the colored resin composition of the present invention is attached to a transparent substrate And a method of forming a pixel image by peeling and image exposure and development, and (5) a method of forming a pixel image with an ink jet printer using the colored resin composition of the present invention as a colored ink.
As a method for producing the color filter, a method suitable for the colored resin composition of the present invention is employed.

<Formation of transparent electrode>
The color filter of the present invention forms a transparent electrode such as ITO on the image as it is and is used as a part of components such as a color display and a liquid crystal display device. However, the surface smoothness and durability are improved. Therefore, if necessary, a top coat layer such as polyamide or polyimide can be provided on the image. In some cases, the transparent electrode may not be formed in applications such as a planar alignment type driving system (IPS mode).

<Liquid crystal display device (panel)>
Next, the manufacturing method of the liquid crystal display device (panel) of this invention is demonstrated. In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter of the present invention, spacers are dispersed on the alignment film, and then bonded to the counter substrate to form a liquid crystal cell. Liquid crystal is injected into the cell and connected to the counter electrode to complete. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of decompression in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or higher, preferably 1 × 10 ⁻³ Pa or higher, and usually 1 × 10 ⁻⁷ Pa or lower, preferably 1 × 10 ⁻⁶ Pa or lower. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.

The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.
The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

<Organic EL display>
When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern (pixel 20 or an adjacent pixel 20 formed on a transparent support substrate 10 by a colored resin composition is formed. Resin black matrix (not shown) in between
An organic EL element can be manufactured by stacking the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40 on the color filter. Note that at least one of the pixels 20 is manufactured using the colored resin composition of the present invention.

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. A method described in, for example, “Organic EL Display” (Ohm Co., Ltd., issued on August 20, 2004, Shizushi Tokito, Chiba Adachi, and Hideyuki Murata) using the organic EL element 100 manufactured in this manner, etc. Thus, an organic EL display can be produced.
The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to description of a following example, unless the summary is exceeded. Further, “%” represents “% by weight” unless otherwise specified.
[1] Synthesis of (D) Binder Resins A and B and (B) Polymerizable Monomers C to E <Synthesis Example 1: Synthesis of Binder Resin A>
A separable flask with a cooling tube was prepared as a reaction tank, while dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate 30 was used as a monomer dropping tank.
Parts, methacrylic acid 68 parts, methacrylic acid cyclohexyl 102 parts, t-butyl peroxy-2-ethylhexanoate (Nippon Yushi Co., Ltd. "Perbutyl O") 7.8 parts, propylene glycol monomethyl ether acetate 60 parts A mixture was prepared, and a chain transfer agent dropping tank was prepared by thoroughly stirring and mixing 3.5 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether.

The reaction vessel was charged with 375 parts of propylene glycol monomethyl ether acetate and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 64.9 parts of glycidyl methacrylate, 0.4 part of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 part of triethylamine were charged into the reaction vessel and left at 110 ° C. for 9 hours. Reacted. Thereafter, propylene glycol monomethyl ether acetate was added and cooled to room temperature to obtain a resin A having a concentration of 30%. Resin A had a weight average molecular weight of 16,200, an acid value of 69 mgKOH / g, and a double bond equivalent of 580.

<Synthesis Example 2: Synthesis of Binder Resin B>
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2,2′-azobis-2-methyl was added. 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours.

Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 18 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the binder resin B thus obtained was about 8400, and the acid value was 32 mgKOH / g.

<Synthesis Example 3: Synthesis of polymerizable monomer C>
In a separable flask, 72.9 parts of propylene glycol monomethyl ether acetate, 17.6 parts of biphenyltetracarboxylic dianhydride (BPDA), pentaerythritol triacrylate / pentaerythritol tetraacrylate mixture (OH value 106.5 mgKOH / g) 91. 7 parts, 2.2 parts of triphenylphosphine and 0.055 part of paramethoxyphenol were added and reacted with stirring at 85 ° C. for 3 hours and then at 110 ° C. for 2 hours to obtain a reaction mixture C ′. The ratio of the polymerizable monomer C corresponding to claim 1 calculated from the OH number of the raw material was 49% in the solid content of the reaction mixture C ′, 51% of pentaerythritol tetraacrylate (partially including triacrylate), The heavy bond equivalent is estimated to be about 148.

<Synthesis Example 4: Synthesis of polymerizable monomer D>
In a separable flask, 93.2 parts of propylene glycol monomethyl ether acetate, 14.7 parts of biphenyltetracarboxylic dianhydride (BPDA), dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture (OH value 53.8 mgKOH / g) 125.1 parts, 2.8 parts of triphenylphosphine and 0.07 part of paramethoxyphenol were added and reacted with stirring at 85 ° C. for 3 hours and then at 110 ° C. for 2 hours to obtain a reaction mixture D ′. The proportion of the polymerizable monomer D corresponding to claim 1 calculated from the OH number of the raw material is 48% in the solid content of the reaction mixture D ′, 52% of dipentaerythritol hexaacrylate (partly including pentaacrylate), The double bond equivalent is estimated to be about 134.

<Synthesis Example 5: Synthesis of polysynthetic monomer E>
In a separable flask, 77.9 parts of propylene glycol monomethyl ether acetate, 58.8 parts of biphenyltetracarboxylic dianhydride (BPDA), 46.4 parts of 2-hydroxyethyl methacrylate, 2.3 parts of triphenylphosphine, paramethoxyphenol 0.058 parts was added, and the mixture was reacted at 85 ° C. for 3 hours with stirring and then at 110 ° C. for 3 hours to obtain a polymerizable monomer E. The double bond equivalent of monomer D is estimated to be about 263 from the calculation.

<Examples 1-3 and Comparative Examples 1-4>
[2] Preparation of colored resin composition (A) As a pigment, C.I. I. 5.99 parts by weight of Pigment Green 58, 3.48 parts by weight of E4GN-GT manufactured by LANXESS, 60.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and (C) Dispersant A shown below as a solid content 2.37 parts by weight and 3.16 parts by weight of the binder resin A of Synthesis Example 1 in terms of solid content and 225 parts by weight of zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container and dispersed for 6 hours in a paint shaker. To prepare a green pigment dispersion.

Then, each component was mixed with the said green pigment dispersion liquid, and the colored resin composition was prepared so that it might become the composition described in Table 1.
<Dispersant A: Dispersant “BYK-LPN6919” manufactured by Big Chemie>
It is a methacrylic acid AB block copolymer, the amine value is 121 mgKOH / g, and the acid value is 1 mgKOH / g or less.

Among the repeating units having a nitrogen atom-containing functional group contained in the B block, about 100 mol% is a structure represented by the following formula (i), and in the A block of the repeating unit represented by the following formula (ii) The ratio was 7.5 mol%.

[3] Production of colored resin film The transparent resin substrate for color filter (AN-100 manufactured by Asahi Glass Co., Ltd.) was spin-coated with the colored resin composition obtained in [2] above, and 3 on an 80 ° C. hot plate. Pre-baking was performed for a minute to form a dry coating film. At the time of application, the rotational speed was adjusted so that the color coordinate y = 0.600 was obtained after the post-baking described below.

The obtained dried coating film is exposed at 60 mJ / cm ² through a mask pattern with a high-pressure mercury lamp, and then sprayed at a pressure of 0.25 MPa using a 0.04 wt% aqueous potassium hydroxide solution (developer temperature 23 ° C.). Developed. It was thoroughly washed with pure water and sufficiently dried with clean air.
Thereafter, post-baking was performed 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.

[4] Measurement of thickness retardation (Rth) of colored resin film Three-dimensional refractive index measurement by rotating analyzer method using RETS-100 manufactured by Otsuka Electronics Co., Ltd., which can measure minute retardation up to 0.1 nm. The value obtained with a non-contact type film thickness meter was used as the film thickness, and the retardation Rth in the thickness direction (z) at a wavelength of 550 nm was obtained. Rth was set to a value of y = 0,600. Table 2 summarizes the measurement results of the thickness retardation of the colored resin films applied with the above colored resin compositions.

[5] Measurement of Y value Using a colored resin film coated with each of the above colored resin compositions, x, y, Y with a C light source is measured with a Hitachi spectrophotometer U-3010, and color coordinate y = 0. The Y value at 600 is calculated and shown in Table 2.

* Polymerizable monomer F: Dipentaerythritol hexaacrylate * Polymerizable monomer G: Pentaerythritol triacrylate The ratio refers to the compound represented by the general formula (i) with respect to the total amount of the polymerizable monomer in the colored resin composition. Indicates the content.

By using the colored resin composition of the present invention, it is possible to adjust the retardation for each pixel in an increasing direction while maintaining excellent compatibility with the contrast ratio control and hue control of the pixel, with excellent development solubility and pixel forming ability. it can.
In addition, by using such a colored resin composition, a color filter having high transmittance, high contrast, and low film thickness can be produced as a result, and there is no coloration even when viewed from an oblique direction. A liquid crystal display device and an organic EL display with good characteristics can be provided.

DESCRIPTION OF SYMBOLS 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims (9)

(A) a pigment, and (B) a polymerizable monomer,
(B) A colored resin composition, wherein the polymerizable monomer is a compound represented by the following general formula (i).

(In the general formula (i), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted phenyl. Or a group having an ethylenic double bond, provided that at least one of R ^{1 to} R ⁴ is a group having an ethylenic double bond.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an arbitrary substituent. )   The colored resin composition according to claim 1, wherein the double bond equivalent of the compound represented by the general formula (i) is 120 or more and 300 or less.   The colored resin composition according to claim 1 or 2, wherein the content of the compound represented by the general formula (i) is 15% by weight or more and 100% by weight or less based on the total amount of the polymerizable monomers. .   Furthermore, (C) A dispersing agent is contained, The colored resin composition of any one of Claims 1-3 characterized by the above-mentioned.   Furthermore, (D) Binder resin is contained, The colored resin composition of any one of Claims 1-4 characterized by the above-mentioned.   The colored resin composition according to any one of claims 1 to 5, further comprising (E) a photopolymerization initiator and / or a thermal polymerization initiator.   A color filter comprising a pixel produced using the colored resin composition according to claim 1.   A liquid crystal display device comprising the color filter according to claim 7. An organic EL display comprising the color filter according to claim 7.

Images