JP2012215850A - Colored resin composition for color filter, color filter, liquid crystal display device, and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition in which the cross-section of a pixel obtained is appropriate, that is, not forming undercut (the pixel is forward-tapered) and to provide a liquid crystal display device and an organic EL display device with pixels of high coloring density and high quality.SOLUTION: A colored resin composition for color filter comprises (A) a dye, (B) a solvent, and (C) a binder resin, and further comprises a compound represented by a specific structure.

Description

  The present invention relates to a colored resin composition for a color filter, a color filter, a liquid crystal display device, and an organic EL display device.

  Conventionally, as a method for producing a color filter used in a liquid crystal display device or the like, a predetermined pattern is formed by forming a coating film of a colored resin composition on a substrate or a substrate on which a light-shielding layer having a desired pattern is previously formed. There is known a method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having, developing and dissolving and removing unexposed portions, and then post-baking. .

In recent years, the trend of technological innovation has been rapid, and liquid crystal display devices (“panels”) having color filters have been required to have high color density, and as a result, the color material density of color filters has been increasing in recent years. It is in.
Further, from the viewpoint of productivity improvement and cost reduction, it has become mainstream to reduce the exposure amount to shorten the tact time. As a result, disconnection of the transparent electrode formed on the color filter, peeling of the pixels, and light leakage are likely to occur, causing display defects and defects in the panel.

In addition, with the trend of energy saving, color filters are required to have higher brightness and higher contrast. Along with this, the development of dyes has also been carried out. However, when dyes are used, when pixels are formed with a desired line width, the pixels are more likely to be peeled off or the edges are missing. .
In order to solve these problems, for example, in Patent Document 1, a vinyl resin having a specific functional group is used, and in Patent Document 2, a polyfunctional monomer having a caprolactam structure and a specific photopolymerization initiator are used. The combination is disclosed. Patent Document 3 discloses the use of a colored resin composition containing a specific acrylic copolymer unit having a tri- or higher functional polyunsaturated double bond.

JP 2010-230957 A JP 2010-217872 A JP 2007-114604 A

However, even with the methods described in Patent Documents 1 to 3, it is difficult to solve the above problems. The main cause of the above problems is that the cross-sectional shape of the pixel forming the color filter is not appropriate, the solubility of the colored resin composition in the developing solution, the adhesion of the obtained pixel to the substrate, and the balance of image formability. I guessed that it came from something difficult to take.
Further, the inappropriateness of the cross-sectional shape of the pixel is considered to be caused by the above-mentioned mainstream “improvement of colorant density” or “transition of colorant from pigment to dye” and “reduction of tact time”. It is done.

In other words, if the concentration of the color material contained in the colored resin composition is increased, the color material may prevent the transmission of ultraviolet rays necessary for photocrosslinking, so that light does not reach the inside of the coating film, resulting in insufficient exposure. It is presumed that it tends to be easy.
In addition, the shortening of the tact time results in a further underexposure, resulting in an undercut in the development process, and a colored pattern having a reverse tapered shape in cross section.

  In addition, when the dye is used, since the dye exists in a substantially monomolecular state, it has been found that the fact that the contact probability with the photopolymerization initiator is large is also a factor that the cross-sectional shape tends to be reversely tapered. In other words, when the coloring resin composition contains a dye, the energy of the photopolymerization initiator easily moves to the dye, so that the radical generation function of the photopolymerization initiator does not function sufficiently, and the plate-making performance of the pixel is insufficient. Presumed to be.

As described above, an object of the present invention is to provide a colored resin composition for a color filter in which the cross-sectional shape of the obtained pixel is appropriate, that is, the undercut is difficult to occur (the pixel is forward tapered).
Another object of the present invention is to provide a colored resin composition having high solubility in a developing solution and high adhesion to the obtained pixel substrate.

  It is another object of the present invention to provide a pixel having a high color density, a high-quality liquid crystal display device, and an organic EL display device.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by containing a specific polymerizable monomer in the colored resin composition for a color filter, and have reached the present invention.
That is, the gist of the present invention is that a colored resin composition containing (A) a color material, (B) a solvent, and (C) a binder resin, and further a compound represented by the following formula (1) (hereinafter referred to as “compound”): (1) ”in some cases). The present invention resides in a colored resin composition for a color filter.

(In the above formula (1),
Y ¹ represents a hydrocarbon ring group which may have a substituent, a heterocyclic group which may have a substituent, or an aromatic ring group which may have a substituent.
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.

R ¹¹ and R ¹² may be bonded to each other to form a ring.
l is an integer from 1 to 12,
m is an integer of 1 to 3,
n represents an integer of 1 to 12.
In addition, when 1 and n and -CR < ¹¹ > R < ¹² >-which are contained plurally are contained in one molecule, they may be the same or different. )
The present invention also resides in a color filter having pixels formed using the colored resin composition for a color filter of the present invention, and a liquid crystal display device and an organic EL display device having the color filter.

A pixel formed using the colored resin composition for a color filter of the present invention has an appropriate cross-sectional shape, that is, is less likely to be undercut (the pixel has a forward taper).
For this reason, even when a pixel having a high color density is formed or when the tact time is shortened, a display defect or a defect due to the cross-sectional shape hardly occurs.
In addition, the colored resin composition of the present invention has high solubility in a developing solution and high adhesion of the resulting pixel to the substrate.

  Thus, by using the colored resin composition of the present invention, it is possible to provide a pixel having a high color density, a high-quality liquid crystal display device, and an organic EL display device.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present 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 colored resin composition for color filters.
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.).

Furthermore, 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 amount of base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later. 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.
In the present invention, “aromatic ring” refers to both “aromatic hydrocarbon ring” and “aromatic heterocycle”.

The “coloring material” in the present invention means both “pigment” and “dye”.
The colored resin composition for a color filter of the present invention contains (A) a color material, (B) a solvent, (C) a binder resin, and a compound (1), and (D) a dispersant and (F) photopolymerization. It is preferable to contain an initiation component and the like.
First, the compound (1) will be described.
[Compound (1)]
The colored resin composition (1) of the present invention contains the compound (1).

(In the above formula (1),
Y ¹ represents a hydrocarbon ring group which may have a substituent, a heterocyclic group which may have a substituent, or an aromatic ring group which may have a substituent.
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.

R ¹¹ and R ¹² may be bonded to each other to form a ring.
l is an integer from 1 to 12,
m is an integer of 1 to 3,
n represents an integer of 1 to 12.
In addition, when 1 and n and -CR < ¹¹ > R < ¹² >-which are contained plurally are contained in one molecule, they may be the same or different. )
(For ^{Y 1)}
Y ¹ represents a hydrocarbon ring group which may have a substituent, a heterocyclic group which may have a substituent, or an aromatic ring group which may have a substituent.

Examples of the hydrocarbon ring group include groups having two free valences, such as a cyclohexane ring, a cyclopentane ring, a cycloheptane ring, and a cyclooctane ring.
The free valence in the present invention is based on the description in “Organic Chemistry / Biochemical Nomenclature” (Nanedo, published May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pages 11-12). It is.

The heterocyclic group (that is, a non-aromatic heterocyclic group) may be a single ring or a condensed ring. The heterocyclic group is a non-aromatic ring group containing at least one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom.
Specific examples include groups having two free valences, such as a pyridinyl ring, a quinolinyl ring, an isoquinolinyl ring, a benzothiazolinyl ring, a phthalimidoyl ring, a piperidinyl ring, and a pyrrolidinyl ring.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 5 to 10. For example, two free valences are And groups such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and is not particularly limited as long as it has 3 to 10 carbon atoms to form the ring. Having a furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, Thienothiophene ring,
Furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, Examples include phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.

Among these, R ¹ is preferably a benzene ring or cyclohexane ring group having two free valences in terms of improving compatibility with the coloring material.
Examples of the substituent that the hydrocarbon ring group, the heterocyclic group, and the aromatic ring group in Y ¹ may have include those described in the following (Substituent Group W). It is not limited to.

(Substituent group W)
Fluorine atom, chlorine atom, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy group, alkyl having 2 to 9 carbon atoms A carboxyl group, a sulfonic acid amide group, a sulfone alkylamide group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, and an alkyl group having 1 to 4 carbon atoms are bonded. A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms.

(About R ¹ )
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
A hydrogen atom or a methyl group is particularly preferable because a crosslinking reaction easily occurs.
Examples of the substituent that the alkyl group in R ¹ may have include those described in the above section (Substituent group W).

(About R ¹¹ and R ¹² )
R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a ring.
When a plurality of —CR ²¹ R ²² — is contained in one molecule, R ²¹ and R ²² may be the same or different from each other, but the compound can be easily synthesized. Plural -CR ²¹ R ^22- are preferably the same.

(About l and n)
l represents an integer of 1 to 12, and n represents an integer of 1 to 12.
In terms of easy synthesis, l is preferably 1 to 5, more preferably 1 to 2.
N is preferably 2 to 5 and more preferably 2 in terms of easy synthesis.
When a plurality of l and n are contained in one molecule, each may be the same or different.

(About m)
m ¹ represents an integer of 1 to 3.
Among them, m ¹ is preferably 1 or 2, particularly preferably 1, in terms of good solubility in an alkali developer and curability of the obtained pixel.
(Molecular weight)
The molecular weight of the compound (1) is usually 400 or more, preferably 500 or more, and usually 2000 or less, preferably 1800 or less.
It is preferable at the point which is easy to manufacture a compound as it is in the said range.

[Specific Examples of Compound (1)]
Although the preferable specific example of a compound (1) is shown below, this invention is not limited to these.

(Synthesis Method of Compound (1))
Compound (1) can be synthesized according to a known method.
For example, pentaerythritol is reacted with an acid anhydride under an amine catalyst. Next, the compound containing an acid group-containing unsaturated bond is reacted under an amine catalyst.
Examples of the acid anhydride include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; trimellitic anhydride And anhydrides of three or more bases such as pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride.

Examples of the compound containing an acid group-containing unsaturated bond include crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like.
Examples of the amine catalyst include 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) and dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.).

(Content)
In the colored resin composition of the present invention, the content of the compound (1) is usually 1% by weight or more, preferably 5% by weight or more, more preferably 8% by weight or more, and usually 70% by weight or less in the total solid content. , Preferably 60% by weight or less, more preferably 40% by weight or less.
Within the above range, it is preferable in that the effect of the present invention can be easily obtained.

Furthermore, photocuring is moderate, and it is preferable because a peeling phenomenon and a drop defect due to poor adhesion at the time of development and a decrease in solubility in a developer in a non-pixel portion hardly occur.
<Reason for effect>
The reason why the compound (1) is effective in that the cross-sectional shape of the obtained pixel is less likely to be undercut, that is, less likely to be inversely tapered, is estimated as follows.

The compound represented by the formula (1) has a carboxy group structure as a substituent of a cyclic structure (Y ¹ : hydrocarbon ring group, heterocyclic group or aromatic ring group). For this reason, since it has alkali solubility and compatibility with the color material, it is easily present in the entire coating film together with the color material without having a distribution. Accordingly, the tendency for only the compound (1) to dissolve in the developer is small. In addition, since it has a cyclic structure, it has moderate resistance to a developer and forms a strong coating film together with an unsaturated double bond group contained in the same molecule.

Furthermore, in the case of the compound (1), the ethylenic double bond group has a long distance from the central carbon atom (the carbon atom to which the group enclosed by {} binds) and has a high degree of freedom. Therefore, the coating film containing the compound (1) tends to form a stronger film by photocuring.
From the above, even in the case of a colored resin composition having a high chromaticity concentration, the inside of the coating film is cured, while the solubility of the alkali developer is high, so that the cross-sectional shape is appropriately formed, that is, reverse taper. The effect of the present invention is difficult.

[(A) Color material]
The colored resin composition of the present invention contains (A) a color material. (A) The color material may be a pigment or a dye.
Each will be described below.
(Pigment)
In the present invention, it is preferable to use a pigment for the colorant (A) from the viewpoint of excellent heat resistance and light resistance.

As the pigment, pigments of various colors such as a red pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be usually used.
Examples of the chemical structure of various pigments include organic pigments such as azo, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition to these, various inorganic pigments can also be used.

Specific examples of pigments that can be used in the present invention are shown below by pigment numbers, but are not limited to these examples.
First, as a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 242, 254, and the like.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like. Of these, C.I. I. Pigment green 7, 36, 58, and the like.
In particular, C.I. I. When the pigment green 58 is used, it is preferable in that the effects of the present invention can be easily obtained.

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

Of these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and the pigment Y described in the above-mentioned 2 publication, and more preferably C.I. I. Pigment yellow 83, 138, 139, 180, and pigment Y described in the above-mentioned 2 publications.
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. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  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.

Alternatively, the pigment dispersion of the present invention may be used to prepare a colored resin composition as will be described later to form a resin black matrix of a color filter. In that case, a black pigment can be used. . In addition, a black pigment may be used independently and may mix and use pigments, such as red, green, and blue. Further, it may be an inorganic pigment or an organic pigment.
Examples of inorganic pigments that can be used in the present invention include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.

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

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

The pigment thus obtained may be used alone, but one or two or more pigments can be mixed and used within a range not impairing the effects of the present invention.
(dye)
In the present invention, it is preferable to use a dye as the colorant (A) in that the obtained pixel has excellent luminance and the like. The dye is not particularly limited as long as it does not impair the effect of the present invention. For example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes Preferred are dyes, cyanine dyes, triarylmethane dyes and the like.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

Examples of triarylmethane dyes include those described in International Publication No. 2009/107734, International Publication No. 2011/162217, and the like.
Further, examples of cyanine dyes include those described in JP-A-2008-242324, JP-A-2009-235392, etc., and preferred embodiments are also the same.
The content of the color material (A) in the present invention is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, and usually 0.1% by weight, based on the total solid content. Above, preferably 0.5% by weight or more, more preferably 1% by weight or more.

  (A) By setting the content of the color material in the above range, the film thickness with respect to the color density does not become excessively large, and it does not adversely affect the gap control or the like when forming a liquid crystal cell, and sufficient image formability is achieved. In addition, the dispersed state of the pigment is maintained, and aggregation and sedimentation hardly occur. As a result, problems such as thickening and lowering of brightness and contrast can be solved.

[(B) Solvent]
The colored resin composition of the present invention contains (B) a solvent.
The solvent (B) in the present invention is not particularly limited as long as it dissolves or disperses each component constituting the colored resin composition and the viscosity becomes appropriate, but preferably has a boiling point of 100 to 200 ° C. A solvent having a boiling point of 120 to 170 ° C. is preferable.
Examples of such solvents include the following.

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
Commercially available solvents corresponding to the above include mineral spirit, Barsol # 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.
Of the above solvents, glycol alkyl ether acetates are preferred from the viewpoint of good dispersibility of the pigment in the solvent. Furthermore, propylene glycol monomethyl ether acetate is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
In addition, it is more preferable to use a glycol monoalkyl ether as a solvent by mixing from the viewpoints of good balance such as applicability and surface tension and relatively high solubility of the components in the composition.

(B) The proportion of glycol monoalkyl ethers in the solvent is preferably 5 to 50% by weight and more preferably 5 to 30% by weight in terms of good storage stability.
Moreover, when using for a slit coat system, it is also preferable to use together the solvent with a boiling point of 150 degreeC or more. In this case, the content of the solvent having a boiling point of 150 ° C. or higher is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, and particularly preferably 3 to 30% by weight based on the total amount of the solvent (B).

If it is within the above range, the drying speed is appropriate, so it is difficult for colorant components to precipitate and solidify at the tip of the slit nozzle, tact failure in the vacuum drying process in the color filter manufacturing process, pre-baking pin marks, etc. Is preferable because
Examples of the solvent having a boiling point of 150 ° C. or higher include glycol alkyl ether acetates, glycol alkyl ethers, and chain or cyclic esters.

Moreover, when using for the inkjet method, it is preferable to use a high boiling-point solvent. This is because the ink emitted from the nozzle is very small, from several to several tens of pL, and the solvent evaporates before landing on the periphery of the nozzle opening or in the pixel bank. This is to prevent drying out.
Specifically, the boiling point of the solvent (B) is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 220 ° C. or higher.

The content of the solvent at 180 ° C. or higher is preferably 50% by weight or higher with respect to the total amount of the (B) solvent. Within the above range, the effect of preventing the solvent from evaporating from the ink droplets is sufficient, which is preferable.
In the colored resin composition of the present invention, the content of the (B) solvent is not particularly limited as long as the effect of the present invention is not impaired, but is usually 75% by weight or more, preferably 80% by weight or more, and more preferably 82%. % By weight or more, and usually 99% by weight or less.
Within the above range, the colored resin composition is preferable in that it has a viscosity suitable for application and can form a coating film satisfactorily.

[(C) Binder resin]
(C) The preferred resin for the binder resin differs depending on the curing means.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, 11-14144, JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and the like can be used. C-1) to (C-5) resins and the like.

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

The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item in 2009-025813. The preferred embodiment is also the same.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. 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 not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides and the like can be mentioned.
Mono (meth) acrylate having a structure represented by

  The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula ^{(8), R} 91 ~R ⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among these, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content of the repeating unit derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.
In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and strength are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenic double bond is mentioned.

  Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position 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 may be used alone or in combination of two or more.

By adding such components, polymerizability can be imparted to the 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%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a 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, succinic anhydride and tetrahydrophthalic 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 binder resin used in the present invention.
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 30 to 80 mol%.

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.
Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

  The polystyrene-reduced weight average molecular weight (Mw) of the binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5,000 to 50,000. If the molecular weight is less than 3000, heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g.
Within the above range, the solubility in a developer is good and film roughness is not likely to occur, which is preferable.
Moreover, content of (C) binder resin is 0.1 to 80 weight% normally in a total solid, Preferably it is 1 to 60 weight%.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.

[(D) Dispersant]
When the colored resin composition of the present invention contains a pigment in (A) the color material, it is preferable to further contain (D) a dispersant. The dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability.
For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. In particular, a block copolymer is preferable, and among these, a block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom is preferable.

Specifically, the B block having a nitrogen atom-containing functional group includes a unit structure having a quaternary ammonium base and / or an amino group in the side chain, while the solvophilic A block includes a quaternary ammonium. Examples include a unit structure having no base and 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 by following formula (VI) especially is preferable.

In the above 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 optionally substituted. Aralkyl groups having 7 to 20 carbon atoms are preferred.
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 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), and the like, preferably —COO—R ³⁶ —.
Examples of the counter anion M ⁻ 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 mg-KOH / 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 include the following: Examples include structures represented by the formulas.

(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 formula is particularly preferably used.

(In the above 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 (e-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 dispersant used in the composition for forming a color filter pixel of the present invention is a (meth) acrylic copolymer, an A block having a partial structure represented by the following formula (VIII) is particularly preferable.

(In the formula (VIII), n represents an integer of 1 to 5, but when there are a plurality of the units, that is, the formula (VIII) in one molecule, n may be the same or different. R ⁸¹ Represents a hydrogen atom or a methyl group, R ⁸² represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁸² is particularly preferably an ethyl group.)
The partial structure represented by the above formula (VIII) is preferably contained in an amount of 3 to 20 mol% in terms of monomers constituting the (meth) acrylic copolymer. Most preferably, it is contained in mol%.

Although the detailed mechanism of action is unknown, it has a partial structure derived from polyalkylene glycol (meth) acrylate, in particular a partial structure represented by the above formula, so that it is possible to increase hydrogen bonding properties, It is thought that the affinity for the dispersion improves and the stability of the dispersion increases.
Two or more partial structures represented by the 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 (D) that can be used in the pigment dispersion 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, a method described in JP-A-2007-270147 can be mentioned.

The amine value of 1 g of the dispersant (D) is usually about 1 to 300 mg-KOH / 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 the ABA block copolymer of the (D) dispersant has a quaternary ammonium base, the amount of the quaternary ammonium base in 1 g of the copolymer is 0.1 It is preferable that it is -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 mg-KOH / g, preferably 1 per gram of the copolymer. -50 mg-KOH / g, more preferably 1-30 mg-KOH / g.

  Further, when the B block does not contain a quaternary ammonium base, the amine value of the copolymer is usually about 50 to 300 mg-KOH / g, preferably 50 to 200 mg-KOH / g, more preferably 80 mg. It is -KOH / g or more and 150 mg-KOH / g or less, More preferably, it is 90-150 mg-KOH / g, Most preferably, it is 100-140 mg-KOH / 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 mg-KOH / g or less, preferably 50 mg- KOH / g or less, more preferably 40 mg-KOH / g or less, most preferably 30 mg-KOH / 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.

[Dispersion aid]
The colored resin composition of the present invention may contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

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

[Dispersion resin]
In the colored resin composition of the present invention, particularly when (A) a pigment is contained as a color material, a part or all of the resin selected from the above-mentioned (C) binder resin or other binder resins is dispersed resin as described below. It may contain as.

  Specifically, when dispersing the pigment of [Method for preparing colored resin composition] to be described later, the component (C) is added by adding (C) a binder resin together with the components (D) dispersant and the like. The binder resin contributes to the dispersion stability of the pigment by a synergistic effect with (D) the dispersant. As a result, there is a possibility that the amount of (D) dispersant added can be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

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

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

[(E) Polymerizable monomer]
The colored resin composition of the present invention may contain (E) a polymerizable monomer in addition to the compound (1) described above.
(E) The polymerizable monomer is not particularly limited as long as it is a low molecular weight compound that can be polymerized. However, an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

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

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

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

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

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

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

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (E) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 120 mg-KOH / g, and particularly preferably 5 to 90 mg-KOH / g.

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

In the colored resin composition of the present invention, the content of the polymerizable monomer (E) is preferably 1% by weight or more, more preferably 5% by weight or more, and particularly preferably 10% by weight or more in the total solid content. It is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower solubility are difficult to place. preferable.

[(F) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (F) a photopolymerization initiation component and / or a thermal polymerization initiation component for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In particular, since the colored resin composition of the present invention contains the compound (1), it has the function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. It preferably contains a photopolymerization initiating component.
The photopolymerization initiating component in the present invention includes a photopolymerization initiator (hereinafter arbitrarily referred to as (F1) component), a polymerization accelerator (hereinafter arbitrarily referred to as (F2) component), and a sensitizing dye (hereinafter referred to as “F1” component). , Optionally referred to as (F3) component).

(Photopolymerization initiation component)
The colored resin composition of the present invention preferably contains a photopolymerization initiation component. The photopolymerization initiating component is usually used as a mixture of (F1) a photopolymerization initiator and an additive such as (F2) a polymerization accelerator and (F3) a sensitizing dye, which are added as necessary. It is a component having a function of generating a polymerization active radical by directly absorbing or photosensitizing to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the (F1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives Oxime ester derivatives described in JP 2000-80068 A (hereinafter referred to as “oxime ester”). It referred to as ether-based initiator "), and the like.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester initiators, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable, and oxime ester initiators are particularly preferable.

  Examples of the oxime ester initiator 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 a compound represented by the following formula (XI).

(In formula (XI), R ¹⁰¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 2 to 25 carbon atoms.
An alkenyl group, a C 3-20 heteroaryl group or a C 4-25 heteroarylalkyl group, any of which may have a substituent. Alternatively, R ¹⁰¹ may be bonded to X or Z to form a ring.
R ¹⁰² represents an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, which are all It may have a substituent.

X represents a divalent aromatic hydrocarbon group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
Z represents an aromatic group which may have a substituent. )
Of the compounds represented by the formula (XI), compounds in which X is a carbazole ring which may have a substituent are preferable. Specifically, compounds represented by the following formula (XII) Among them, the compound represented by the following formula (XIII) is particularly preferable.

(Wherein R ¹⁰¹ , R ¹⁰² and Z have the same meanings as in formula (XI), R ^103.
To R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent. )

(In the formula, R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (XIIIa).

(Wherein R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom, a phenyl group or an N-acetyl-N-acetoxyamino group.
* Represents a binding site. )
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Z ^a represents an even better naphthyl group optionally substituted by also phenyl group or a morpholino group substituted with an alkyl group. )
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester initiators are more preferable, and oxime ester initiators are particularly preferable.
Examples of the (F2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

These (F1) photopolymerization initiators and (F2) polymerization accelerators may be used alone or in combination of two or more.
Further, (F3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(F3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content of these (F) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight based on the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less.
Within the above range, the sensitivity to the exposure light beam is good, the solubility of the unexposed part in the development station is good, and it is preferable in that it is difficult to induce poor development.

(Thermal polymerization initiation component)
Specific examples of the thermal polymerization initiation component (thermal polymerization initiator) 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. More specifically, for example, a thermal polymerization initiator described in International Publication No. 2009/107734 pamphlet or the like can be used.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

[Other ingredients]
In addition to the above components, the colored resin composition of the present invention comprises a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface It may further contain a protective agent, an adhesion improver, a development improver and the like. As these other components, for example, various compounds described in JP-A-2007-113000 can be used.
In addition, about surfactant, it is as follows.

[Surfactant]
The colored resin composition of the present invention may further contain a surfactant. Various types of 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.

As the surfactant, for example, those described in JP-A-2009-25813 can be used.
The content of these surfactants is preferably 0.001% by weight or more, more preferably 0.005% by weight or more, and still more preferably 0.01% by weight in the total solid content of the colored resin composition of the present invention. That's it. Further, it is preferably used in the range of 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less.

[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, the (A) color material, (B) solvent, (C) binder resin, compound (1) and other additives can be used. It can be prepared by mixing together.
(A) When a pigment is contained in the color material, a more preferable preparation method is as follows. In the presence of a pigment in a solvent, (D) a dispersing agent and a dispersing aid to be added if necessary, (C) a binder resin. A pigment dispersion is prepared by mixing and dispersing with a part of the above, for example, using a paint shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer and the like. The pigment dispersion is prepared by adding and mixing the compound (1), (C) binder resin, and additives and dyes such as (E) polymerizable monomer and (F) photopolymerization initiation component as necessary. The method of doing can be mentioned.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the following examples, “part” represents “part by weight”.
[1] Synthesis of Resin <Synthesis Example 1: Synthesis of Resin A>
Prepare a separable flask with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while stirring to raise the temperature of the reaction tank to 90 ° C. did.

  Meanwhile, 30 parts by weight of dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, 60 parts by weight of methacrylic acid, 110 parts by weight of cyclohexyl methacrylate, t-butylperoxy-2-ethyl Charge 5.2 parts by weight of hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate, charge 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate to the chain transfer agent tank, and temperature of the reaction tank After stabilizing at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, 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, 39.6 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were charged into the reaction vessel at 110 ° C. as it was. For 9 hours. The weight average molecular weight Mw measured by GPC of the resin A thus obtained was 8000, and the acid value was 101 mg-KOH / g.

<Synthesis Example 2: Synthesis of Resin B>
114.0 g of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while performing nitrogen bubbling. To this, 114.4 g (0.65 mol) of benzyl methacrylate, 25.9 g (0.35 mol) of methacrylic acid, and 4.9263 g (0.03 mol) of 2,2′-azobis (isobutyronitrile) were added to propylene glycol monomethyl ether acetate. It melt | dissolved in 96.45g and it was dripped over 4 hours. After dropping, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. To this, 0.6628 g (4 × 10 ⁻³ mol) of tetraethylammonium chloride was added, stirred and dissolved at 80 ° C., and further 15.93 g (0.088 mol) of 3,4-epoxycyclohexyl-1-methyl acrylate, propylene A solution in which 23.90 g of glycol monomethyl ether acetate was mixed was added dropwise over 1 hour. The reaction solution was stirred for 30 hours while maintaining at 80 ° C. to obtain Resin B having a weight average molecular weight of 20,000 and an acid value of 90 mg-KOH / g.

<Synthesis Example 3: Synthesis of Resin C>
While stirring, 183.1 parts by weight of propylene glycol monomethyl ether acetate was replaced with nitrogen, 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 FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and 2.2′-azobis-2-methyl 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 for 12 hours at 100 ° C. Thereafter, 56.2 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 resin C thus obtained was about 8400, and the acid value was 80 mg-KOH / g.

<Synthesis Example 4: Synthesis of Resin D>
In Synthesis Example 1, 60 parts by weight of methacrylic acid was changed to 90 parts by weight of acrylic acid, 110 parts by weight of cyclohexyl methacrylate was changed to 80 parts by weight, and 39.6 parts by weight of glycidyl methacrylate was changed to 63.4 parts by weight. A resin D having a weight average molecular weight Mw of 8000 and an acid value of 101 mg-KOH / g was obtained.
[2] Synthesis of Dye <Synthesis Example 5: Synthesis of Dye A>

Reaction 1: Phosphorus oxychloride (1.8 ml) was added to a mixture of compound 3 (5.61 g), compound 4 (2.65 g) and toluene (15 ml), and the mixture was stirred at 115 ° C. for 2 hours. After returning to room temperature, saturated brine (30 ml) was added, and the mixture was extracted twice with chloroform. Silica gel column chromatography (silica gel 300 g, chloroform / methanol 1 / 0-10 / 1/7 /
The product obtained after purification in 1) was washed with hexane to obtain Compound 5 (9.23 g).
Reaction 2: A mixture of compound 5 (11.40 g), compound 7 (4.88 g) and methanol (146 ml) was stirred at 50 ° C. for 1 hour, added to water, and the solid was collected by filtration. The solid was washed with methanol / water: 2/1 (220 ml) and again washed with methanol / water /: 2/1 (72 ml) to obtain Dye A.
[3] Synthesis of photopolymerization initiator (compound IV)

Under a nitrogen atmosphere, Compound I (0.98 g, 5 mmol) and methylene chloride (17 mL) were added to a 50 ml three-necked flask. After cooling this to 3 ° C., o-toluoyl chloride (0.77 g, 5 mmol) was added dropwise. To this, aluminum chloride (0.67 g, 5 mmol) was slowly added over 1 hour. After completion of the addition, the mixture was further stirred at 3 ° C. for 2 hours, and methylene chloride (8 mL) was added. Next, glutaric anhydride (0.68 g, 6 mmol) was added over 30 minutes, and then aluminum chloride (1.90 g, 14 mmol) was added over 30 minutes.

  After completion of the addition, the mixture was further stirred at 3 ° C. for 2 hours, and the reaction solution was poured into ice water (400 mL) little by little. Sodium chloride (80 g) was added to the aqueous layer, and extraction was performed 5 times with methylene chloride (50 mL). The organic layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain Compound II (2.13 g, crude yield 100%). This was used in the next reaction without purification.

Under a nitrogen atmosphere, Compound II (2.13 g, 5 mmol), methanol (22 mL) and concentrated sulfuric acid (5 mg) were placed in a 50 ml three-necked flask and heated under reflux for 3 hours. After cooling, the solvent was concentrated and water (10 mL) and ethyl acetate (30 mL) were added.
The organic layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain Compound III (1.72 g, crude yield 78%). This was used in the next reaction without purification.

  In a nitrogen atmosphere, Compound III (1.00 g, 2.26 mmol) and methylene chloride (10 mL) were placed in a 50 mL three-necked flask and cooled to 10 ° C. To this was added 1N hydrogen chloride in diethyl ether (4.68 mL). Next, amyl nitrite (0.36 g, 3.04 mmol) was added and reacted at 10 ° C. for 4 hours. After adding water (10 mL), it wash | cleaned in order with saturated sodium hydrogencarbonate aqueous solution and saturated sodium chloride aqueous solution, and anhydrous magnesium sulfate was added and it dried. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain a pale yellow solid (0.88 g). This was recrystallized and purified with toluene (3.5 mL) to obtain Compound IV (0.45 g, yield 42%).

[4] Preparation of pigment dispersion
[4-1] Preparation of green pigment dispersion (1)
As a pigment, C.I. I. Pigment Green 58 (manufactured by DIC; hereinafter abbreviated as “G58”) at 18.00 parts by weight, “BYK-LPN6919” (methacrylic acid AB block copolymer, amine value 121 mg-KOH / g, acid as a dispersant) 1 mg-KOH / g or less) (by Big Chemie) in terms of solid content is 4.50 parts by weight, resin A synthesized in Synthesis Example 1 is 6.00 parts by weight in terms of solids, and propylene glycol monomethyl ether acetate as a solvent A stainless steel container was filled with 114.00 parts by weight of zirconia beads having a diameter of 0.5 mm and dispersed in a stainless steel container for 6 hours to prepare a green pigment dispersion (1).

[4-2] Preparation of yellow pigment dispersion (1)
Resin synthesized in Synthesis Example 1 with 18.00 parts by weight of “E4GN-GT” (manufactured by LANXESS) as the pigment and 4.50 parts by weight of “BYK-LPN6919” (manufactured by BYK Chemie) as the dispersant A is 6.00 parts by weight in terms of solid content, 114.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 225 parts by weight of zirconia beads having a diameter of 0.5 mm are filled in a stainless steel container and dispersed for 6 hours in a paint shaker. A yellow pigment dispersion (1) was prepared.

[4-3] Preparation of blue pigment dispersion (1) C.I. I. Pigment Blue 15: 6 (hereinafter abbreviated as “B15: 6”), 8.50 parts by weight, C.I. I. 1.50 parts by weight of Pigment Violet 23, Dispersbyk 2000 (manufactured by Big Chemie) as a dispersant is 5.00 parts by weight in terms of solids, and resin B synthesized in Synthesis Example 2 is 5.00 parts by weight in terms of solids. Zirconia beads 22 having 80.86 parts by weight of propylene glycol monomethyl ether acetate as a solvent and a diameter of 0.5 mm
5 parts by weight were filled in a stainless steel container and dispersed for 6 hours with a paint shaker to prepare a blue pigment dispersion (1).

[4-4] Preparation of Blue Pigment Dispersion (2) 10 parts by weight of B15: 6 as a pigment, Disperbyk 2000 (manufactured by Big Chemie) as a dispersant, 5.00 parts by weight in terms of solid content, and further synthesized in Synthesis Example 2 The resin B was 3.33 parts by weight in terms of solid content, 73.2 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 225 parts by weight of zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container, and 6 in a paint shaker. A blue pigment dispersion (2) was prepared by time dispersion.

[3-5] Preparation of red pigment dispersion (1) C.I. I. Pigment Red 254, 12.00 parts by weight, C.I. I. Pigment Red 177 is 3.00 parts by weight, Dispersbyk 2000 (manufactured by Big Chemie) as a dispersant is 6.00 parts by weight in terms of solids, and resin B synthesized in Synthesis Example 2 is 5.00 parts by weight in terms of solids. 10 propylene glycol monomethyl ether acetate as solvent
4.00 parts by weight and 225 parts by weight of zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion.

[5] Preparation of colored resin composition in which coloring material is pigment only [4-1] to [4-3], [4-5] The dispersion prepared in propylene glycol monomethyl ether acetate (hereinafter, “ PGMEA ”) and ethyl 3-ethoxypropionate (hereinafter referred to as“ EEP ”), Resin C synthesized in Synthesis Example 3 as a binder resin, a polymerizable monomer, a photopolymerization initiation component, and DIC as a surfactant A propylene glycol monomethyl ether acetate solution (solid content: 1% by mass) of F-475 (fluorinated surfactant) manufactured by F-475 was mixed at a ratio shown in Table 1 to prepare colored resin compositions of Examples and Comparative Examples. . In addition, the numerical value of Table 1 is content (weight part).

In addition, all the numerical values in Table 1 represent parts by weight of each component to be added.
Moreover, each compound in Table 1 is as follows.

TO2349 (manufactured by Toa Gosei Co., Ltd.): Polybasic acid-modified acrylic oligomer (acid value 68)
M-510 (manufactured by Toa Gosei Co., Ltd.): polybasic acid-modified acrylic oligomer M-520 (manufactured by Toagosei Co., Ltd.): polybasic acid-modified acrylic oligomer IRGACURE907 (manufactured by BASF): 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one IRGACURE OXE02 (manufactured by BASF): Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime)
BI: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole EAB-F (Hodogaya Chemical Co., Ltd.) 4,4 'Bisdiethylaminobenzophenone 2MBT: 2-mercaptobenzothiazole F-475 (manufactured by DIC)
In the same manner as above, mixing was performed at the ratio shown in Table 2 to prepare colored resin compositions of Examples and Comparative Examples. In addition, the numerical value of Table 2 is content (weight part) of solid content.

[6] Preparation of Colored Resin Composition Containing Dye Blue Pigment Dispersion Liquid (2) Prepared in [4-4], PGMEA as Solvent, Resin D Synthesized in Synthesis Example 4 as Binder Resin, Polymerizable Monomer, Photopolymerization A starting resin and a propylene glycol monomethyl ether acetate solution (solid content: 1% by mass) of a fluorosurfactant RS-72-K (manufactured by DIC) are mixed at a ratio shown in Table 3, and the colored resin of the example A composition was prepared. In addition, the numerical value of Table 3 is content (weight part).

[7] Manufacture of pattern (pixel) [7-1] Examples 1-4, Reference Examples 1-6, Comparative Examples 1-4
Each of the colored resin compositions was spin-coated on a glass substrate on which chromium was deposited, and prebaked for 3 minutes on a hot plate at 80 ° C. After the post-baking, Examples 1 to 4, Reference Examples 13 and 6, and Comparative Examples 1 and 2 have color coordinates y = 0.599, and Reference Example 4 and Comparative Example 3 have color coordinates y = 0. In 085, Reference Example 5 and Comparative Example 4 were adjusted so that the color coordinate y = 0.303.

Next, after exposing the sample at 50 mj / cm ² through a linear mask pattern having a width of 50 μm and a length of 3 mm with a high-pressure mercury lamp, a 0.04 wt% potassium hydroxide aqueous solution was used,
Spray development was performed at a developer temperature of 23 ° C. and a pressure of 0.25 MPa. The development time was set to twice the dissolution time of the colored resin composition measured in advance.
The dissolution time measurement will be described later. After development, the substrate was rinsed with sufficient water and then dried with clean air. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes. Table 2 shows the dry film thickness.

[7-2] Examples 5 to 8 and Reference Example 7
Each of the colored resin compositions was spin-coated on a glass substrate AN100 (Asahi Glass Co., Ltd.) and vacuum-dried for 1 minute. The coating rotation speed was adjusted to be 3.2 μm after post-baking.
Next, the sample was exposed at 40 mj / cm ² through a linear mask pattern having a width of 50 μm and a length of 3 mm with a high-pressure mercury lamp, and spray development was performed at a developer temperature of 26 ° C. and a pressure of 0.15 MPa using an aqueous carbonate solution. The development time was set to +10 seconds of the dissolution time of the colored resin composition measured in advance.
After development, the substrate was rinsed with sufficient water and then dried with clean air. Thereafter, measurement was performed.

[8] Measurement of dissolution time Similar to the production of the pattern (pixel), when the colored resin composition was applied, dried, exposed and developed on the cleaned glass substrate AN100 (Asahi Glass Co., Ltd.), The time when the colored resin composition was completely dissolved in the developer and the substrate was exposed was defined as the dissolution time of the colored resin composition.

[9] Measurement of adhesion The narrowest line width among the remaining line patterns among the linear patterns obtained as described above was defined as the adhesion value.
[10] Measurement of taper shape The cross-sectional shape of the 50 μm-wide linear pattern obtained as described above was observed with SEM (Hitachi S-4500).

[11] Measurement of linearity
The shape of the 50 μm-wide linear pattern obtained as described above is observed with a microscope at 50 ×, and ◎ indicates that there is no scratch, ○ indicates that there is almost no linearity, and ○ indicates that there are several protrusions and irregularities. Δ, and what is often observed is ×.
The results are shown in Table 4.

As shown in Table 5, the pixel formed using the colored resin composition for a color filter of the present invention has an appropriate cross-sectional shape, that is, a forward taper.
For this reason, even when a pixel having a high color density is formed or when the tact time is shortened, a display defect or a defect due to the cross-sectional shape hardly occurs.
As shown in Table 6, when the colored resin composition for a color filter of the present invention is used, the adhesiveness is excellent, and display defects and defects are hardly caused in the same manner.
That is, by using the colored resin composition of the present invention, a pixel having a high color density, and a high-quality liquid crystal display device and organic EL display device can be formed.

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

Claims (7)

(A) Colored resin, (B) solvent, (C) Colored resin composition containing binder resin, further containing a compound represented by the following formula (1), a colored resin for a color filter Composition.

(In the above formula (1),
Y ¹ represents a hydrocarbon ring group which may have a substituent, a heterocyclic group which may have a substituent, or an aromatic ring group which may have a substituent.
R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
R ¹¹ and R ¹² may be bonded to each other to form a ring.
l is an integer from 1 to 12,
m is an integer of 1 to 3,
n represents an integer of 1 to 12.
In addition, when 1 and n and -CR < ¹¹ > R < ¹² >-which are contained plurally are contained in one molecule, they may be the same or different. )   The colored resin composition for a color filter according to claim 1, wherein the content of the compound represented by the formula (1) is 1% by weight or more and 70% by weight or less in the total solid content. .   Furthermore, (F) The photopolymerization start component is contained, The colored resin composition for color filters of Claim 1 or 2 characterized by the above-mentioned. As (F) photopolymerization initiation component, (F1) contains a photopolymerization initiator,
The colored resin composition for a color filter according to claim 3, wherein the (F1) photopolymerization initiator is an oxime ester-based initiator.   It has a pixel formed using the colored resin composition for color filters as described in any one of Claims 1-4, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 5.   An organic EL display device comprising the color filter according to claim 5.

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