JP2010145857A - Colored resin composition for color filter, color filter, liquid crystal display, and organic el display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored resin composition for a color filter capable of effectively increasing retardation without lowering the transmittance of pixels, while keeping compatibility between contrast ratio control and hue control. <P>SOLUTION: The colored resin composition for a color filter contains (A) a pigment, (B) a dispersant and (C) a binder resin, wherein the pigment (A) contains C.I. Pigment Green 58 and the binder resin (C) contains a resin (C-9) having a weight average molecular weight Mw and a double bond equivalent each within a specific range. The use of the colored resin composition is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

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

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

  Also, C.I. which is a brominated zinc phthalocyanine-based green pigment. I. (Color Index) Pigment Green 58 has an extremely high transmittance as compared with a green pigment conventionally used for the application, and therefore studies using this pigment have been promoted in recent years. C. I. In order to take advantage of the properties of Pigment Green 58, it is preferable to make the primary particle size of the pigment sufficiently small and improve the contrast of the pixels formed by using this, but as the contrast is improved, there is no problem with the conventional method. There has been a demand for optimization of pixel retardation.

In order to perform phase difference compensation of this liquid crystal display device or the like, a phase difference film may be used together (see Patent Document 1). As the retardation film, a film obtained by stretching a polycarbonate film or the like, or a film obtained by applying a liquid crystal material having birefringence anisotropy to a triacetyl cellulose film or the like is usually used.
However, in the above-described retardation film, the retardation amount is kept uniform in the plane. Therefore, the optimum retardation amount is not always set for each actually displayed pixel, and the optimum retardation compensation is not necessarily performed. Is not done. One reason for this is that the phase difference and refractive index of the liquid crystal itself have a wavelength dependency of the transmitted light, so the phase difference depends on the display pixel color (actually the wavelength of the transmitted light) of each color constituting the color filter The amount of retardation required for the film is also different.

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

  Another reason is that when each colored display pixel constituting the color filter has retardation, a phase difference occurs in the transmitted light, so that the viewing angle dependency of the liquid crystal display device is increased and display characteristics are deteriorated. Is mentioned. For example, as described in Patent Documents 3 to 5, for example, a colored polymer thin film corresponding to a pixel of a color filter contains a polymer having a planar structure group in a side chain or is colored. There has been proposed an attempt to reduce the amount of retardation of a color filter by containing birefringence reducing particles having birefringence opposite to that of a polymer in a polymer thin film.

  However, this method has a problem that the solubility in the colored resin composition is insufficient and a necessary amount cannot be added, and a pixel transmittance decreases due to coloration due to the addition. Further, in order to provide a color filter in which the retardation is controlled in each of the red, green, and blue color display pixels, as described in Patent Documents 6 and 7, the selection of the pigment type and the degree of atomization ( There has been proposed a method of controlling the thickness direction retardation value of each color display pixel by controlling the primary particle size of the pigment).

However, this method has a problem that it is difficult to achieve both contrast ratio control and hue control.
On the other hand, it is also assumed that the retardation of a specific color is intentionally increased in order to balance each color. However, in the above known technique, the direction in which the retardation is changed is small. There are many that do (that is, eliminate the phase difference), and no technique has been found for increasing retardation while overcoming all the above problems.
JP-A-10-153802 JP-A-2005-148118 JP 2000-136253 A JP 2000-187114 A JP 2003-344655 A JP 2008-152140 A JP 2007-293061 A

The present invention has been made in view of the above-mentioned problems, and its object is as follows.
(1) In general, with respect to a green pixel that is used as a reference in optical design of a liquid crystal display device or the like, retardation is effectively reduced without reducing the transmittance of the pixel and maintaining both contrast ratio control and hue control. To provide a colored resin composition that can be increased.
(2) By using such a colored resin composition, it is possible to produce a color filter with high transmittance, high contrast, and low film thickness as a result.
(3) By providing such a color filter, a liquid crystal display device and an organic EL display having good visibility without coloring even when observed from an oblique direction are provided.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have controlled retardation of the green pixel of the color filter by controlling the structure of the (C) binder resin to be used together when a specific green pigment is used. The inventors have found that it can be increased, and have reached the present invention.
That is, the gist of the present invention is as follows.
(1) A colored resin composition for a color filter containing (A) a pigment, (B) a dispersant, and (C) a binder resin,
(A) The pigment is C.I. I. Pigment Green 58,
(C) Binder resin
(C-9) Resin: a resin having a weight average molecular weight Mw of more than 12000 and 40000 or less, and a double bond equivalent of less than 1000,
A colored resin composition for a color filter, comprising:
(2) The colored resin composition for a color filter according to (1), wherein the (C-9) resin contains a repeating unit derived from methacrylic acid and a repeating unit derived from a methacrylic ester as essential components.
(3) The colored resin composition for a color filter as described in (2) above, wherein the methacrylic acid ester contains benzyl methacrylate or cyclohexyl methacrylate.
(4) The colored resin composition for a color filter according to any one of (1) to (3), further comprising (E) a polymerizable monomer.
(5) The colored resin composition for a color filter according to any one of (1) to (4), further comprising (F) a photopolymerization initiator system (6) of (1) to (5) The color filter which has a pixel formed using the colored resin composition as described in any one.
(7) A liquid crystal display device comprising the color filter according to (6).
(8) An organic EL display comprising the color filter according to (6).

  By using the colored resin composition of the present invention, it is possible to effectively increase the retardation of the green pixel without reducing the transmittance of the pixel and while maintaining both the contrast ratio control and the hue control. In addition, by using such a colored resin composition, a color filter with high transmittance, high contrast, and low film thickness can be produced as a result, and there is no coloration even when viewed from an oblique direction. Liquid crystal display device and organic EL display can be provided.

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.
In the present invention, the “retardation” of the color filter pixel means R _th represented by the following equation.

In the above formula, _nx and _ny are refractive indexes in two in-plane orthogonal directions, _nz is a refractive index in the film thickness direction, and d is a film thickness. In the case of the pixel for a color filter, typically for an in-plane isotropy, n _x and n _y affect the value of even R _th is set to any direction of the plane it is considered that there is no.
“(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”. “Acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

“Total solid content” means all components other than the solvent components described later, which are contained in the pigment dispersion or the colored resin composition.
Moreover, in this invention, unless there is particular notice, a weight average molecular weight refers to the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography). “C.I.” means a color index (C.I.).
Furthermore, in the present invention, “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the weight of the base amount per 1 g of the solid content of the dispersant and the equivalent weight of KOH. is there. The measuring method will be described later. On the other hand, “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

<Coloring resin composition for color filter>
Subsequently, each component of the colored resin composition of the present invention will be described. The colored resin composition according to the present invention includes (A) a pigment, (B) a dispersant, and (C) a binder resin as essential components, and if necessary, may contain additives other than the above components. Good.
<(A) Pigment>
The pigment (A) used in the colored resin composition of the present invention is C.I. I. Pigment Green 58 is contained as an essential component. “CI” means a color index.
C. a brominated zinc phthalocyanine pigment. I. Pigment Green 58 exhibits extremely high transmittance as compared with a green pigment conventionally used in a composition for a color filter, but in order to further utilize the characteristics, the primary particle size of the pigment is made sufficiently small, It is preferable to improve the contrast of the pixel formed using this.
The refinement of the primary particle size can be performed by, for example, a solvent salt milling method or a solvent boiling method. There are no particular restrictions on the method of miniaturization, but it is preferable to employ a solvent salt milling treatment in that pigment growth can be easily suppressed and pigment particles having a large specific surface area can be obtained.

  C. I. The average primary particle size of Pigment Green 58 is usually 0.1 μm or less, preferably 0.05 μm or less, more preferably 0.04 μm or less, and usually 0.005 μm or more. By controlling the average primary particle size within this range, it maintains excellent depolarization characteristics, achieves high contrast and transmittance, and has good dispersion stability and excellent heat resistance and light resistance. A colored resin composition can be obtained.

  In addition, the average particle diameter of a pigment can be calculated | required with the following method. That is, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). In the case of an organic pigment, the particle diameter of each pigment particle is defined as an area equivalent circle diameter converted to the diameter of a circle having the same area, and after calculating the particle diameter for each of the plurality of pigment particles, the following formula Calculate the average particle size by calculating the number average value as follows.

The particle diameter of each pigment _{particle: X 1, X 2, X} 3, X 4, ····, X i, ······ X m

Average particle size = ΣX _i / m

  Thus obtained C.I. I. The pigment green 58 may be used alone, but may be used by mixing with brominated phthalocyanine in which the central metal is substituted with another metal as long as the effects of the present invention are not impaired. By changing the chlorination rate and bromination rate, or by changing the central metal, it is expected that the color tone of the pigment will change and that variations in the reproducible hue will increase. In addition, C.I. I. You may mix with halogenated copper phthalocyanines, such as pigment green (PG) 36 or 7.

  For adjusting the hue, it is effective to combine with at least one yellow pigment. Examples of yellow pigments include C.I. I. Pigment Yellow (P.Y.) 1, 1: 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,1 2,185,187,199,200,202,203,204,205,206,207,208,215, and include pigments described in JP-A-2005-325350, and among them P. Y. 83, 138, 139, 150, 180, 185, 215, and the pigments described in JP-A-2005-325350 are preferable. Y. 138, 150, 185, and pigments described in JP-A-2005-325350 are preferred. These can be used alone or in combination of two or more.

The average primary particle diameter of these yellow pigments is usually 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.04 μm or less.
Further, the pigment content in the colored resin composition for color filters of the present invention is usually 75% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, based on the total solid content. It is 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more.

  If the amount of the pigment is too large, it is difficult to maintain the dispersed state of the pigment, and aggregation and sedimentation may occur, resulting in problems such as thickening, luminance and a decrease in contrast. There is a possibility of a problem that it is thin and does not sufficiently function as a color filter.

<(B) Dispersant>
The colored resin composition of the present invention contains (B) a dispersant as one of the essential components. (B) The type of the dispersant is not particularly limited as long as the effects of the present invention are not impaired. For example, (B-1) a graft copolymer containing a nitrogen atom,
(B-2) an acrylic block copolymer containing a nitrogen atom, and (B-3) a urethane resin dispersant,
It is preferable to contain at least one dispersant selected from
In any of these (B-1) to (B-3), the nitrogen atom contained therein has an affinity for the pigment surface, and the portion other than the nitrogen atom increases the affinity for the medium as a whole. It is estimated that it contributes to the improvement of dispersion stability.

(B) The performance of the dispersant greatly depends on the adsorption behavior to the solid surface. Regarding the relationship between the molecular architecture and the adsorption behavior, it is known that when the same unit is used, the adsorption behavior is excellent in the order of random copolymerization <graft copolymer <block copolymer ( For example, Jones and Richards, “Polymers at Surfaces and Interfaces” p281).
Although the detailed mechanism is unknown, the following can be inferred.
That is, in the case of a normal random copolymer, the monomer constituting the copolymer has a high probability of being stably arranged in the copolymer sterically and / or electrically during the formation of the polymer. . The portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, and thus may be an obstacle when adsorbed to the pigment. In contrast, for resins with a controlled molecular arrangement, such as graft copolymers or block copolymers, the part that prevents the adsorption of the dispersant should be placed at a position away from the adsorption part of the pigment and the dispersant. Can do. That is, an optimum portion for adsorption can be arranged in the adsorption portion between the pigment and the dispersant, and a portion suitable for it can be arranged in the portion requiring solvent affinity. In particular, for the dispersion of pigments containing pigments having a small crystallite size, it is presumed that this molecular arrangement affects good dispersibility.

<(B-1) Graft copolymer containing nitrogen atom>
(B-1) A graft copolymer containing a nitrogen atom (hereinafter sometimes referred to as “(B-1) dispersant”) is preferred in that (A) the pigment can be dispersed very efficiently. The reason is not clear, but because it has a structure that can actively eliminate the part (molecule) that hinders the adsorption of the pigment and the dispersant around the adsorption part to the pigment. As the graft copolymer containing a nitrogen atom, one having a repeating unit containing a nitrogen atom in the main chain is preferable, among which the repeating unit represented by the following general formula (I) and / or the following: It preferably has a repeating unit represented by the general formula (II).

(In the general formula (I), R ⁵¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any one of the following general formulas (III) to (V).)
In the general formula (I), R ⁵¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group or a propylene group, preferably 2 to 3 carbon atoms, An ethylene group is preferred.

  A represents a hydrogen atom or any one of the following general formulas (III) to (V), preferably the following general formula (III).

(In said general formula (II), R ^{< 51>} , A is synonymous with R ^<51> , A in said general formula (I) respectively.)

(In the above general formula (III), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, among which an alkylene group having 4 to 7 carbon atoms such as a butylene group, a pentylene group or a hexylene group is present. (P represents an integer of 1 to 20, preferably an integer of 5 to 10.)

(In the general formula (IV), Y ₁ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as an ethylene group or a propylene group, or a carbon number 1 such as an ethyleneoxy group or a propyleneoxy group. An alkyleneoxy group having a carbon number of ˜4 is preferable, and W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as an ethylene group, a propylene group, or a butylene group, and more particularly a carbon number such as an ethylene group or a propylene group. Preferred is an alkylene group having _{2 to 3.} Y ₂ represents a hydrogen atom or —CO—R ⁵² (wherein R ⁵² represents an alkyl group having 1 to 10 carbon atoms such as an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group). Among them, an alkyl group having 2 to 5 carbon atoms such as an ethyl group, a propyl group, a butyl group, and a pentyl group is preferable.) Q represents an integer of 1 to 20, and preferably an integer of 5 to 10. )

(In the general formula (V), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, and in particular, 10 to 10 carbon atoms such as a stearyl group. A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as an alkyl group of 20 or a monohydroxystearyl group is preferred.
(B-1) The content of the repeating unit represented by the general formula (I) or the general formula (II) in the dispersant is preferably higher, and is usually 50 mol% or more, preferably 70 mol% or more. is there. The repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) may be both present, and the content ratio is not particularly limited, but the general formula (I) It is preferable to contain a large number of repeating units. The total number of repeating units represented by the general formula (I) or the general formula (II) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50 in one molecule.

The (B-1) dispersant may contain a repeating unit other than the general formula (I) and the general formula (II). Examples of the other repeating unit include an alkylene group and an alkyleneoxy group. .
The terminal of the graft copolymer (B-1) is preferably —NH ₂ and —R ⁵¹ —NH ₂ (R ⁵¹ is synonymous with R ^{51 of} formula (I)).

In addition, as long as the (B-1) dispersant is a graft copolymer, the main chain may be linear or branched.
(B-1) The amine value of a dispersing agent is 5-100 mgKOH / g normally, Preferably it is 10-70 mgKOH / g, More preferably, it is 15-40 mgKOH / g or less. If the amine value is too low, the dispersion stability may decrease and the viscosity may become unstable. On the other hand, if the amine value is too high, the residue may increase or the electrical characteristics after the liquid crystal panel is formed may decrease. is there.

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

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)

(B-1) The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of the dispersant is preferably 3000 to 100,000, particularly preferably 5000 to 50000. If the weight average molecular weight (Mw) is less than 3000, pigment aggregation cannot be prevented and the viscosity or gelation may occur. Conversely, if the weight average molecular weight (Mw) exceeds 100000, the viscosity itself increases. The solubility in organic solvents may be insufficient.
(B-1) A known method can be adopted as a method for synthesizing the dispersant, and for example, a method described in JP-B-63-30057 can be used.
In the present invention, as the (B-1) dispersant, a commercially available graft copolymer having the same structure as that described above can also be applied.

<(B-2) Acrylic Block Copolymer>
(B-2) An acrylic block copolymer (hereinafter sometimes referred to as “(B-2) dispersant”) is preferable in that (A) the pigment can be dispersed extremely efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed on the pigment.

(B-2) The acrylic block copolymer of the dispersant is preferably a block copolymer composed of an A-block having solvophilicity and a B-block having a functional group containing a nitrogen atom.
Specifically, the B-block includes a B-block having a quaternary ammonium base and / or an amino group as a nitrogen atom-containing functional group in the side chain, and the solvophilic A-block includes a quaternary. A-blocks having no ammonium base and / or amino group can be mentioned. An AB block copolymer and / or an ABA block copolymer composed of these A blocks and B blocks are preferable. Hereinafter, these will be described in detail with reference to examples.
The quaternary ammonium base is preferably —N ⁺ R ³¹ R ³² R ³³ · Z ⁻ (wherein R ³¹ R ³² and R ³³ are each independently a hydrogen atom, or an optionally substituted cyclic or chain form) Or two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure, Z ⁻ represents a counter anion). 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.

As the cyclic structure formed by combining two or more of R ³¹ , R ^32, and R ³³ in —N ⁺ R ³¹ R ³² R ³³ · Z ^— , for example, a 5- to 7-membered nitrogen-containing heterocyclic ring Examples thereof include a single ring or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

(In the above general formula, R represents any group of R ³¹ , R ³² , and R ^33. These cyclic structures may further have a substituent.)
More preferred as ^{R 31,} R ^{32, R 33} in ^{-N + R 31 R 32 R 33} , each independently, optionally substituted alkyl group having 1 to 3 carbon atoms, or a substituent It is a phenyl group which may have, or a benzyl group which may have a substituent.

  As the B-block having a quaternary ammonium base, those containing a partial structure represented by the following general formula (VI) are preferable.

(In the general formula (VI), R ³¹ , R ³² , and R ³³ each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ³¹ , R ³² And two or more of R ³³ may be bonded to each other to form a cyclic structure, R ³⁴ represents a hydrogen atom or a methyl group, X ¹ represents a divalent linking group, Z ^- represents a counter anion).
In the general formula (VI), the hydrocarbon groups of R ³¹ , R ³² and R ³³ are each independently preferably a substituent having an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms. . 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, a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.

In the general formula (VI), examples of the divalent linking group X ¹ include an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ³⁵ —, —COO—R ³⁶ — (provided that R ³⁵ and R ³⁶ is 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, and is preferably —COO—R ³⁶ —.

Further, Z ⁻ of the counter anion includes Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.
As the nitrogen atom-containing functional group of the B-block, a primary to tertiary amino group is also preferable. The content ratio of the primary to tertiary amino groups is preferably 20 mol% or more, more preferably 50 mol% or more of the entire nitrogen atom-containing functional group. Of the primary to tertiary amino groups, tertiary amino groups are particularly preferred. As the tertiary amino group, specifically, —NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² each independently represents a cyclic or chain-like alkyl group which may have a substituent, or a substituent. And an allyl group which may have, or an aralkyl group which may have a substituent. Examples of the repeating unit having such a structure include structures represented by the following general formula.

^{(However, R 41} and ^{R 42} has the same meaning as above ^{R 41} and ^{R 42, R 43} is 1 or more alkylene groups having a carbon ^{number, R 44} represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably a methyl group, and R ⁴³ is preferably a methylene group or an ethylene group. R ⁴⁴ is preferably a hydrogen atom or a methyl group, more preferably a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following structural formula is particularly preferably used.

(Wherein R ⁴⁴ has the same meaning as described above.)
Moreover, as a most preferable structural formula, the structure represented by the following structural formula can also be mentioned.

  Two or more kinds of partial structures containing the specific quaternary ammonium base and / or amino group as described above may be contained in one B-block. In that case, two or more quaternary ammonium bases and / or amino group-containing partial structures may be contained in the B-block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base and / or amino group may be contained in the B-block, and examples of the partial structure are derived from the (meth) acrylic acid ester monomer described later. And the like. The content of the partial structure containing no quaternary ammonium base and / or amino group in the B-block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the base and / or amino group-free partial structure is not contained in the B-block.

On the other hand, (B-2) the solvophilic A-block constituting the acrylic block copolymer of the dispersant does not have a nitrogen atom-containing functional group such as the amino group described above, and the B-block described above. If it consists of a monomer copolymerizable with the monomer which comprises, there will be no restriction | limiting in particular.
(B-2) Examples of the solvophilic A-block constituting the acrylic block copolymer of the dispersant include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, (meta ) Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl ( (Meth) acrylate monomers such as (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; (meth) acrylic acid chloride (meth) ) Acrylate Monomers; vinyl acetate monomers; allyl glycidyl ether, polymer structure obtained by copolymerizing comonomers including glycidyl ether monomers such as crotonic acid glycidyl ether.

  Among them, as an A-block, polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate is included as a copolymerization component (that is, a partial structure derived from polyalkylene glycol (meth) acrylate). In particular, an A-block having a partial structure represented by the following general formula (VII) is preferred.

(In the general formula (VII), g represents an integer of 1 to 5, and R ⁶⁰ represents a hydrogen atom or a methyl group.)
As for the partial structure represented by the said general formula (VII), it is especially preferable that 5-40 mol% is contained in A-block.
Although the details of the mechanism of action are unknown, it is possible to increase the steric repulsion of the dispersant molecule by having a partial structure derived from polyalkylene glycol (meth) acrylate, particularly the partial structure represented by the above general formula. It is considered that the stability of the dispersion increases. When the repeating unit represented by the general formula (VII) is less than 5 mol% in the A-block, this effect may not be sufficiently exhibited, and even when the amount exceeds 40% mol, the dispersion stability is increased. The improvement tends to reach a peak.

In addition, the A-block is a (meth) acrylic acid ester type represented by the following general formula (VIII), particularly in terms of improving the familiarity with the nonpolar portion of the solvent by imparting appropriate hydrophobicity. It preferably contains a partial structure derived from a monomer.

(In the general formula (VIII), R ³⁹ represents a hydrogen atom or a methyl group. R ⁴⁰ may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents a good aryl group or an aralkyl group which may have a substituent.)
R ⁴⁰ is preferably a cyclic group from the viewpoint of high affinity with the pigment and good compatibility.

Two or more types of partial structures derived from the (meth) acrylic acid ester monomer may be contained in one A-block. Of course, the A-block may further contain a partial structure other than these. When two or more types of monomer-derived partial structures are present in the solvophilic A-block, each partial structure is contained in the A-block in any form of random copolymerization or block copolymerization. Also good. When the A-block contains a partial structure other than the partial structure derived from the (meth) acrylic acid ester monomer, the content of the partial structure other than the (meth) acrylic acid ester monomer in the A-block is , Preferably 0 to 99% by weight, more preferably 0 to 85% by weight.

(B-2) The dispersant contains a copolymer composed of an A-block and a B-block as described above, preferably an AB block or an ABA block copolymer. Among these, an AB block copolymer is preferable. Such a block copolymer is prepared, for example, by the living polymerization method shown below.
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.

(B-2) The amine value of 1 g of the dispersant is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferred range is when the B-block has a quaternary ammonium base and when it does not have. And different.
That is, when the B-block of the AB block copolymer and the ABA block copolymer of the (B-2) dispersant has a quaternary ammonium base, the quaternary in 1 g of the copolymer The amount of ammonium base is preferably 0.1 to 10 mmol. Outside this range, it may not be possible to combine good heat resistance and dispersibility. Such a block copolymer may contain an amino group generated in the production process, and its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 50 mgKOH per 1 g of the copolymer. / G, more preferably 1 to 30 mg KOH / g.

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

  If there are too few nitrogen atom-containing functional groups, the adsorptive power of the dispersant molecules on the pigment surface will be insufficient, and it will be difficult to obtain sufficient dispersion stability. On the other hand, if the amine value is too high, it means that the molecular weight of the A block is relatively small, and therefore, the pigment aggregation preventing function cannot be sufficiently exhibited and the dispersion stability may be insufficient. . In other words, the amine value is in the above range in order to develop the optimum dispersibility. The method for measuring the amine value is as described above.

  The acid value of this block copolymer is generally lower, although it depends on the presence and type of acidic groups that form the acid value. The molecular weight is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-reduced weight average molecular weight (Mw) measured by GPC. When the molecular weight of the block copolymer is too small, the dispersion stability is lowered, and when it is too large, the developability and the resolution tend to be lowered.

  (B-2) A commercially available acrylic block copolymer having the same structure as that described above can also be used as the dispersant. In particular, 20% by mole or more of the repeating units having a functional group containing a nitrogen atom in the B-block is a repeating unit having a nitrogen atom-containing functional group, so that a sufficient adsorptive power can be obtained and high dispersion stability can be obtained. It is preferable because of its property.

<(B-3) Urethane resin dispersant>
(B-3) As a urethane resin dispersant (hereinafter sometimes referred to as “(B-3) dispersant”), a polyisocyanate compound, a compound having one or two hydroxyl groups in the same molecule, A urethane resin obtained by reacting an active hydrogen and a compound having a tertiary amino group in the same molecule is particularly preferred.

  Examples of the polyisocyanate compounds include aromatics such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω ' -Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane; xylylene diisocyanate, α, α, α ', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate; lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate And triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane) and tris (isocyanatephenyl) thiophosphate; and their trimers, water adducts, and polyol adducts thereof.

Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination of two or more. .
As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, and carboxylates. For example, after the trimerization is stopped by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, or one terminal hydroxyl group of these compounds is an alkyl group having 1 to 25 carbon atoms and alkoxy. Or a mixture of two or more of these.
Examples of the polyether glycol include polyether diol, polyether ester diol, or a mixture of two or more of these.

  As the polyether diol, those obtained by homopolymerizing or copolymerizing alkylene oxide, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, Or the mixture of 2 or more types of those is mentioned.

Examples of the polyether ester diol include those obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or an anhydride thereof, or by reacting polyester glycol with an alkylene oxide. And oxytetramethylene) adipate.
Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Examples of the polyester glycol include dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and phthalic acid, or anhydrides thereof, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene. Glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neo Pentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentane Diol, 1,6-hexanediol, 2-methyl-2 4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene Aliphatic glycols such as glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene Obtained by polycondensation with a diol such as N-alkyldialkanolamine such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, or the like; The diols The polylactone diol or polylactone monool obtained by using a monohydric alcohol having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone, or mixture of two or more thereof. Most preferred as the polyester glycol is a polycaprolactone glycol or polycaprolactone starting from an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. is there.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like.
Of these compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred.

In addition, the number average molecular weight of the compound which has one or two hydroxyl groups in the same molecule is 300-10,000 normally, Preferably it is 500-6,000, More preferably, it is 1,000-4,000.
In the compound having an active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom includes a hydroxyl group, an amino group, a thiol group, etc. Among these, a hydrogen atom in the functional group is mentioned, and an amino group, particularly a primary amino group hydrogen atom is preferable. As the tertiary amino group, for example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, or the like, and the dialkylamino group are linked to form a heterocyclic structure. More specifically, an imidazole ring or a triazole ring can be mentioned. Among them, a dimethylamino group and an imidazole ring are preferable because of excellent dispersion stability.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  As the tertiary amino group is a nitrogen-containing heterocycle, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include nitrogen-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring; nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. It is done.

  Further, specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H. -1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino Examples include -1,4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole.

Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4- Triazole and the like are preferable.
The preferred use ratio of these urethane resin dispersant raw materials is that the compound having one or two hydroxyl groups in the same molecule is usually 10 to 200 parts by weight, preferably 20 to 190 parts by weight per 100 parts by weight of the polyisocyanate compound. Parts, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

If the content of a compound having one or more hydroxyl groups in the same molecule is more than the above range, the synthesis may be difficult, such as gelation due to too many reaction points during compound synthesis, If the amount is less than the above range, the so-called tail portion of the dispersant is shortened, which may result in insufficient dispersibility.
In addition, if the content of the compound having active hydrogen and amino group in the same molecule is more than the above range, the number of free adsorbing groups that do not adsorb to the pigment increases, and these are considered to be reaction points in the colored resin composition. Storage stability may be adversely affected. When the amount is less than the above range, the dispersant is difficult to be adsorbed to the pigment and may not function sufficiently as a dispersant.

  (B-3) Manufacture of a dispersing agent is performed according to the well-known method of urethane resin manufacture. As the solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone; esters such as ethyl acetate, butyl acetate, cellosolve acetate; benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, some alcohols such as isopropanol, sec-butanol and tert-butanol; halogenated hydrocarbons such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide An aprotic polar solvent such as N-methylpyrrolidone or dimethyl sulfoxide is used. Moreover, as a catalyst at the time of manufacture, a normal urethanization reaction catalyst is used. For example, tin systems such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate; iron systems such as iron acetylacetonate and ferric chloride; tertiary amine systems such as triethylamine and triethylenediamine Can be mentioned.

The amount of the compound having active hydrogen and tertiary amino group introduced in the same molecule is preferably controlled within the range of 1 to 100 mgKOH / g, more preferably 5 based on the amine value of the urethane resin obtained by the reaction. It is the range of -80 mgKOH / g, More preferably, it is the range of 10-60 mgKOH / g. When the amine value is less than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered. In addition, when an isocyanate group remains in the urethane resin obtained by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the time stability of the urethane resin is increased.

  The weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the urethane resin (B-3) dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3, It is in the range of 000 to 50,000. When the molecular weight is less than 1,000, the dispersibility and dispersion stability tend to be inferior. When it exceeds 200,000, the solubility is lowered, and the dispersibility is inferior, and at the same time, it is difficult to control the reaction.

<(B-4) Other dispersant>
(B) As a dispersing agent, dispersing agents other than said various (B-1) dispersing agent-(B-3) dispersing agent (it may be hereafter called "(B-4) dispersing agent") are contained. You may do it.
(B-4) Examples of the dispersant include a polyallylamine-based dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene diester-based dispersant, and a polyether. A phosphoric acid type dispersing agent, a polyester phosphoric acid type dispersing agent, a sorbitan aliphatic ester type dispersing agent, an aliphatic modification polyester type dispersing agent, etc. can be mentioned.

  Specific examples of such a dispersant include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (manufactured by Shinetsu) Chemical products), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and other series names can be mentioned.

The above-mentioned (B-1) dispersant to (B-4) dispersant may be used alone or in combination of two or more.
The colored resin composition of the present invention includes (B-1) a graft copolymer containing a nitrogen atom, (B-2) an acrylic block copolymer containing a nitrogen atom, among the various dispersants described above, and It is preferable to include one or more dispersants selected from (B-3) urethane resin dispersants, and it is particularly preferable to include (B-2) an acrylic block copolymer containing a nitrogen atom.

C., which is an essential component of the present invention. I. From the point that Pigment Green 58 can be most satisfactorily dispersed, (B-2) Among acrylic block copolymers containing a nitrogen atom, in particular, it has an amino group in the side chain as a nitrogen atom-containing functional group, and A dispersant having an amine value of 80 mgKOH / g or more and 150 mgKOH / g or less (in terms of effective solid content) is most preferable.
In the colored resin composition of the present invention, the content of the (B) dispersant is preferably about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the (A) pigment. . (B) By controlling the content ratio of the dispersant within this range, a necessary and sufficient amount of the dispersant adheres to the pigment surface, so that the aggregation is effective without reducing the coloring power of the colored resin composition. In addition, since high viscosity or gelation can be avoided, high dispersion stability can be ensured.

<(C) Binder resin>
<(C-9) Resin>
The colored resin composition of the present invention contains (C-9) a resin: a resin having a weight average molecular weight Mw of more than 12,000 to 40000 and a double bond equivalent of less than 1000 as (C) a binder resin. It is characterized by doing. By containing the (C-9) resin, the retardation of the color filter pixel formed using the composition can be effectively increased. In addition, in the dispersion | distribution process process mentioned later, the effect increases further by using (C-9) resin as a dispersion resin.

  Without being bound by any theory, and the details are unclear, the reason why an increase in retardation is achieved by using a resin having a weight average molecular weight and a double bond equivalent in the above specific ranges is as follows. Estimated as follows. That is, the retardation of the color filter layer is relatively small as an absolute value, but the cause of this expression is presumed as follows. Depending on the production method of the pigment, there are some crystallinity and anisotropy of the particle shape. In pigment dispersions and color filters, in order to adsorb to the pigment, the dispersing agent and binder resin surrounding it are also functional groups that adsorb to the pigment and other functional groups that do not adsorb but exist in the molecule. It is conceivable that the functional group is similarly somewhat oriented and anisotropic.

  When the weight average molecular weight is large, it is speculated that the binder resin relatively strengthens the positional relationship with the pigment (that is, the conformation is relatively difficult to change and the orientation during dispersion is easy to maintain). It is speculated that the larger the number of unsaturated groups, the greater the π-π affinity with the pigment and the steric hindrance, so that it will be strengthened in the same way, and this will increase the anisotropy of the functional group. The

  The weight average molecular weight of (C-9) resin is usually 12000 or more and 40000 or less, preferably 12000 or more and 35000 or less, more preferably 13000 or more and 30000 or less. If the weight average molecular weight is too large, the viscosity of the resin becomes very high and synthesis may be difficult, or the viscosity of the dispersion may be too high. Conversely, if it is too small, the retardation cannot be increased sufficiently.

The (C-9) resin preferably has a smaller double bond equivalent, usually 1000 or less, more preferably 800 or less. When the double bond equivalent is too large, the retardation cannot be increased.
In addition, the content of the (C-9) resin in the colored resin composition of the present invention is preferably 10 to 50% by weight, more preferably 25 based on the total amount of the (A) pigment contained in the composition. -35% by weight. (C-9) If the amount of the resin is too small, there is a possibility that the retardation cannot be increased sufficiently. Conversely, if the amount is too large, other properties such as developability, coloring power, and curability may be deteriorated. There is.

  In addition, as the (C) binder resin in the colored resin composition of the present invention, only the above-mentioned (C-9) resin may be used. However, from the viewpoint of improving the solubility in a developer, (C-9) It is preferable to use a resin other than a resin, that is, a resin having a weight average molecular weight smaller than that of the (C-9) resin, a double bond equivalent of 1000 or more, or a resin having both.

When the (C) binder resin also contains a resin other than the (C-9) resin, when the content is added to the content of the (C-9) resin, the (C) binder in the colored resin composition What is necessary is just to adjust so that content (after-mentioned) of resin may be satisfy | filled.
(C-9) The type of resin is not particularly limited, but the modification of the resin structure is relatively easy, the electrical characteristics of the obtained color filter are good, and the transmittance decrease due to yellowing after heat curing is small. As a raw material, a resin containing methacrylic acid and a methacrylic acid ester is preferable, and among them, the methacrylic acid ester is preferably benzyl methacrylate or cyclohexyl methacrylate because of high dispersibility and affinity of the pigment.

In addition, since the retardation increasing effect of the obtained pixel is large, it will be described later (C-4).
As the resin, those prepared so that the weight average molecular weight and the double bond equivalent satisfy the above-mentioned ranges are particularly preferable as the (C-9) resin.
On the other hand, the above-mentioned “resin other than (C-9) resin contained in (C) binder resin” is not particularly limited, but has excellent color characteristics, development residue, electrical characteristics, and the like. The (C-1) resin described later is preferable.
<(C) Binder resin other than (C-9) resin>
As described above, the (C-9) resin can be used without particular limitation as long as it is a kind of resin that can be used for a color filter. The (C) binder resin may also contain a resin other than the (C-9) resin (that is, a resin whose weight average molecular weight and double bond equivalent are not controlled within the above-mentioned ranges).

Below, the kind of resin which can be used as (C) binder resin in this invention is demonstrated. In addition, as (C-9) resin, the preferable thing is as above-mentioned, However, It can select arbitrarily from the resin described below fundamentally.
As the type of (C) binder resin in the present invention, for example, a thermosetting resin composition used in a so-called lift-off type color filter manufacturing process described in JP-A-60-184202, JP-A-2004-220036, and the like. Examples thereof include a thermosetting resin composition used in an ink jet type color filter manufacturing process described in Japanese Patent Publication No. Gazette and the like, and a photopolymerizable resin composition described later. A suitable type of resin composition may be selected depending on the means by which the colored resin composition is cured to produce a color filter. When the colored resin composition is a photopolymerizable composition, it preferably contains a photopolymerization initiation system described later.

As described later, the colored resin composition of the present invention is preferably used for the production of a color filter by a photolithography method or an inkjet method, and is photopolymerizable (in the case of a photolithography method or an inkjet method) or thermosetting. It is preferable that it is a property (inkjet system).
Hereinafter, although the case where the colored resin composition of the present invention is a photopolymerizable resin composition and the case of being a thermosetting resin composition will be described in detail, the present invention is not limited thereto. .

When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of (C) binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, and JP-A-11. It is possible to use known polymer compounds described in various publications such as JP-A No. 140144, JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and JP-A No. 2007-270147. But preferably,
(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. An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction or the hydroxyl group produced by the addition reaction;
(C-2): a linear alkali-soluble resin containing a carboxyl group in the main chain,
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the carboxyl group-containing resin,
(C-4): (meth) acrylic resin,
(C-5): An epoxy (meth) acrylate resin having a carboxyl group and the like can be mentioned.

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

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

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

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

In the above general formula, R ^{81 to} R ⁸⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, but R ⁸⁷ and R ⁸⁸ may be linked to each other to form a ring. .
In general formula (1), the ring formed by connecting R ⁸⁷ and R ⁸⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and has 5 to 6 carbon atoms. Is preferred.
Especially, as a structure represented by General formula (1), the structure represented by following formula (1a), (1b), or (1c) is preferable.

(C) By introducing these structures into the binder resin, when the colored resin composition of the present invention is used for a color filter or a liquid crystal display element, the heat resistance of the colored resin composition is improved, or the coloring resin composition is colored. It is possible to increase the strength of the pixel formed using the resin composition.
In addition, the mono (meth) acrylate which has a structure represented by General formula (1) may be used individually by 1 type, and may use 2 or more types together.

  As the mono (meth) acrylate having the structure represented by the general formula (1), various known ones can be used as long as it has the structure, and those represented by the following general formula (2) are particularly preferable. .

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

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

  Among these “other radically polymerizable monomers”, at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is used to impart excellent heat resistance and strength to the colored resin composition. It is effective to use In particular, in the repeating unit derived from “another radical polymerizable monomer”, the content of the repeating unit derived from at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 70 mol. %, 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. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; Propylene glycol monoalkyl ether acetates; Acetic esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, and butyl carbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl Ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane Petroleum petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more.

The amount of these solvents used is usually 30 to 1000 parts by weight, preferably 50 to 800 parts by weight, with respect to 100 parts by weight of the resulting copolymer. When the amount of the solvent used is outside this range, it becomes difficult to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can do. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

  Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy-2-ethyl. Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxide Oxydicarbonate, diisopropyl -Oxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1- Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like can be mentioned.

Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide.
Among these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 weight part with respect to a total of 100 weight part of the monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.

  The copolymerization reaction may be performed by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or by adding the monomer to which the radical polymerization initiator is added. Alternatively, the reaction may be performed dropwise in a solvent that has been heated and stirred. Alternatively, the monomer may be added dropwise while the radical polymerization initiator is added to the solvent and the temperature is raised. The reaction conditions can be freely changed according to the target molecular weight.

  (C-1) In the resin, as the 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 a repeating unit derived from another radical polymerizable monomer is preferably 10 to 95 mol%, more preferably the former 20 to 80 mol% and the latter 80 to 20 mol%. The former 30 to 70 mol% and the latter 70 to 30 mol% are particularly preferable.

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

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

By adding such a component, it is possible to impart polymerizability to the (C-1) resin.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of unsaturated monobasic acid is too small, there is a concern about the adverse effect of the remaining epoxy group on the temporal stability of the colored resin composition. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

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

By adding such a component, alkali solubility can be imparted to the (C-1) resin. In addition, when manufacturing an ink-jet color filter, the wettability of the composition (in the pixel formation area surrounded by the black matrix in the pixel bank) (hereinafter simply referred to as “wet spreadability of the composition”). There is an improvement.
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%. Adjustment of the addition ratio within this range is considered to be effective for controlling the wettability of the composition. If the addition ratio is too large, the remaining film ratio at the time of development may decrease, and if it is too small, the solubility may be insufficient. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

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

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

The resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.
When using (C-1) resin mentioned above as (C) binder resin other than (C-9) resin in the colored resin composition of this invention, the weight average molecular weight (Mw) of polystyrene conversion measured by the GPC Is preferably from 3,000 to 100,000, particularly preferably from 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.

  (C-1) The acid value of the resin is usually 10 to 200 mgKOH / g, preferably 15 to 150 mgKOH / g, and more preferably 25 to 100 mgKOH / g. By controlling the acid value within these ranges, it is possible to prevent the solubility in the developer from decreasing or the film from being roughened.

<(C-2) Linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as (C-2) resin >>
(C-2) The linear alkali-soluble resin containing a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group, and usually obtained by polymerizing a polymerizable monomer containing a carboxyl group. It is done.

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

Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
Moreover, (C-2) resin may copolymerize the other polymerizable monomer which does not have a carboxyl group with said carboxyl group-containing polymerizable monomer.
Other polymerizable monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (
(Meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylates, glycerol mono (meth) acrylates, tetrahydrofurfuryl (meth) acrylates, tricyclodecanyl (meth) acrylates, isobornyl (meth) acrylates, adamantyl (meth) acrylates, etc .; styrene and Vinyl aromatics such as derivatives thereof; Vinyl compounds such as N-vinylpyrrolidone; N-positions such as N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide Maleimides; macromonomers such as polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer, etc. . These may be used in combination.

  Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, They are butyl (meth) acrylate, isobutyl (meth) acrylate, tricyclodecanyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide.

  (C-2) The resin may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like. It is done. By copolymerizing these with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.

  (C-2) Specifically, for example, (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate A copolymer of a polymerizable monomer containing no hydroxyl group such as cyclohexylmaleimide and a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; Copolymer of (meth) acrylic acid and (meth) acrylic acid ester such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate; Meta) Acu Copolymers of Le anhydride and styrene; a copolymer of (meth) acrylic acid and styrene and α- methylstyrene; a copolymer of (meth) acrylic acid and cyclohexyl maleimide. From the viewpoint of excellent pigment dispersibility, a copolymer resin containing benzyl (meth) acrylate is particularly preferable.

(C-2) The acid value of the resin is usually 30 to 500 mgKOH / g, preferably 40 to 350 mgKOH / g, more preferably 50 to 300 mgKOH / g. By controlling the acid value within these ranges, it is possible to prevent the solubility in the developer from decreasing or the film from becoming rough.
In addition, when using (C-2) resin mentioned above as (C) binder resin other than (C-9) resin in the colored resin composition of this invention, the weight average molecular weight of polystyrene conversion measured by the GPC is as follows. Usually, it is 2000-80000, Preferably it is 3000-50000, More preferably, it is 4000-30000. If the weight average molecular weight is too small, the stability of the colored resin composition tends to be inferior. If it is too large, the solubility in the developer tends to deteriorate.

<Resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-3) (C-2) (hereinafter sometimes referred to as (C-3) resin)>
A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the (C-2) linear alkali-soluble resin containing a carboxyl group in the main chain is also particularly preferable.
The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.
For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- An acyclic epoxy group-containing unsaturated compound such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but from the viewpoint of heat resistance and the dispersibility of the pigment (A) described later, an alicyclic epoxy group-containing unsaturated compound. Saturated compounds are preferred.

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

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

These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Among these, a compound represented by the general formula (3c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
In order to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the (C-2) resin, a known method can be used. For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride. A quaternary ammonium salt such as pyridine, triphenylphosphine, etc., in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours to react with the carboxyl group of the resin. Saturated compounds can be introduced.

The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 mgKOH / g, preferably 20 to 150 mgKOH / g, more preferably 30 to 150 mgKOH / g. By controlling the acid value within these ranges, it is possible to prevent the solubility in the developer from decreasing or the film from becoming rough.
When the above-mentioned (C-3) resin is used as a (C) binder resin other than the (C-9) resin in the colored resin composition of the present invention, the polystyrene-equivalent weight average molecular weight measured by GPC is usually It is 2000-100000, Preferably it is 4000-50000, More preferably, it is 5000-30000. If the weight average molecular weight is too small, the stability of the colored resin composition tends to be inferior. If it is too large, the solubility in the developer tends to deteriorate.

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

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

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

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

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

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

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

  Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Monomers having a carboxylic acid anhydride group may be mentioned, but among these, (meth) acrylic acid is particularly preferable, and in terms of relatively low decrease in transmittance due to yellowing of pixels during heat curing, etc. Most preferred is methacrylic acid.

Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.
Only one type of monomer for introducing these acid groups may be used, or two or more types may be used.

(C-4) When the monomer component for obtaining the resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited, but is usually 5 to 70% by weight in the total monomer component, preferably Is from 10 to 60% by weight. By adjusting the amount of the monomer for introducing the acid group within this range, good electrical characteristics and developability can be obtained.
Moreover, (C-4) resin may have a radically polymerizable double bond.

(C-4) In order to introduce a radical polymerizable double bond into a resin, for example, “monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter “monomer for introducing a radical polymerizable double bond”) )) As a monomer component, and then a treatment for imparting a radical polymerizable double bond as described later may be performed.
Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomers: Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

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

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

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

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

  Of these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. Most preferred are cyclohexyl (meth) acrylate and benzyl (meth) acrylate. These other copolymerizable monomers may be used alone or in combination of two or more.

(C-4) When the monomer component for obtaining the resin also includes the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by weight or less, more preferably 85% by weight or less. . When there is too much a content rate, developability may deteriorate.
Next, (C-4) resin production method (polymerization method) will be described.
There is no particular limitation on the method for polymerizing the monomer component, and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. , Depending on the molecular weight of the target polymer. The polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C. Regarding the polymerization concentration, the polymerization concentration is preferably 5 to 50%, more preferably 10 to 40%.

  Moreover, when using a solvent at the time of superposition | polymerization, what is necessary is just to use the solvent used by normal radical polymerization reaction. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform; Dimethyl sulfoxide and the like Is mentioned. These solvents may be used alone or in combination of two or more.

  When the monomer component is polymerized, a polymerization initiator may be used as necessary. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amyl. Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) and the like. These polymerization initiators may be used alone or in combination of two or more.

The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight without gelation. The amount is usually from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight, based on the total monomer components, in that thousands to tens of thousands of polymers can be obtained.
Further, a chain transfer agent may be added for adjusting the molecular weight. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and α-methylstyrene dimer. Preferred are n-dodecyl mercaptan and mercaptoacetic acid, which can be reduced and easily obtained. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but without gelation It is usually 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer components, in that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained.

In addition, when the compound of the general formula (4) is used as an essential monomer component, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously in the polymerization reaction. The conversion rate is not necessarily 100 mol%.
(C-4) When obtaining a resin, when an acid group is introduced by using the above-mentioned monomer capable of imparting an acid group as a monomer component, it is necessary to perform a treatment for imparting an acid group after polymerization There is. The treatment varies depending on the type of monomer used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride An acid anhydride such as a product may be added. When a monomer having an epoxy group such as glycidyl (meth) acrylate is used, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or first ( An acid such as meth) acrylic acid may be added, and an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like may be added to the resulting hydroxyl group. When a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

(C-4) When the resin is obtained, the radical polymerizable double bond is introduced by using the monomer capable of imparting the radical polymerizable double bond described above as the monomer component. It is necessary to perform a process for imparting a double bond.
The treatment varies depending on the type of monomer used. For example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( A compound having an epoxy group and a radically polymerizable double bond such as (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate is added. Just do it. When a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether is used, ) A compound having an acid group such as acrylic acid and a radical polymerizable double bond may be added.

  When (C-4) resin is used as (C) binder resin other than (C-9) resin in the colored resin composition of the present invention, its weight average molecular weight is not particularly limited, but preferably by GPC The measured polystyrene equivalent weight average molecular weight is 2000 to 200000, more preferably 4000 to 100,000. When the weight average molecular weight exceeds 200,000, the viscosity may become too high to form a coating film, and when it is less than 2,000, sufficient heat resistance tends to be hardly exhibited.

(C-4) When resin has an acid group, a preferable acid value is 5-500 mgKOH / g, More preferably, it is 10-400 mgKOH / g. When the acid value is less than 5 mgKOH / g, it may be difficult to apply to alkali development. Moreover, when it exceeds 500 mgKOH / g, there exists a tendency for it to become high viscosity and to form a coating film difficult.
In addition, when an acid value is comparatively high, since it becomes difficult to produce the time-dependent change (thickening) of a viscosity of the colored resin composition containing this, when an acid value is comparatively low, the colored resin composition containing this is preferable. This is preferable because a change (decrease) in contrast with time is less likely to occur.

  Examples of the copolymer having the (C-4) resin, that is, the compound represented by the general formula (4) as an essential monomer component include, for example, JP-A-2004-300203 and JP-A-2004-300204. The compounds described in the publication can be mentioned.

<(C-5) Epoxy Acrylate Resin Having Carboxyl Group (hereinafter, may be referred to as (C-5) resin>)
(C-5) The epoxy acrylate resin is obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to the epoxy resin, and further adding a polybasic acid anhydride. It is synthesized by reacting the product. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc., manufactured by Japan Epoxy Resin Co., Ltd.), Epoxy resin obtained by reaction of alcoholic hydroxyl group and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, manufactured by Japan Epoxy Resin Co., Ltd.) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc."), epoxy resins obtained by reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (for example, Nippon Kayaku) “NE” -7406 "(epoxy equivalent 350, softening point 66 ° C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example," YX-4000 "manufactured by Japan Epoxy Resin), phenol novolac type epoxy resin (for example, Nippon Kayaku) “EPPN-201” manufactured by Yakuhin, “EP-152”, “EP-154” manufactured by Japan Epoxy Resin, “DEN-438” manufactured by Dow Chemical Co., Ltd.), (o, m, p-) cresol novolak Type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), trisphenol Methane type epoxy resin (for example, “EPPN-501”, “EP” manufactured by Nippon Kayaku Co., Ltd.) -502 "," EPPN-503 "), fluorene epoxy resin (for example, cardo epoxy resin" ESF-300 "manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (" Celoxide 2021P "manufactured by Daicel Chemical Industries, Ltd.) , “Celoxide EHPE”), dicyclopentadiene type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example, “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “EXA” manufactured by Dainippon Ink & Chemicals, Inc. -7200 "," NC-3000 "," NC-7300 "manufactured by Nippon Kayaku Co., Ltd.), and an epoxy resin represented by the following structural formula (see JP-A-4-355450), etc. are preferably used. it can.

These may be used alone or in combination of two or more.
Another example of the epoxy resin is a copolymer type epoxy resin. Examples of the copolymerization type epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “first component of copolymerization type epoxy resin”) and one other than these. Functional ethylenically unsaturated group-containing compound (hereinafter referred to as “second component of copolymerization type epoxy resin”), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Ethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono (meth) acrylate, the following general formula (8 From the compound represented by One or more barrels are reacted city include a copolymer obtained by.

In the general formula ^{(8), R 61} is hydrogen or ethyl ^{group, R 62} represents an alkyl group having 1 to 6 carbon hydrogen or carbon, r is an integer of 2 to 10.
Examples of the compound represented by the general formula (8) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate and tetraethylene glycol mono (meth) acrylate; methoxy Examples include alkoxy polyethylene glycol (meth) acrylates such as diethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

As for the molecular weight of the said copolymerization type epoxy resin, about 1000-200000 is preferable. The amount of the first component of the copolymerization type epoxy resin used is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably 70% by weight based on the second component of the copolymerization type epoxy resin. % By weight or less, particularly preferably 50% by weight or less.
As such a copolymerization type epoxy resin, specifically, “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, “CP-50S”, “CP-50M”, “CP-20MA” and the like are exemplified.

Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is highly reactive. Therefore, it is preferable.
The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred. These may be used alone or in combination of two or more.

  The addition reaction of an α, β-unsaturated monocarboxylic acid or ester thereof with an epoxy resin can be carried out by using a known method, for example, by reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. can do. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

  The amount of α, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. Equivalent range. If the amount of α, β-unsaturated monocarboxylic acid or ester thereof used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with the polybasic acid anhydride becomes insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β-unsaturated monocarboxylic acid or ester thereof remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  The polybasic acid anhydride to be further added to the epoxy resin to which the α, β-unsaturated carboxylic acid or ester thereof is added includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetra Carboxylic acid dianhydride and the like, preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Biphenyltetracarboxylic dianhydride Particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be carried out by continuing the reaction under the same conditions as the addition reaction of α, β-unsaturated carboxylic acid or ester thereof.
The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mgKOH / g, more preferably in the range of 20 to 140 mgKOH / g. If the acid value of the resin is too small, the alkali developability is poor, and if the acid value of the resin is too large, the curing performance tends to be inferior.

  In addition, as the (C-5) epoxy acrylate resin having a carboxyl group, for example, a naphthalene-containing resin described in JP-A-6-49174; JP-A 2003-89716, JP-A 2003-165830, JP-A 2005-325331, Examples include fluorene-containing resins described in JP-A-2001-354735; resins described in JP-A-2005-126684, JP-A-2005-55814, JP-A-2004-295084, and the like.

In addition, a commercially available (C-5) epoxy acrylate resin having a carboxyl group can also be used, and examples of commercially available products include “ACA-200M” manufactured by Daicel Corporation.
Moreover, as (C-5) resin, the acrylic resin as described in Unexamined-Japanese-Patent No. 2005-154708 etc. can also be used, for example.

<(C) Binder resin content, etc.>
The colored resin composition of the present invention may contain a binder resin other than the (C) binder resin as long as the effects of the present invention are not impaired.
Moreover, as (C) binder resin used for the colored resin composition of this invention, 1 type may be used independently among (C-1) resin-(C-5) resin, and 2 or more types are used together. May be.
Further, the content ratio of (C) binder resin is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, preferably 60% by weight or less in the total solid content. . (C) When there is too little content of binder resin, a film | membrane will become weak and the adhesiveness to a board | substrate may fall. On the other hand, when the amount is too large, the permeability of the developing solution to the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.

<(D) Solvent>
In the colored resin composition of the present invention, (D) the solvent dissolves or disperses the components other than those mentioned above in addition to (A) pigment, (B) dispersant, (C) binder resin, and viscosity. It has a function to adjust.

Any solvent can be used as long as it can dissolve or disperse each component.
Such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol. -T-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3 -Methoxybutanol, trie Glycol monomethyl ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl 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, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like 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, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
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;
Examples thereof include 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.

<When forming color filter pixels by photolithography>
When forming pixels of a color filter by photolithography, a solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa], hereinafter the same applies to the boiling point) is selected. Is preferred. More preferably, it has a boiling point of 120-170 ° C. If the boiling point is too low, air bubbles may remain on the surface of the coating film due to bumping, resulting in defects. On the other hand, if the boiling point is too high, drying of the coating film may not be completed within a predetermined time, and problems such as color unevenness may occur in the pixels.

Glycol alkyl ether acetates are preferred from the viewpoints of good balance between the coating properties and surface tension in the solvent, and relatively high solubility of the constituent components in the composition.
The glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferable. Among these, propylene glycol monomethyl ether is particularly preferable because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by weight to 30% by weight and more preferably 5% by weight to 20% by weight in the whole solvent.

  It is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but it has the effect of making it difficult for the pigment dispersion liquid to break down due to rapid drying. The content of the high boiling point solvent is preferably 3% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 5% by weight to 30% by weight with respect to the whole solvent. If the amount of the high boiling point solvent is too small, for example, coloring material components may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too much, the drying speed of the composition will be slow, which will be described later. There is a concern that it may cause problems such as tact defects in the vacuum drying process and pre-baked pin marks in the color filter manufacturing process.

  The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .

<When forming color filter pixels by inkjet method>
When forming a pixel of a color filter by the ink jet method, a solvent having a boiling point of usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower is appropriate. When the boiling point is too low, the uniformity of the resulting coating film tends to be poor. Conversely, if the boiling point is too high, as described later, the effect of inhibiting the drying of the colored resin composition is high, but there are many residual solvents in the coating film even after thermal firing, causing problems in quality, In some cases, the drying time in vacuum drying or the like becomes long, resulting in problems such as an increase in tact time.

The solvent vapor pressure is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.
In addition, in the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable to include a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. Further, the high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by weight or more, more preferably 70% by weight or more, in the whole solvent contained in the colored resin composition for a color filter of the present invention. 90% by weight or more is most preferable. When the high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the droplets may not be sufficiently exhibited.

  Preferred high boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

  Furthermore, it is also effective to partially contain a solvent having a boiling point lower than 180 ° C. in order to adjust the viscosity of the pigment dispersion or the colored resin composition and the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferable.

On the other hand, when the solvent contains alcohols, the ejection stability in the ink jet method may deteriorate. Therefore, the alcohol is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less in the entire solvent.
The content of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by weight or less. When the solvent exceeds 99% by weight, the amount of (A) pigment, (B) dispersant, etc. is too small to form a coating film. On the other hand, the lower limit of the solvent content is usually 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more in consideration of viscosity suitable for coating.

<(E) Polymerizable monomer>
The colored resin composition of the present invention preferably further contains (E) a polymerizable monomer as required. (E) The polymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but it is an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred). The ethylenic compound means that when the colored resin composition of the present invention is irradiated with actinic rays, it is cured by addition polymerization by the action of the above-mentioned photopolymerization initiator system, or when heated. It is a compound having an ethylenic double bond that is cured by addition polymerization by the action of the thermal polymerization initiator. In addition, the (E) polymerizable monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept also containing a dimer, a trimer, and an oligomer other than the monomer of a narrow sense.

  Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester thereof with a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, An ester, a polyisocyanate compound and a (meth) acryloyl-containing hydroxy compound obtained by an esterification reaction with a saturated carboxylic acid and a polyvalent carboxylic acid and the polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound; And an ethylenic compound having a urethane skeleton obtained by reacting.

  Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate. And acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, 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. Typical examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol. And condensates of glycerin and the like.

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; cyclohexane diisocyanate and isophorone diisocyanate. Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- (Meth) acryloyl group-containing hydroxy compounds such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane Reaction products thereof.

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are also useful.
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These ethylenic compound monomers may be used singly, but since it is difficult to use a single compound for production, two or more of them may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be inferior. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  In the colored resin composition of the present invention, more preferred polyfunctional monomers having an acid group are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture mainly composed of succinic acid ester. Other polyfunctional monomers can be used in combination with this polyfunctional monomer.

  The content of these (E) polymerizable monomers is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, based on the total solid content of the colored resin composition of the present invention. It is 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The ratio to (A) pigment is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably 100%. % By weight or less, more preferably 80% by weight or less. (E) When there are too many polymerizable monomers, when it is set as a composition, it is possible that the solubility with respect to an alkali developing solution falls remarkably. On the other hand, if the amount is too small, the crosslink density may decrease and the curability may decrease.

<(F) Photopolymerization initiator system and / or thermal polymerization initiator>
The colored resin composition of the present invention preferably further comprises (F) a photopolymerization initiator system and / or a thermal polymerization initiator for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.

In particular, when the colored resin composition of the present invention includes (C) a resin having an ethylenic double bond as a binder resin component, or (E) includes an ethylenic compound as a polymerizable monomer component, light is emitted. A photopolymerization initiator system that has a function of generating a polymerization active radical by directly absorbing or photosensitizing to cause a decomposition reaction or a hydrogen abstraction reaction, and / or a thermal polymerization initiator that generates a polymerization active radical by heat. It is preferable to contain. In the present invention, the component (F) as the photopolymerization initiator system is a photopolymerization initiator (hereinafter sometimes referred to as (F-1) component) and a polymerization accelerator (hereinafter referred to as (F-2). ), A sensitizing dye (hereinafter, sometimes referred to as (F-3) component), and the like.

<Photopolymerization initiator system>
The (F) photopolymerization initiator system which may be contained in the colored resin composition of the present invention is usually (F-1) a photopolymerization initiator and (F-3) added as necessary. A function that is used as a mixture with an additive such as a dye-sensitizing agent and (F-2) a polymerization accelerator and directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical It is a component having

  (F) The photopolymerization initiator constituting the photopolymerization initiator system (F-1) includes, for example, titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; Hexaarylbiimidazole derivatives described in JP-A-10-300922, JP-A-11-174224, JP-A-2000-56118, etc .; Halomethylated oxadiazoles described in JP-A-10-39503 Derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A and the like .

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

  As biimidazole derivatives, 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole 2 amount 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl)- 4,5-diphenylimidazole dimer etc. are mentioned.

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

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

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

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime) and the like.
In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- ( acetophenone derivatives such as p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone are also included.

Among these (E-1) photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, and thioxanthone derivatives are more preferable.
In addition, the colored resin composition of the present invention may further contain (F-2) a polymerization accelerator, if necessary, particularly when it contains (F) a photopolymerization initiator system. (F-2) Examples of the polymerization accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

One of these (F-1) photopolymerization initiator and (F-2) polymerization accelerator may be used alone, or two or more thereof may be used in combination.
In the colored resin composition of the present invention, (F-3) sensitizing dye may be used in the photopolymerization initiator system for the purpose of increasing the sensitivity. (F-3) As the sensitizing dye, an appropriate dye is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc. A coumarin dye having a heterocyclic ring described in JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin described in JP-A-3-239703, JP-A-5-289335, etc. Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP No. 5-107761, JP-A-5-210240, it may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

  Among these (F-3) sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. (F-3) Particularly preferred as the sensitizing dye is, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone. Benzophenone compounds such as 3,3′-diaminobenzophenone and 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethyl) Aminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzo Azole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1, 3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, p-dialkylaminophenyl group-containing compounds such as p-diethylaminophenyl) pyrimidine. Of these, 4,4'-dialkylaminobenzophenone such as 4,4'-dimethylaminobenzophenone and 4,4'-diethylaminobenzophenone is most preferred.

(F-3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, these (F) photopolymerization initiator systems ((F-1) photopolymerization initiator, (F-2) polymerization accelerator, and (F-3) sensitizing dye) are contained. The ratio is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight or less, preferably 30% by weight or less in the total solid content. If the content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if the content is extremely high, the solubility of the unexposed part in the developer is reduced, leading to poor development or an initiator. Due to the influence of the light itself, that is, due to the light absorption characteristics of the initiator itself, the luminance may decrease when the transmittance of the pixel decreases.

<Thermal polymerization initiator>
Specific examples of the 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.

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

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

In addition, some of the above-described (F-1) photopolymerization initiators also function as thermal polymerization initiators such as α-aminoalkylphenone derivatives. Therefore, you may use the compound selected from the examples given as an example of (F-1) photoinitiator as a thermal-polymerization initiator.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
If the proportion of the thermal polymerization initiator in the colored resin composition is too small, the film is not sufficiently cured, and the durability as a color filter may be insufficient. If the amount is too large, the degree of thermal shrinkage increases, and cracking and cracking may occur after thermosetting. Moreover, the tendency for storage stability to fall is seen. Accordingly, the content of the thermal polymerization initiator is preferably in the range of 0 to 30% by weight, particularly 0 to 20% by weight, based on the total solid content of the colored resin composition of the present invention.

<Dispersing aid>
The colored resin composition of the present invention may contain a pigment derivative or the like as a dispersion aid for improving the dispersibility of the pigment and improving the dispersion stability. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Derivatives such as pyrrole and dioxazine pigments may be mentioned. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, isoindoline pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, Examples thereof include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.

  The addition amount of the pigment derivative is usually 0.1% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight based on the pigment (A). % Or less. If the addition amount is small, the effect tends to be difficult to be exerted. Conversely, if the addition amount is too large, the dispersibility and dispersion stability may be deteriorated. It may cause a decrease).

<Dispersed resin>
The colored resin composition according to the present invention can be prepared by preparing a pigment dispersion in advance and adding other components to the pigment dispersion as described later. The pigment dispersion is prepared by dispersing these at least using (A) a pigment, (B) a dispersant, and (C) a solvent. In this dispersion treatment step, a part or all of the resin selected from the aforementioned (C) binder resin may be contained in the pigment dispersion. As described above, the (C) binder resin used in the dispersion treatment step may be particularly referred to as a dispersion resin.

  More specifically, in the dispersion treatment step in the preparation of the pigment dispersion described later, the binder resin (C) is contained together with the dispersant (B) described above, whereby the binder resin (C) becomes (B) It contributes to the dispersion stability of the pigment (A) by a synergistic effect with the dispersant. As a result, the amount of (B) dispersant added may 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.

Among the binder resins (C) in the present invention, the essential component (C-9) resin is preferable because it increases the retardation increase effect by adding it during dispersion of the pigment.
The dispersion resin is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of pigment in the pigment dispersion.

  The acid value of the dispersion resin is preferably 0 mgKOH / g or more, more preferably 1 mgKOH / g or more, most preferably 5 mgKOH / g or more, more preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less. Most preferred. If the acid value is too high, the viscosity tends to be high and synthesis and handling tend to be difficult, and if it is too low, it may be difficult to apply to alkali development.

  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. If the molecular weight is too large, it tends to be difficult to apply to alkali development, and if the molecular weight is too small, the dispersion stability may be lowered.

<Other ingredients>
The colored resin composition of the present invention may contain components other than those described above as necessary. Examples of such components include surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion improvers, development improvers, and dyes.

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

  Examples of anionic surfactants include alkyl sulfate ester surfactants such as “Emar 10” manufactured by Kao Corporation, and alkylnaphthalene sulfonate surfactants such as “Perex NB-L” manufactured by Kao Corporation. And special polymer surfactants such as “Homogenol L-18” and “Homogenol L-100” manufactured by Kao Corporation. Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

  Examples of the cationic surfactant include alkylamine salt surfactants such as “Acetamine 24” manufactured by Kao Corporation, and quaternary ammonium salt interfaces such as “Cotamine 24P” and “Coatamine 86W” manufactured by Kao Corporation. Examples include activators. Of these, quaternary ammonium salt surfactants are preferred, and stearyltrimethylammonium salt surfactants are more preferred.

  Nonionic surfactants include, for example, “SH8400” manufactured by Tore Silicone; silicone surfactants such as “KP341” manufactured by Silicone; “FC430” manufactured by Sumitomo 3M; Dainippon Ink and Chemicals, Inc. "F470" manufactured by KK; fluorine-based surfactants such as "DFX-18" manufactured by Neos; polyoxyethylene-based surfactants such as "Emulgen 104P" and "Emulgen A60" manufactured by Kao Corporation, etc. . Of these, silicone surfactants are preferable, and so-called polyether-modified or aralkyl-modified silicone surfactants having a structure in which a side chain of a polyether group or an aralkyl group is added to polydimethylsiloxane are more preferable.

Two or more kinds of surfactants may be used in combination, for example, silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer. And combinations of surfactants. Among these, a combination of silicone surfactant / fluorine surfactant is preferable.
Examples of the combination of the silicone surfactant / fluorine surfactant include a combination of a polyether-modified silicone surfactant / oligomer type fluorine surfactant. Specifically, for example, “TSF4460” manufactured by GE Toshiba Silicone / “DFX-18” manufactured by Neos, “BYK-300” manufactured by BYK Chemie / “S-393” manufactured by Seimi Chemical Co., “KP340 manufactured by Shin-Etsu Silicone Co., Ltd.” "F-478" manufactured by Dainippon Ink & Chemicals, "SH7PA" manufactured by Tore Silicone, "DS-401" manufactured by Daikin, "L-77" manufactured by Nihon Unicar, and "FC4430" manufactured by Sumitomo 3M The combination of is mentioned.

  The content of these surfactants is usually 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more in the total solid content. Further, it is usually used in the range of 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less. By controlling the surfactant content within this range, there is no possibility that the overcoat will be repelled when the overcoat is applied in the actual line, and the coating film may be cracked after curing. The film is less likely to wrinkle.

<Thermal polymerization inhibitor>
As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0% by weight to 3% by weight with respect to the total solid content of the composition.

<Plasticizer>
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The blending amount of these plasticizers is preferably in the range of usually 10% by weight or less with respect to the total solid content of the composition.

<Preparation method of colored resin composition>
The colored resin composition of the present invention may be prepared by mixing the materials constituting the composition at once or sequentially. However, as described below, a pigment dispersion is prepared in advance, It is preferred to mix the components.
Hereinafter, although an example of the method of preparing the colored resin composition of this invention is demonstrated, there is no restriction | limiting in particular in a preparation method, It is not necessarily limited to the method described below.
As described above, the colored resin composition of the present invention is preferably used as a material for forming a color filter pixel. The colored resin composition for a color filter of the present invention may be photocurable (photopolymerizable) or thermopolymerizable depending on the production process of the color filter to be applied.

  The colored resin composition of the present invention comprises at least (A) a pigment, (B) a dispersant, and optionally a dispersion aid, a dispersion resin (preferably part or all of (C) a binder resin), (D) Prepare a pigment dispersion containing a solvent and the like, (C) binder resin (remainder), and optionally used (E) polymerizable monomer, (F) photopolymerization initiator system and / or thermal polymerization. It is preferable to prepare by mixing other components such as an initiator.

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

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

  (C) Binder resin and (E) polymerizable monomer, (E) photopolymerization initiator, and / or thermal polymerization initiator, surface activity A colored resin composition is obtained by mixing other components such as an agent to obtain a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and a mixing process, since fine refuse may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.

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

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

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

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

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

The black matrix is formed on the transparent substrate using a light shielding metal thin film or a coating liquid for forming a black matrix (which may be the colored resin composition of the present invention). As the light shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate and perchloric acid and / or nitric acid are applied to chromium. Other materials are etched using an etchant appropriate for the material, and finally the positive photoresist is stripped with a special stripper to form a black matrix. can do.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the colored resin composition on the thin film, the coating film is exposed and developed using a photomask having a repeated pattern such as stripes, mosaics, and triangles to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

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

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

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

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

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

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

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

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

<Drying of coating film>
Drying of the coating film formed by applying the colored resin composition to the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried.

  The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

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

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

The light source used for said image exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples thereof include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.
When the color filter of the present invention is produced by a photolithography method, the process proceeds to a development step.

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

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

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

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, 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.

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

In the case of producing a color filter by an ink jet method, if the colored resin composition of the present invention is photopolymerizable, after the exposure step, if it is thermosetting, after the coating step by the ink jet method, thermosetting Process. Preferred conditions for the thermosetting treatment are the same as described above.
In addition to the manufacturing method described above, the color filter of the present invention can also be produced by a method of forming a pixel image with an ink jet printer using the colored resin composition of the present invention as a colored ink.
As a method for producing the color filter, a method suitable for this is employed according to the composition of the colored resin composition of the present invention.

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

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

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

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

The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.
There are no particular restrictions on the type of liquid crystal, and it is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

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

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, published on August 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 thus manufactured, etc. Thus, an organic EL display can be produced. The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to description of a following example, unless the summary is exceeded.
[1] (C) Synthesis of Binder Resins A to H [Synthesis Example 1: (Synthesis of Binder 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, 20 parts by weight of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 32 parts by weight of methacrylic acid, 40 parts by weight of methyl methacrylate, 108 parts by weight of benzyl methacrylate, t- Charge 5.2 parts by weight of butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate, and add 4 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate to the chain transfer agent tank. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer vessel and the chain transfer agent vessel, and polymerization was started. While maintaining the temperature at 90 ° C., the dropwise addition was carried out over 135 minutes, and after 60 minutes from the completion of the dropwise addition, the temperature was raised and the reaction vessel was set to 1
10 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature and a weight average molecular weight of 96
A 30% by weight binder resin A polymer solution having an acid value of 00 and an acid value of 104 mgKOH / g was obtained.

[Synthesis Example 2: Synthesis of Binder Resin B]
In Synthesis Example 1, the same method except that t-butylperoxy-2-ethylhexanoate was changed to 7.8 parts by weight was carried out in the same manner as described above, but a 30% by weight binder resin B heavy having a weight average molecular weight of 6400 and an acid value of 105 mgKOH / g. A coalesced solution was obtained.

[Synthesis Example 3: Synthesis of Binder Resin C]
In Synthesis Example 1, a 30 wt% binder resin C polymer solution having a weight average molecular weight of 8900 and an acid value of 104 mgKOH / g was obtained by the same method except that 108 parts by weight of benzyl methacrylate was used instead of 108 parts by weight of benzyl methacrylate. It was.

[Synthesis Example 4: Synthesis of Binder Resin D]
30% by weight binder resin D polymer having a weight average molecular weight of 15000 and an acid value of 105 mgKOH / g by the same method except that t-butylperoxy-2-ethylhexanoate was changed to 2.6 parts by weight in Synthesis Example 1. A solution was obtained.

[Synthesis Example 5: Synthesis of Binder Resin E]
A separable flask equipped with a cooling tube as a reaction tank was prepared, while as a monomer dropping tank, 30 parts by weight of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 68 parts by weight of methacrylic acid, A mixture of 102 parts by weight of benzyl methacrylate, 7.8 parts by weight of t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) and 60 parts by weight of propylene glycol monomethyl ether acetate was mixed well. A chain transfer agent dropping tank was prepared, which was prepared by thoroughly stirring and mixing 8 parts by weight of n-dodecanethiol and 32 parts by weight of propylene glycol monomethyl ether.

  The reaction vessel was charged with 375 parts by weight of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed over 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started.

  Next, 64.9 parts 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. Thereafter, propylene glycol monomethyl ether acetate was added and cooled to room temperature to obtain a binder resin E polymer solution having a concentration of 30%. The binder resin E had a weight average molecular weight of 13,100, an acid value of 72 mgKOH / g, and a double bond equivalent of 580.

[Synthesis Example 6: Synthesis of Binder Resin F]
A binder resin F polymer solution was obtained in the same manner except that cyclohexyl methacrylate was used instead of 102 parts by weight of benzyl methacrylate in Synthesis Example 5 and the amount of glycidyl methacrylate used was changed to 49.5 parts by weight. The weight average molecular weight of the binder resin was 8000, the acid value was 99 mgKOH / g, and the double bond equivalent was 715.

[Synthesis Example 7: Synthesis of Binder Resin G]
A separable flask equipped with a cooling tube was prepared as a reaction tank, while as a monomer dropping tank, 5.3 parts by weight of tricyclodecanyl methacrylate, 43 parts by weight of styrene, 31.2 parts by weight of hydroxyethyl methacrylate, 28 of methacrylic acid 4 parts by weight and 9.7 parts by weight of t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) and 60 parts by weight of propylene glycol monomethyl ether acetate Got ready.

  The reaction vessel was charged with 102 parts by weight of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, a gas introduction pipe was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started.

  Next, 21.3 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. Thereafter, propylene glycol monomethyl ether acetate was added and cooled to room temperature to obtain a binder resin G polymer solution having a concentration of 40%. The binder resin G had a weight average molecular weight of 7,200, an acid value of 80 mgKOH / g, and a double bond equivalent of 862.

[Synthesis Example 8: Synthesis of Binder Resin H]
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2,2′-azobis-2-methyl was further added. 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours.

Next, the inside of the reaction vessel was purged with air, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 28.5 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 binder resin H thus obtained has a weight average molecular weight Mw measured by GPC of about 8
The acid value was 400 mg and 33 mgKOH / g.

<Examples 1-3 and Comparative Examples 1-4>
[2] Preparation of colored resin composition (A) As a pigment, C.I. I. 8.24 parts by weight of Pigment Green 58 (manufactured by DIC), 0.92 parts by weight of E4GN-GT manufactured by LANXESS, 60.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and (B) the following dispersant as a dispersant A is 2.47 parts by weight in terms of solid content, and (C) binder resin, 3.38 parts by weight in terms of solid content and 225 parts by weight of zirconia beads having a diameter of 0.5 mm are stainless steel. The container was filled and dispersed in a paint shaker for 6 hours to prepare a green pigment dispersion.
Then, each component was mixed with the said green pigment dispersion liquid, and the colored resin composition was prepared so that it might become a composition described in Table-1.

[Dispersant A: Dispersant “BYK-LPN6919” manufactured by Big Chemie]
It is a methacrylic acid AB block copolymer, the amine value is 121 mgKOH / g, and the acid value is 1 mgKOH / g or less.
Among the repeating units having a nitrogen atom-containing functional group contained in the B block, about 100 mol% is a structure represented by the following formula (i), and the A block of the repeating unit represented by the following formula (ii) The ratio in was 11 mol%.

[3] Production of colored resin film Each of the colored resin compositions obtained in [2] was spin-coated on a transparent glass substrate for color filters (Anahi Glass AN-100) for 3 minutes on a hot plate at 80 ° C. Pre-baking was performed to form a dry coating film. At the time of application, after the following post-baking, the rotation speed was adjusted so that the film thickness was such that the color coordinate y = 0.6.
The resulting dried coating film is exposed at 60 mJ / cm @ 2 through a mask pattern with a high-pressure mercury lamp, and then spray-developed at a pressure of 0.25 MPa using a 0.04 wt% aqueous potassium hydroxide solution (developer temperature 23 DEG C.). Went. It was thoroughly washed with pure water and sufficiently dried with clean air.
Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes to form a colored resin film. The thickness of the colored resin film after drying was about 3.0 μm.

[7] [Measurement of thickness retardation of color filter]
Using RETS-100 manufactured by Otsuka Electronics Co., Ltd., which can measure minute retardation down to 0.1 nm, three-dimensional refractive index measurement is performed by the rotary analyzer method, and the value obtained by a non-contact type film thickness meter is obtained. It used as a film thickness and calculated _| required retardation Rth of the thickness direction (z) in wavelength 550nm. R _th is a value per thickness 3.00. The results are shown in Table-2.

In Table-2 above, the “type” of the dispersion resin means the binder resins A to G obtained in Synthesis Examples 1 to 7. Among the binder resins A to C, among the binder resins (C) in the present invention, “(C-9) resin: weight average molecular weight Mw exceeds 12,000 and is not more than 40000, and / or the double bond equivalent is 1000. Less than.
In Table 2 above, the double bond equivalent “−” means that the double bond equivalent is infinite, that is, a resin having no double bond.
As is clear from Table 2, it can be seen that the retardation of the pixel can be easily increased by forming the color filter pixel using the colored resin composition of the present invention.

  By using the colored resin composition of the present invention, it is possible to effectively increase the retardation of the green pixel without reducing the transmittance of the pixel and while maintaining both the contrast ratio control and the hue control. In addition, by using such a colored resin composition, a color filter with high transmittance, high contrast, and low film thickness can be produced as a result, and there is no coloration even when viewed from an oblique direction. Liquid crystal display device and organic EL display can be provided.

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

Explanation of symbols

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

Claims (8)

A colored resin composition for a color filter containing (A) a pigment, (B) a dispersant, and (C) a binder resin,
(A) The pigment is C.I. I. Pigment Green 58,
(C) Binder resin
(C-9) Resin: a resin having a weight average molecular weight Mw of more than 12000 and 40000 or less, and a double bond equivalent of less than 1000,
A colored resin composition for a color filter, comprising:   (C-9) The colored resin composition for a color filter according to claim 1, wherein the resin contains a repeating unit derived from methacrylic acid and a repeating unit derived from methacrylic acid ester as essential components.   The colored resin composition for a color filter according to claim 2, wherein the methacrylic acid ester comprises benzyl methacrylate or cyclohexyl methacrylate.   The colored resin composition for a color filter according to any one of claims 1 to 3, further comprising (E) a polymerizable monomer.   The colored resin composition for a color filter according to any one of claims 1 to 4, further comprising (F) a photopolymerization initiator system.   The color filter which has a pixel formed using the colored resin composition as described in any one of Claims 1 thru | or 5.   A liquid crystal display device comprising the color filter according to claim 6.   An organic EL display comprising the color filter according to claim 6.

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