JP2010039060A - Colored curable resin composition for color filter by ink-jet method, color filter, liquid crystal display and organic el display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable resin composition satisfying both of wet spreadability of a coloring ink and reduction of film defects in pixels, which are liable to have the relation of trade-off so far in the formation of pixels of a color filter by an ink-jet method. <P>SOLUTION: The colored curable resin composition for a color filter by an ink-jet method comprises at least a pigment, a dispersant, a binder resin and an organic solvent, wherein the dispersant is an A-B block copolymer and/or an A-B-A block copolymer comprising B blocks having an amino group in a side chain and A blocks having no amino group, the copolymer having an amine value of ≥20 mgKOH/g in terms of available solid content, and the binder resin has a weight average molecular weight of 4,000-50,000 in terms of polystyrene as measured by GPC and has an acid value of ≤150 mgKOH/g. Uses of the colored curable resin composition are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored curable resin composition that can be suitably used in the case of forming a pixel portion of a color filter by an inkjet method, and an application thereof.

  In a liquid crystal display device (LCD), a color filter is widely used for color display. For example, in an active matrix type LCD using a thin film transistor (TFT), a film having excellent light-shielding properties called a black matrix (BM) is patterned, and the three primary colors red (R) and green (G) are formed thereon. , With a blue (B) coloring pattern. By turning on or off the electrodes corresponding to the R, G, and B pixels, the liquid crystal operates as a shutter, and light passes through each of the R, G, and B pixels, and color display is performed. An arbitrary color is visually displayed on the retina according to an additive color mixing principle in which liquid crystal shutters corresponding to pixels of two or more colors are opened and mixed. Conventional color filters are manufactured by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. In the case of a TFT-LCD, the pigment dispersion method is the mainstream.

In general, in the pigment dispersion method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and a monochromatic pattern is obtained by patterning the photosensitive resin layer. Further, this process is repeated three times to form R, G, and B color filter layers.
Still other methods include an electrodeposition method, a method in which a pigment is dispersed in a thermosetting resin, R, G, and B are printed three times, and then the resin is thermoset.

However, in any method, it is necessary to repeat the same process three times in order to color the three colors of R, G, and B, and there is a problem that the cost is high, and the yield decreases because the process is repeated There's a problem.
As a color filter manufacturing method that solves these problems, color is a method in which a pixel is formed by driving colored ink into a substantially rectangular recessed area surrounded by a black matrix by an inkjet method in the pixel bank. Filter manufacturing technology has been put into practical use. At this time, the properties required for the ink are two things: good wetting and spreading within the pixel bank, and the absence of coating film defects such as wrinkles and cracks after drying under reduced pressure. Is important.

  However, the mechanism of wetting and drying of the fine droplets landed on the substrate by the inkjet method has not yet been theoretically sufficiently elucidated, and it is excellent in wetting and spreading, and coating film defects are unlikely to occur. It was often a trade-off.

  On the other hand, as a pigment dispersant, an AB block copolymer having an A-block having an amino group in the side chain and a B block not having an amino group in the side chain and having an amine value of a certain level or more and / or The ink containing the ABA block copolymer has high pigment dispersibility. However, depending on the composition of the ink containing the dispersant, wetting and spreading may be insufficient, and film defects such as wrinkles and cracks may occur after drying under reduced pressure. It was difficult to apply to.

As a result of intensive studies to solve the above problems, the present inventors have used a binder that is used in combination when a specific block copolymer having an amine value of a certain level or more is used as a dispersant for a color ink for an inkjet color filter. By controlling the molecular weight and acid value of the resin within a specific range, it has been found that a colored ink having good wetting and spreading within the pixel bank and having few coating film defects of the obtained pixel can be obtained. It came.

That is, the present invention is as follows.
[1] Contains at least (A) a pigment, (B) a dispersant, (C) a binder resin, and (D) an organic solvent,
(B) A AB block having a B-block having an amino group in the side chain and an A-block having no amino group and having an amine value of 20 mgKOH / g or more in terms of effective solid content. A polymer and / or an ABA block copolymer,
(C) The binder resin contains a resin (C1) having a polystyrene-equivalent weight average molecular weight measured by GPC of 4,000 or more and 50,000 or less and an acid value of 150 mgKOH / g or less. A colored curable resin composition for an ink jet color filter.
[2] The colored curable resin composition according to [1], wherein the (C1) resin has an epoxy group and / or a carboxyl group.
[3] The (C1) resin is (a) a mono (meth) acrylate having a structure represented by the following general formula (1), and (b) an epoxy group-containing (meth) acrylate or (meth) acrylic acid, The colored curable resin composition according to the above [1] or [2], which is a (meth) acrylic copolymer obtained by reacting an ethylenically unsaturated group-containing monomer containing.

(In formula (1), R ^{1 to} R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ and R ⁸ each independently represent a hydrogen atom or 1 to carbon atoms. 3 represents an alkyl group or is linked to each other to form a ring.)
[4] The ethylenic unsaturated, wherein the (C1) resin includes (a) a mono (meth) acrylate having a structure represented by the general formula (1), and (b1) an epoxy group-containing (meth) acrylate. The colored curable resin composition according to [3], which is a (meth) acrylic copolymer obtained by polymerizing a group-containing monomer.
[5] Ethylenically unsaturated, wherein the (C1) resin includes (a) mono (meth) acrylate having the structure represented by the general formula (1), and (b1) epoxy group-containing (meth) acrylate. A group-containing monomer is polymerized to obtain a trunk resin, and (c) an unsaturated monobasic acid is reacted with at least a part of the epoxy group derived from (b1) in the trunk resin, and at least a part of the resulting hydroxyl group (D) The colored curable resin composition according to [3], which is a (meth) acrylic copolymer obtained by reacting a polybasic acid or an anhydride thereof.
[6] The backbone resin of the (C1) resin is (a) a mono (meth) acrylate having a structure represented by the general formula (1), (b1) an epoxy group-containing (meth) acrylate, and (e1) The colored curable resin composition according to [5], which is obtained by polymerizing an ethylenically unsaturated monomer having an aromatic hydrocarbon group.
[7] The ethylenically unsaturated group containing (C1) resin containing (a) mono (meth) acrylate having the structure represented by the general formula (1) and (b2) (meth) acrylic acid The colored curable resin composition according to [3], which is a (meth) acrylic copolymer obtained by reacting a monomer.
[8] The (C1) resin is (a) a mono (meth) acrylate having a structure represented by the general formula (1), (b2) (meth) acrylic acid, and (e1) an aromatic hydrocarbon group. The colored curable resin composition according to the above [7], which is a (meth) acrylic copolymer obtained by reacting an ethylenically unsaturated monomer with
[9] Any of the above [1] to [8], wherein the organic solvent (D) contains a solvent having a boiling point of 180 ° C. or higher (boiling point under pressure of 101.25 [hPa]). The colored curable resin composition according to any one of the above.
[10] The above [9], wherein the organic solvent (D) contains 50% by weight or more of a solvent having a boiling point of 180 ° C. or higher (boiling point under a pressure of 101.25 [hPa]). Colored curable resin composition.
[11] The colored curable resin composition according to any one of [1] to [10], further including a monomer (E).
[12] The colored curable resin composition according to any one of [1] to [11], further including (F) a polymerization initiator.
[13] A color filter having pixels formed using the colored curable resin composition according to any one of [1] to [12].
[14] A liquid crystal display device, wherein the color filter according to [13] and a liquid crystal driving substrate are opposed to each other, and liquid crystal is sealed therebetween.
[15] An organic EL display including the color filter according to [13].

For appropriate wetting and spreading within the pixel bank of the colored curable resin composition of the present invention, it is preferable that the (C) binder resin contained therein contains a resin having a hydrophilic group. As described in [2], it is preferable to contain a resin (C1) having an epoxy group and / or a carboxyl group.
In particular, the (C1) resin is preferably a (meth) acrylic copolymer using (meth) acrylate having an alicyclic structure. Specific examples include the copolymers described in the above [3] to [8], but the present invention is not limited to these.

  In the present invention, “colored ink” and “ink” are synonymous with “colored curable resin composition”, and each represents a material for forming a pixel for an inkjet color filter.

  The colored curable resin composition (colored ink) of the present invention has good wetting and spreading in the pixel bank when subjected to color filter pixel formation by an ink jet method, and also exhibits coating film defects in the resulting pixel. Since generation is suppressed, a high-quality color filter can be manufactured with high yield.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to the gist thereof. It is not limited to the contents of.
In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ". In addition, “(co) polymer” means “single polymer (homopolymer) and / or copolymer (copolymer)”.
“Total solid content” means all components other than the solvent components described later, which are contained in the colored curable resin composition.
A weight average molecular weight shows the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).
The “amine value” represents an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the weight of KOH equivalent to the amount of base per 1 g of the solid content of the dispersant. The measuring method will be described later.

[1] Colored curable resin composition
The colored curable resin composition for an inkjet color filter of the present invention contains at least (A) a pigment, (B) a dispersant, (C) a binder resin, and (D) an organic solvent,
(B) A AB block having a B-block having an amino group in the side chain and an A-block having no amino group and having an amine value of 20 mgKOH / g or more in terms of effective solid content. Containing a polymer and / or an ABA block copolymer,
(C) Binder resin contains resin (C1) whose weight average molecular weight of polystyrene conversion measured by GPC is 4,000 or more and 50,000 or less, and whose acid value is 150 mgKOH / g or less. And

[1-1] (A) Pigment
The colored curable resin composition of the present invention comprises (A) a pigment as an essential component.
(A) As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Specific examples of pigments that can be used are shown below by pigment numbers. In addition, “CI” described below means a color index (CI).

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 4
7, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 5
0: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 254, and the like.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 6
7, 68, 71, 72, 73, 74, 75, 76, 78, 79, and the like. Of these, C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, and the like. Of these, C.I. I. Pigment green 7, 36, 58, and the like.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, etc., more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180, and the like.

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

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

A plurality of the above-mentioned various pigments can be used in combination. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
These pigments are used after being subjected to a dispersion treatment so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.3 μm or less.

In the present invention, the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering DLS. For particle size measurement, a sufficiently diluted colored curable resin composition (usually diluted and prepared to have a pigment concentration of about 0.005 to 0.2% by weight. However, if there is a concentration recommended by the measuring instrument, According to its concentration) and measured at 25 ° C.
In the colored curable resin composition of the present invention, the ratio of the (A) pigment to the total solid content is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and particularly preferably 40% by weight. %, Usually 90% by weight or less, preferably 80% by weight or less, more preferably 60% by weight or less.

  (A) If the content ratio of the pigment is too small, the coloring power becomes low, the film thickness becomes too large with respect to the color density, and there is a possibility of adversely affecting the gap control during the liquid crystal cell formation. On the other hand, if the pigment content is too high, the dispersion stability deteriorates and problems such as reaggregation and thickening may occur.

[1-2] (B) Dispersant
The colored curable resin composition of the present invention comprises (B) a dispersant as an essential component, and (B) the dispersant has an amine value of 20 mgKOH / g or more in terms of effective solid content and has an amino group in the side chain. It contains an AB block copolymer or an ABBA block copolymer composed of a B-block and an A-block having no amino group.
In the colored curable resin composition of the present invention, either one of the AB block copolymer and the ABA block copolymer may be used, or these may be used in combination. Also good. In addition, as for the AB block copolymer and the ABA block copolymer, one type of copolymer may be used alone, or a plurality of types may be used in combination.
As the copolymer, an acrylic block copolymer is particularly preferable. Hereinafter, the dispersant (B) will be described taking an example of an acrylic block copolymer as an example.

The B-block has an amino group. The amino group is preferably —NR ⁴¹ R ⁴² (provided that R ⁴¹ and R ⁴² each independently have a cyclic or chain-like alkyl group which may have a substituent, or a substituent. A preferred aryl group or a tertiary amino group represented by (which represents an aralkyl group which may have a substituent) and a partial structure containing this is represented by the following formula, for example.

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

  Two or more kinds of the partial structure containing an amino group as described above may be contained in one B-block. In that case, two or more amino group-containing partial structures may be contained in the B-block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing an amino group may be partially contained in the B-block as long as the effects of the present invention are not impaired. Examples of such a partial structure include (meth) acrylic acid esters. And a partial structure derived from a monomer. The content of such a partial structure not containing an amino group in the B-block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably it is not included.

On the other hand, the A-block constituting the block copolymer is not particularly limited as long as it is copolymerizable with the monomer constituting the B-block and is composed of a monomer having no amino group. No.
For example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Octyl acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) (Meth) acrylic acid ester monomers such as acrylate; (meth) acrylic acid monomers such as (meth) acrylic acid chloride; vinyl acetate monomers; allyl glycidyl ether, crotonic acid glycidyl ether Any polymer structure obtained by copolymerizing comonomers including glycidyl ether monomers.

  Among them, the A-block includes a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate 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 formula is preferred.

(In the formula, n represents an integer of 1 to 5, and R ⁴⁵ represents a hydrogen atom or a methyl group.)
The partial structure represented by the above formula is particularly preferably contained in the A-block in an amount of 5 to 40 mol%.
Having a partial structure derived from polyalkylene glycol (meth) acrylate, particularly a partial structure represented by the above formula, is preferable because an appropriate anti-aggregation effect is recognized and contributes to the stabilization of the dispersion.

An AB block or an ABA block copolymer composed of such an A block and a B block is prepared by, for example, 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. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

In synthesizing such an acrylic block copolymer, JP-A-60-89452, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 ( 1984), BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), K. Hatada, K. Ute, et al, Polym. J.18, 1037 (1986), Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737
(1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987), K. Matyaszewski et al, Chem. Rev. 2001, A known method described in US Pat.

The amine value in 1 g of the AB block copolymer and the ABA block copolymer according to the present invention is usually 20 mgKOH / g or more, preferably 50 mgKOH / g or more, more preferably 80 mgKOH / g or more, in particular. Preferably it is 100 mgKOH / g or more. Moreover, it is about 300 mgKOH / g or less normally.
The higher the amine value, the better the pigment dispersibility. However, if the amine value is too high or too low, the dispersion stability may decrease and the viscosity may become unstable. On the other hand, if it is too high, the electrical characteristics after the liquid crystal panel is formed may deteriorate.

The amine value of the dispersant in the present invention 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. The inflection point of the titration pH curve is taken as the titration end point, and the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W: Dispersant sample weighed [g], V: Titration amount at the end of titration [mL], S: Dispersant sample solid content concentration [wt%].)
Further, the acid value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but generally it is preferably lower, usually 10 mg KOH / g or less, and its molecular weight is GPC. The measured polystyrene average weight average molecular weight (Mw) is usually in the range of 1000 or more and 100,000 or less. 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.

In the present invention, a commercially available acrylic block copolymer having the same structure as described above can also be applied.
The (B) dispersant of the present invention may contain an optional dispersant in addition to the above-described block copolymer as long as the effects of the present invention are not impaired.
Examples of optional dispersants include urethane dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, polyoxyethylene alkyl ether dispersants, and polyoxyethylene. Examples include diester dispersants, ethylene diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants. Specific examples of such a dispersant include trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol) , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like. One of these dispersants may be used alone, or two or more of the dispersants including the above-described dispersant composed of the block copolymer may be mixed and used in an arbitrary combination and ratio. .

  In the colored curable resin composition of the present invention, the content ratio of the (B) dispersant is usually 95% by weight or less, preferably 65% by weight or less, more preferably 50% by weight or less with respect to the (A) pigment. In addition, it is usually 5% by weight or more, preferably 7% by weight or more, and particularly preferably 10% by weight or more. (B) If the content ratio of the dispersant is too small, (A) the adsorption to the pigment is insufficient, aggregation cannot be prevented, and the viscosity or gelation may occur. In addition, problems such as re-aggregation and thickening may occur. On the other hand, if the amount is too large, the ratio of the pigment (A) is relatively reduced, so that the coloring power is lowered, and the film thickness becomes too thick with respect to the color density. In some cases, cell gap control failure may occur.

  In addition, the colored curable resin composition of this invention is a role as a dispersing agent by containing a part of (C) binder resin mentioned later with the said (B) dispersing agent in the dispersion processing process mentioned later. You may be allowed to bear.

[1-3] (C) Binder resin
The colored curable resin composition of the present invention comprises (C) a binder resin as an essential component.
(C) Binder resin of this invention contains resin (C1) whose weight average molecular weight of polystyrene conversion measured by GPC is 4,000 or more and 50,000 or less, and whose acid value is 150 mgKOH / g or less. .

  (C1) When the weight average molecular weight of the resin exceeds the above range, the viscosity of the colored resin composition increases, and the discharge stability from the nozzle during application by the ink jet method tends to decrease. There is a possibility that the shrinkage rate at the time of curing of the resin composition is increased, the surface of the coating film is roughened, and the ejection stability from the nozzle at the time of application by the ink jet method is lowered. The weight average molecular weight is preferably 15,000 or less, more preferably 10,000 or less, and preferably 4,000 or more, more preferably 5,000 or more.

The acid value of the (C1) resin of the present invention is 150 mgKOH / g or less. When the acid value of the (C1) resin exceeds the above range, compatibility with the above-described (B) dispersant may be deteriorated, and problems such as turbidity may occur, and the storage stability tends to decrease. (C1) The acid value of the resin is preferably 120 mgKOH / g or less.
In addition, the (C1) resin in the present invention may be any resin as long as it satisfies the specific molecular weight and acid value described above, but has a hydrophilic group in order to achieve an appropriate wetting and spreading property within the pixel bank. Is preferred. Specifically, it preferably has an epoxy group and / or a carboxyl group.

When it has an epoxy group, the epoxy equivalent is preferably 150 or more. Moreover, 400 or less is preferable and 350 or less is more preferable. If the epoxy equivalent is too low, wet spreadability may be insufficient.
Moreover, when (C1) resin has a carboxyl group in this invention, the upper limit of the acid value is as above-mentioned. Moreover, it is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more. In spite of having a carboxyl group, when the acid value is too low, there is a possibility that the effect of improving the wet spreading property and the effect of improving the adhesion to the substrate cannot be sufficiently obtained.

The (C1) resin may have both a carboxyl group and an epoxy group in the same molecule.
When forming the pixel of a color filter by the inkjet method, a solvent having a high boiling point (for example, 180 ° C. or higher) is generally used for the purpose of preventing clogging of the nozzle portion of the inkjet head. Therefore, it is necessary to increase the heating and drying temperature after coating, and (C) the binder resin is required to have heat resistance.

(C) Binder resin that has high heat resistance and can easily realize “appropriate wetting and spreading in the pixel bank and suppression of occurrence of coating film defects”, which is a problem to be solved by the present invention. As the essential component (C1) resin, for example, mono- (meth) acrylates having specific alicyclic hydrocarbon groups described in [1-3-1] to [1-3-3] below are used. The (meth) acrylic copolymer used is mentioned.
[1-3-1] ethylene containing (a) mono (meth) acrylate having a structure represented by the following general formula (1) and (b) epoxy group-containing (meth) acrylate or (meth) acrylic acid (Meth) acrylic copolymer obtained by reacting a polymerizable unsaturated group-containing monomer. (Hereinafter, this copolymer is simply referred to as “[1-3-1] copolymer”.)
[1-3-1] The copolymer has (a) a partial structure derived from mono (meth) acrylate having a structure represented by the following general formula (1) as an essential component.

(In formula (1), R ^{1 to} R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ and R ⁸ each independently represent a hydrogen atom or 1 to carbon atoms. 3 represents an alkyl group or is linked to each other to form a ring.)
In the formula (1), the ring formed by connecting R ⁷ and R ⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms. .
Especially, as a structure represented by General formula (1), the structure represented by following formula (1a), (1b), or (1c) is preferable.

(C1) By introducing these structures into the resin, when the colored curable resin composition of the present invention is used in a color filter, the heat resistance of the composition is improved or formed using the composition. It is possible to increase the intensity of the processed pixels.
In addition, the mono (meth) acrylate which has a structure represented by the said 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 the structure has the structure, and those represented by the following general formula (2) are particularly preferable. .

In formula (2), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents a structure represented by the general formula (1).
The [1-3-1] copolymer is composed of (b) epoxy group-containing (meth) acrylate (hereinafter referred to as “(b1) epoxy group-containing (meth) acrylate”) or (meth) acrylic acid (hereinafter referred to as “(b)) epoxy group-containing (meth) acrylate”). A partial structure derived from “(b2) (meth) acrylic acid” is an essential component.

  (B1) Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl. Examples include (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.

  In the copolymerization reaction between (a) mono (meth) acrylate having the structure represented by the general formula (1) and (b1) epoxy group-containing (meth) acrylate or (b2) (meth) acrylic acid. A known solution polymerization method is applied. 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.

  Specific 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; acetate 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 has been added. Alternatively, the reaction may be carried out by dropping in a heated and stirred solvent. Further, the monomer may be dropped while a 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.

As described above, (a) mono (meth) acrylate having the structure represented by the general formula (1) and (b1) epoxy group-containing (meth) acrylate or (b2) (meth) acrylic acid as essential components. The copolymer obtained by the reaction may further contain (e) a partial structure derived from another monomer.
(E) There is no restriction | limiting in particular as another monomer, What is necessary is just a compound which can be copolymerized with (a) and (b1).

Specifically, for example, vinyl aromatics such as styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene, Dienes such as 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) acrylic acid isoamyl, (meth) acrylic acid hexyl, (meta ) -2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Cyclopentyl acid, cyclohexyl (meth) acrylate, (meth) acrylate-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid naphthyl, (meth) acrylic acid anthracenyl, (meth) acrylic acid anthraninonyl, (meth) acrylic acid piperonyl, (meth) acrylic acid salicylate, (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, (meth) acrylic acid-1 , 1,1-trifluoro Ethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as cumyl, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; (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, (Meth) acrylic amides such as N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide; (meth) Vinyl compounds such as acrylyl anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate; diethyl citraconic acid, diethyl maleate, Unsaturated dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; N- (meta ) Acrylyl phthalimide and the like.

Among these (e) other monomers, in order to impart excellent heat resistance, coating strength, and pigment dispersibility to the colored curable resin composition, styrene, benzyl (meth) acrylate, etc. (E1) An ethylenically unsaturated monomer having an aromatic hydrocarbon group is preferred.
When the partial structure derived from this (e1) ethylenically unsaturated monomer having an aromatic hydrocarbon group is contained in the [1-3-1] copolymer, the content is 1 to 70 mol%. Some are preferred, and more preferably 3 to 50 mol%.

  [1-3-2] (a) An ethylenically unsaturated group-containing unit comprising a mono (meth) acrylate having a structure represented by the general formula (1) and (b1) an epoxy group-containing (meth) acrylate. Polymers are obtained to obtain a trunk resin, and (c) an unsaturated monobasic acid is reacted with at least part of the epoxy group derived from (b1) in the trunk resin, and (d) at least part of the resulting hydroxyl group. A (meth) acrylic copolymer obtained by reacting a polybasic acid or an anhydride thereof.

  (C1) The resin is the “(a) mono (meth) acrylate having the structure represented by the general formula (1), and (b1) epoxy group-containing (meth) acrylate (and, if necessary, ( (e) Reacting (adding) an unsaturated monobasic acid to at least a part of the epoxy group derived from (b1) of (meth) acrylic copolymer obtained by reacting e) other monomer) And (d) a copolymer obtained by reacting at least part of the resulting hydroxyl group with a polybasic acid anhydride (hereinafter, this copolymer is simply referred to as “[1-3-2] copolymer”). .).

(C) As unsaturated monobasic acid, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These 1 type may be used independently and may use 2 or more types together.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These (c) unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group derived from (b1) in the copolymer, preferably 30 to 100 mol%, more preferably 50 to 50 mol%. Add to 100 mol%. (C) If the addition ratio of unsaturated monobasic acid is too small, wetting and spreading may be insufficient. In addition, as a method of adding (c) unsaturated monobasic acid to the epoxy group of a copolymer, a well-known method is employable.

Furthermore, as the polybasic acid or anhydride thereof added to the hydroxyl group produced when (c) an unsaturated monobasic acid is added to the epoxy group derived from (b1), known ones can be used.

For example, dibasic acids such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid; trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid Examples of the acid include bases or higher, or anhydrides thereof.

Of these, acid anhydrides are preferable, and tetrahydrophthalic anhydride and / or succinic anhydride are particularly preferable. These (d) polybasic acids or anhydrides thereof may be used alone or in combination of two or more.
By adding such components, wetting and spreading properties and adhesion to the substrate can be imparted to the binder resin used in the present invention.

  These (d) polybasic acids or anhydrides thereof are usually 10 to 100 of hydroxyl groups generated by adding (c) unsaturated monobasic acid to the epoxy group derived from (b1) of the copolymer. Although it is made to add to mol%, Preferably it is added to 20-90 mol%, More preferably, it is added to 30-80 mol%. If the amount is too small, the spreadability improving effect and the adhesion improving effect may not be sufficiently exhibited. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

In addition, the trunk resin in the [1-3-2] copolymer also has a partial structure derived from the above-mentioned (e) other monomer as in the [1-3-1] copolymer. Also good. (E) Other monomers include the same compounds as in the [1-3-1] copolymer, and preferred ones are also (e1) aromatics such as styrene and benzyl (meth) acrylate. It is an ethylenically unsaturated monomer having a hydrocarbon.
[1-3-3] (a) Ethylenically unsaturated group-containing monomer containing mono (meth) acrylate having the structure represented by the general formula (1) and (b2) (meth) acrylic acid (Meth) acrylic copolymer obtained by reacting.

The (C1) resin in the present invention contains (a) a mono (meth) acrylate having a structure represented by the general formula (1), and (b2) an ethylenically unsaturated group-containing single group containing (meth) acrylic acid. It may be a (meth) acrylic copolymer obtained by reacting a monomer (hereinafter, this copolymer is simply referred to as “[1-3-3] copolymer”).
The [1-3-3] copolymer may also have a partial structure derived from the above-mentioned (e) other monomer, similarly to the [1-3-1] copolymer. (E) Other monomers include the same compounds as described in the section of [1-3-1] copolymer, among which (e1) aromatic hydrocarbons such as styrene and benzyl (meth) acrylate An ethylenically unsaturated monomer having is preferred.

When the partial structure derived from this (e1) ethylenically unsaturated monomer having an aromatic hydrocarbon group is contained in the [1-3-1] copolymer, the content is 1 to 70 mol%. Some are preferred, and more preferably 3 to 50 mol%.
Of the various types of (C1) resins described above, from the viewpoint of good wetting and spreading within the pixel bank, [1-3-2] copolymer, that is, “(a) represented by the general formula (1)”. (B1) in the trunk resin obtained by polymerizing an ethylenically unsaturated group-containing monomer containing a mono (meth) acrylate having a structure and (b1) an epoxy group-containing (meth) acrylate. Particularly preferred is a copolymer obtained by reacting (c) an unsaturated monobasic acid with at least part of the derived epoxy group and reacting (d) a polybasic acid anhydride with at least part of the resulting hydroxyl group. Among them, “the trunk resin is (a) a mono (meth) acrylate having a structure represented by the general formula (1), (b1) an epoxy group-containing (meth) acrylate, and (e) an aromatic hydrocarbon group. Having ethylenically unsaturated single If it is intended to polymerize the body comprising "it is particularly preferred.

  In addition, when a color filter pixel is formed, coating defects such as wrinkles and cracks do not occur, and the function of the dispersant is not hindered. Polymerization of an ethylenically unsaturated group-containing monomer including a polymer, ie, “(a) mono (meth) acrylate having a structure represented by the general formula (1)” and (b2) (meth) acrylic acid The copolymer obtained in this way is particularly preferable, and among them, “(a) mono (meth) acrylate having the structure represented by the general formula (1), (b) (meth) acrylic acid, and (e) aroma” The case of “polymerizing an ethylenically unsaturated monomer having an aromatic hydrocarbon group” is particularly preferred.

Note that when forming a pixel of a color filter by an inkjet method, it is common to provide an alignment film directly without providing an overcoat layer on the pixel. Therefore, the pixel is required to have high resistance to a solvent such as N-methylpyrrolidone used for the alignment film provided in the vicinity.
From the point that a pixel excellent in chemical resistance can be obtained, and when the pixel is formed by thermosetting the composition, from the point of thermosetting, among the [1-3-1] copolymers, “(a) the above-mentioned (Meth) obtained by polymerizing an ethylenically unsaturated group-containing monomer including a mono (meth) acrylate having a structure represented by the general formula (1) and (b1) an epoxy group-containing (meth) acrylate “Acrylic copolymers” are particularly preferred.

[1-3-4] Other resins The colored curable resin composition for an ink-jet color filter of the present invention contains a resin other than the above-described (C1) resin as long as the effects of the present invention are not impaired. Also good. Examples of such resins include resins generally used for pixel forming materials for color filters, such as (meth) acrylic resins and epoxy resins. Among them, compounds represented by the following general formula (4) are exemplified. A resin as an essential monomer component (hereinafter referred to as [1-3-4] copolymer) is preferred.

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; and the like.

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 in terms of heat resistance. Note that R ^1a and R ^2a may be the same type of substituent or different substituents.
Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like. Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be used alone or in combination of two or more.

  The ratio of the ether dimer in the monomer component in obtaining the [1-3-4] copolymer is not particularly limited, but is usually 2 to 60% by weight, preferably 5 in the total monomer components. It is -55 weight%, More preferably, it is 5-50 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, the transparency, heat resistance, etc. There is a possibility that the performance of the coating film becomes insufficient.

[1-3-4] When the copolymer has an acid group, the colored curable resin composition containing the copolymer has a crosslinking reaction (hereinafter referred to as “acid”) in which an acid group and an epoxy group react to form an ester bond. -It may be referred to as “epoxy curing”. As the acid group,
Although it does not restrict | limit in particular, For example, a carboxyl group, a phenolic hydroxyl group, a carboxylic anhydride group etc. are mentioned. These acid groups may be only one kind or two or more kinds.

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

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

These monomers for introducing an acid group may be only one type or two or more types.
When the monomer for introducing an acid group is included, the content is not particularly limited, but usually 5 to 70% by weight in the total monomer components constituting the [1-3-4] copolymer, Preferably it is 10 to 60% by weight. If the amount is too large, the acid value becomes too high, and as described above, compatibility with the dispersant may be deteriorated, which may cause problems such as turbidity, and storage stability tends to decrease. .

[1-3-4] The monomer component for obtaining the copolymer may contain other copolymerizable monomers, if necessary, in addition to the essential monomer component.
Other copolymerizable monomers are not particularly limited, but methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene have good transparency and impair heat resistance. It is preferable in terms of difficulty. These other copolymerizable monomers may be used alone or in combination of two or more.

When the other copolymerizable monomer is included, the content is not particularly limited, but is preferably 95% by weight or less, and more preferably 85% by weight or less.
In addition, it is preferable to use this [1-3-4] copolymer for a dispersion treatment process with (B) a dispersing agent so that it may mention later. Preference is given to using benzyl acid. The content of benzyl (meth) acrylate is usually 1 to 70% by weight, preferably 5 to 60% by weight, based on all monomer components constituting the [1-3-4] copolymer. .

  The molecular weight of the [1-3-4] copolymer is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 2,000 to 200,000, more preferably 4,000 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.

The [1-3-4] copolymer can be produced, for example, by the method described in JP-A-2004-300203 and JP-A-2004-300204.
As will be described later, the colored curable resin composition of the present invention may be photocurable, thermosetting, or cured by both actions.

  In the case of curing using a thermosetting action, as the binder resin, among those described as [1-3-1] copolymer, “(a) mono (having a structure represented by the general formula (1) ( (Meth) acrylate, and (b1) a (meth) acrylic copolymer obtained by polymerizing an ethylenically unsaturated group-containing monomer, including an epoxy group-containing (meth) acrylate, or otherwise It is preferable to use an epoxy group-containing compound or resin in combination.

Note that when forming color filter pixels by the inkjet method, a photopolymerization initiator that can reduce luminance is not required, and the photocuring process can be omitted to increase productivity. It is preferable to use a natural colored curable resin composition.
In the colored curable resin composition of the present invention, the content ratio of (C) the binder resin is usually 1% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably in the total solid content. Is 60% by weight or less. (C) When content of binder resin is less than this range, a film | membrane becomes weak and the adhesiveness to a board | substrate may fall, or heat resistance and a brightness | luminance may fall. On the other hand, if the amount is larger than this range, the coloring power may be insufficient or it may be difficult to adjust the film thickness to an appropriate thickness.

[1-4] (D) Organic solvent
The colored curable resin composition of the present invention contains (D) an organic solvent as an essential component. (D The organic solvent has the function of dissolving or dispersing each component contained in the composition and adjusting the viscosity.
Such (D) organic solvent may be any one that can dissolve or disperse each component constituting the colored curable resin composition.
Examples of the solvent that (D) the organic solvent can contain include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether , 3-methyl-3-methoxybutanol, triethylene Recall monomethyl ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol monomethyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, 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 mono-n-butyl 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 Glycols such as methyl monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate Alkyl ether acetates;
Triacetin;
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, benzyl alcohol, ethylene glycol, propylene glycol, butanediol, triethylene glycol, methoxymethylpentanol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;

Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as propyl, butyl 3-methoxypropionate, 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.
The boiling point of the solvent is usually 130 ° C. or higher and 300 ° C. or lower (under a pressure of 101.25 [hPa]. The same applies to the boiling points hereinafter), and preferably 150 ° C. or higher and 280 ° C. or lower. When the boiling point is too low, the uniformity of the resulting coating film tends to be poor. If the boiling point is too high, the effect of preventing evaporation of the solvent from the ink droplets is high, as will be described later, but there are many residual solvents in the coating 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, more preferably 5 mmHg or less, and still 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, a few 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, the organic solvent preferably contains 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. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by weight or more in the organic solvent, more preferably 70% by weight or more, and most preferably 90% by weight or more. When the high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited.

  Preferred examples of the high boiling point solvent include 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-hexanediol. Examples thereof include diacetate and triacetin. Of these, diethylene glycol mono-n-butyl ether acetate is particularly preferable.

  Further, (D) the organic solvent may partially contain a solvent having a boiling point lower than 180 ° C. in order to adjust the viscosity of the ink 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, acetates, 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 organic solvent (D) contains alcohols, there may be a problem that the ejection stability in the ink jet method is deteriorated. Therefore, the alcohol is preferably 20% by weight or less in the (D) organic solvent, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.

  The proportion of the organic solvent (D) in the colored curable resin composition of the present invention is not particularly limited, but is usually 50% by weight or more, preferably 60% by weight or more, and usually 99% by weight or less, preferably 95% by weight or less. (D) If the organic solvent is too much, the solid content concentration becomes too low, making it unsuitable for forming a coating film. Conversely, if the amount is too low, the viscosity of the ink becomes too high. There are cases where problems such as hindering the stability of the ink occur, and when applied to the ink jet method, the ejection stability may be lowered.

[1-5] (E) Monomer
The colored curable resin composition of the present invention preferably contains (E) monomer. (E) The monomer is not particularly limited as long as it is a polymerizable low molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

  When the colored curable resin composition of the present invention is irradiated with actinic rays, the ethylenic compound is added by the action of a photopolymerization initiation system described later or by the action of a thermal polymerization initiator described later by heating. It is a compound having an ethylenic double bond that polymerizes and cures. In addition, the 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 unsaturated carboxylic acid such as (meth) acrylic acid, ester of monohydroxy compound and unsaturated carboxylic acid, ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid, aromatic polyhydroxy Esters obtained by esterification reaction of an ester of a compound with an unsaturated carboxylic acid, an unsaturated carboxylic acid and a polyvalent carboxylic acid and a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound, poly Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting an isocyanate compound with a (meth) acryloyl group-containing hydroxy compound.

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meta) ) Acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, triglycerol di (meth) acrylate Isopropyloxy of diglycerol di (meth) acrylate, etc. (meth) acrylic acid ester. Moreover, itaconic acid ester in which the (meth) acrylic acid portion of these acrylates is replaced with itaconic acid portion, crotonic acid ester in which crotonic acid portion is replaced, or maleic acid ester in which maleic acid portion is replaced.

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

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

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferred, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. These monomers may be used alone, but since it is difficult to obtain a single compound in production, two or more kinds 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. 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 are within the above range. It is preferable to adjust so that it may enter.
In the present invention, a more preferred polyfunctional monomer having an acid group is succinic acid of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate commercially available as “TO1382” manufactured by Toagosei Co., Ltd. It is a mixture mainly composed of ester. A combination of this polyfunctional monomer and another polyfunctional monomer can also be used.

  In addition, since the colored curable resin composition of the present invention is used for production of an ink jet color filter, the ink has good wetting and spreading properties. Therefore, the monomer is linear or has a relatively small molecular weight. For example, ethoxylated trimethylolpropane tri (meth) acrylate, triglycerol di (meth) acrylate, isopropyloxylated diglycerol di (meth) acrylate and the like are preferable. Such compounds are commercially available as “70PA”, “80MFA” (both trade names, manufactured by Kyoeisha Chemical Co., Ltd.), “A-TMPT-3EO” (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. Has been.

  In the colored curable resin composition of the present invention, the content ratio of these (E) monomers is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. In addition, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The ratio to the pigment (A) 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. It is preferably 100% by weight or less, more preferably 80% by weight or less.

[1-6] (F) Polymerization initiator
The colored curable resin composition of the present invention preferably contains (F) a polymerization initiator such as a photopolymerization initiator system and / or a thermal polymerization initiator for the purpose of curing the coating film. However, the method of curing the composition may be other than the method using (F) polymerization initiator.

  In particular, when the colored curable resin composition of the present invention contains (C) a resin having an ethylenic C = C double bond as a binder resin, or (E) an ethylenic compound as a monomer, A photopolymerization initiator that directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction and has a function of generating a polymerization active radical and / or a thermal polymerization initiator that generates a polymerization active radical by heat. It is preferable to contain. In the present invention, the “photopolymerization initiation system” is a photopolymerization initiator (hereinafter, arbitrarily referred to as component (f1)), or an accelerator (hereinafter, arbitrarily referred to as necessary). (Referred to as component (f2)).

[1-6-1] Photopolymerization initiation system
The colored curable resin composition of the present invention may contain a photopolymerization initiation system. The photopolymerization initiating system is usually (f1) a photopolymerization initiator or used as a mixture with (f2) a polymerization accelerator added to this if necessary, and (f3) is increased if necessary. A dye is used in combination. It is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause decomposition reaction or hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiation system (f1) include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1 monoyl), 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.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl). ) Imidazole dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4 ′ -Methoxyphenyl) -4,5-diphenylimidazole dimer and the like.

  Examples of 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-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  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 and the like.

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 It is.

  The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime) and the like.

  Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (pmethoxyphene Nil) acridine derivatives such as acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone.

  Examples of the (f2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; or mercapto compounds such as aliphatic polyfunctional mercapto compounds.

Each of these photopolymerization initiators and polymerization accelerators may be used alone or in combination of two or more.
In the colored curable resin composition of the present invention, the content of these photopolymerization initiation systems is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight in the total solid content. Hereinafter, it is preferably 30% by weight or less. If this content is extremely low, the sensitivity to exposure light may be insufficient.

In addition, (f3) sensitizing dye is used for the purpose of increasing the sensitivity as required. (F3) 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 and JP-A-4-219756; Coumarin dyes having a heterocyclic ring described in Kaihei 3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes described in JP-A-3-239703, JP-A-5-289335, etc. Pyrromethene dyes described in JP-A-6-19240, etc .; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP-A 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP No. -107761, JP-A-5-210240, JP-A-4-288
Examples thereof include dyes having a dialkylaminobenzene skeleton described in each publication of No. 818.

  Among these 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. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p- Ethylaminophenyl) 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-diethylaminophenyl) pyrimidine P-dialkylaminophenyl group-containing compounds such as Of these, 4,4'-dialkylaminobenzophenone is most preferred. A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

  In the colored curable resin composition of the present invention, the content of the sensitizing dye (f3) is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% in the total solid content. It is in the range of not less than wt%, usually not more than 20 wt%, preferably not more than 15 wt%, more preferably not more than 10 wt%.

[1-6-2] Thermal polymerization initiator
Specific examples of the thermal polymerization initiator used in the present invention include azo compounds, organic peroxides and hydrogen peroxide. Of these, azo compounds are preferably used.
As the azo compound, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-1-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-cyclohexyl- 2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionate), 2,2'-azobis (2,4 , 4-Trimethylpen Emissions), or the like can be cited, 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 peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide , Di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 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-hex Silperoxyisopropyl monocarbonate, t-butylperoxymaleic 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-di-methyl-2 , 5-Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl4,4-di- ( t-Butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide) Oxy) f Sun, 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) peroxide And a mixture of benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide.
In addition, some of the above-described (f1) 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 (f1) photoinitiator as a thermal-polymerization initiator.

  If the proportion of the thermal polymerization initiator is too small, the film may be insufficiently 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. In addition, the storage stability may be reduced. Therefore, it is preferable to select in the range of 0.1 to 30% by weight, particularly 1 to 20% by weight, based on the total solid content of the curable resin composition of the present invention.

[1-7] Optional components
The colored curable resin composition of the present invention includes a surfactant, a dye, a dispersion aid, an organic acid and / or an anhydride thereof, a plasticizer, a dye, a thermal polymerization inhibitor, and a storage stabilizer, in addition to the above components. , Surface protective agents, adhesion improvers, development improvers and the like may be contained.

Various types of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but they may adversely affect various properties such as voltage holding ratio and compatibility with organic solvents. It is preferable to use a nonionic surfactant in terms of low properties.
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, silicone surfactants such as “SH8400” manufactured by Tore Silicone, “KP341” manufactured by Silicone; “FC430” manufactured by Sumitomo 3M; Dainippon Ink and Chemicals, Inc. Fluorine-based surfactants such as “F470” and “F475” manufactured by Neos Corporation; “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.

  In addition, the colored curable resin composition of the present invention may be used in combination with a dye as long as the effects of the present invention are not impaired in terms of color tone adjustment and the like. Examples of dyes that can be used include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Dispersing aids are used to improve the dispersibility of pigments, improve the dispersion stability, etc. , Derivatives of anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine pigments and the like.
Examples of the substituent of these pigment derivatives include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. These substituents may be directly bonded to the pigment skeleton, or may be bonded via an alkyl group, an aryl group, a heterocyclic group or the like. Of the substituents, a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group are preferable, and a sulfonic acid group is more preferable.
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 sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, diketo Examples include sulfonic acid derivatives of pyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments. Among these, sulfonic acid derivatives of Pigment Yellow 138, sulfonic acid derivatives of Pigment Yellow 139, sulfonic acid derivatives of Pigment Red 254, sulfonic acid derivatives of Pigment Red 255, sulfonic acid derivatives of Pigment Red 264, and sulfonic acid of Pigment Red 272 are preferable. A sulfonic acid derivative of Pigment Red 209, a sulfonic acid derivative of Pigment Violet 23, and a sulfonic acid derivative of Pigment Yellow 138, and a sulfonic acid derivative of Pigment Red 254.

  In the colored curable resin composition of the present invention, the content ratio of these dispersion aids is usually 0.1% by weight or more, and usually 30% by weight or less, preferably with respect to the pigment (A). It is 200% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. If the addition amount is small, the effect may not be sufficiently exhibited. Conversely, if the addition amount is too large, the dispersibility and dispersion stability may be deteriorated.

The colored curable resin composition of the present invention may contain an organic acid having a molecular weight of 1000 or less and / or an anhydride thereof for improving storage stability. Examples of the organic acid include carboxylic acid, sulfonic acid, phosphonic acid, phosphoric acid and the like.
Specific examples of the organic carboxylic acid include aliphatic carboxylic acids and aromatic carboxylic acids.

  Aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, 3-phenylpropionic acid, 2-bromopropionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, n-octanoic acid, myristic acid, palmitic acid, stearic acid , Lactic acid, cinnamic acid, phenylpropiolic acid, levulinic acid, glycolic acid, (meth) acrylic acid, etc .; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid And dicarboxylic acids such as cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid; and tricarboxylic acids such as tricarballylic acid and aconitic acid. Aromatic carboxylic acids include benzoic acid, 2-hydroxybenzoic acid, 2-bromobenzoic acid, p-toluic acid, phthalic acid, 2-naphthoic acid, isonicotinic acid, etc. Examples thereof include a carboxylic acid having a carboxyl group bonded from an aromatic ring via a carbon bond, such as a carboxylic acid having a group bonded thereto, and mandelic acid. Among the acids mentioned above, anhydrides of polybasic acids may be used.

Examples of the sulfonic acid include p-toluenesulfonic acid, 4-chlorobenzenesulfonic acid, 2-naphthalenesulfonic acid (hydrate) and the like.
Examples of phosphonic acid include phenylphosphonic acid, and examples of phosphoric acid include polyphosphoric acid.
Among these, those having a molecular weight of 600 or less are preferable, and those having a molecular weight of 50 to 500 are particularly preferable.

  In the colored curable resin composition of the present invention, the content of these organic acids and / or anhydrides thereof is usually 1 to 40% by weight, preferably 1 to 30% by weight, based on the pigment (A). . Moreover, it is 0.3 to 20 weight% normally in the total solid of a colored curable resin composition, Preferably it is 0.3 to 15 weight%. If the content of the organic acid and / or its anhydride is too large, the surface of the coating film may be roughened, the contrast of the resulting pixels may be decreased, the viscosity of the ink may be increased, and if it is too small, the ink storage stability may be increased. There is a possibility that the property improving effect is not sufficiently exhibited.

The colored curable resin composition of the present invention may contain a plasticizer. Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, and tricresyl. Examples thereof include phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The content of these plasticizers is preferably in the range of 10% by weight or less based on the total solid content.

The colored curable resin composition of the present invention may contain a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6- Examples include t-butyl-p-cresol, β-naphthol and the like. The content of these thermal polymerization inhibitors is preferably in the range of 3% by weight or less based on the total solid content.

[2] Method for preparing colored curable resin composition
Next, a method for preparing the colored curable resin composition of the present invention will be described.

The colored curable resin composition of the present invention may be prepared by mixing other components into a pigment dispersion prepared in advance, or all components may be mixed together. Below, the case where it prepares according to the former method is demonstrated to an example, However, It is not limited to this.
The colored curable resin composition of the present invention may be photocurable (photopolymerizable) or thermopolymerizable depending on the production process to be applied. Hereinafter, the case where the composition is thermally polymerizable will be described as an example, but the present invention is not limited thereto.

  First, (A) pigment, (B) dispersant and (D) organic solvent are weighed in predetermined amounts, and (A) the pigment is dispersed in a dispersion treatment step to obtain a 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 (A) is finely divided, so that the coating characteristics of the colored curable resin composition are improved, and the transmittance of the product, such as a color filter substrate, is improved.

(A) When dispersing the pigment, it is preferable to use (C) a part of the binder resin and a dispersion aid as appropriate. Note that the (C) binder resin used in this dispersion treatment step may be particularly referred to as “dispersion resin”.
Moreover, when performing a dispersion process 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 pigment dispersion, the size of the sand grinder apparatus, and the like.

In addition, components other than the pigment dispersion in the colored curable resin composition may be mixed in advance to prepare a clear base, which may be mixed with the pigment dispersion.
In addition to the pigment dispersion obtained by the above dispersion treatment, (C) a binder resin, (D) an organic solvent, and optionally an optional component (E) monomer, (F) a polymerization initiator, In addition, a colored curable resin composition is obtained by mixing the other components to obtain a uniform dispersion solution. In addition, since fine dust may be mixed in each of the dispersion treatment step and the mixing step, the obtained pigment dispersion is preferably subjected to filtration treatment with a filter or the like.

[3] Application of colored curable resin composition
The colored curable 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 the color filter components.
Hereinafter, a color filter using the colored curable resin composition of the present invention, a liquid crystal display device (panel) using the color filter, and a method for manufacturing an organic EL display will be described.

[3-1] Color filter
The manufacturing method of the color filter by the inkjet method using the colored curable resin composition of this invention is demonstrated.
In the inkjet method, first, a partition pattern (black matrix) is provided on a substrate, and ink for pixel formation is directly supplied in the pattern, that is, in a pixel bank, 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 (BM) 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 inks that are driven into the pixels from being mixed. Compared to the case of a color filter by lithography, the film thickness is thick (usually a film thickness of 1.5 μm or more, preferably about 1.8 to 2.5 μm, more preferably about 2.0 to 2.3 μm. There is a feature. Further, 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 containing a black pigment from a conventionally used chromium compound such as chromium metal, chromium oxide, chromium nitride, or a black matrix made of a light-shielding metal material such as nickel and tungsten alloy. A resin black matrix (BM) is preferred.
In the color filter of the present invention, the resin black matrix (BM) may be formed by a general photolithography method. The obtained resin BM is subjected to hydrophilic treatment on the surface of the transparent substrate and repellency of the BM pattern by chemical treatment or physical treatment, respectively.

  Next, in the substantially rectangular recessed area (inside the pixel bank) surrounded by the resin BM pattern, the colored curable resin composition of the present invention is used for drawing with an ink jet apparatus, drying, photocuring and / or thermosetting. A color filter is obtained by completely curing the composition and forming pixels. As the colored curable resin composition for pixel formation, three colors of R (red), G (green), and B (blue) are often used, but are not limited thereto.

  The material of the transparent substrate used in the color filter of the present invention is not particularly limited. For example, polyester such as polyethylene terephthalate, polypropylene, polyolefin such as polyethylene, thermoplastic such as polycarbonate, polymethyl methacrylate, polysulfone, etc. Examples thereof include a thermosetting plastic sheet such as a plastic sheet, an epoxy resin, a polyester resin, and a poly (meth) acrylic resin, or various glass plates. In particular, a glass plate and a heat-resistant plastic plate are preferably used from the viewpoint of heat resistance.

  For drying the coating film of the colored curable resin composition, heat drying such as a hot plate, IR oven, convection oven or the like can be used. Preferred drying conditions are 40 to 150 ° C., and drying time is 10 seconds to 60 minutes. It is a range. Further, reduced pressure (vacuum) drying can be used, and preferable drying conditions are 0.1 to 1 Torr, and drying time is in the range of 10 seconds to 60 minutes. Furthermore, both can be used together and can also be performed sequentially or simultaneously.

In addition, when hardening the colored curable resin composition of this invention by heating, as an apparatus used for a heating, oven, a hotplate, etc. are mentioned, for example. For example, the temperature is generally in the range of 100 to 300 ° C., and the heating time is generally in the range of 10 to 120 minutes.
When the colored curable resin composition of the present invention is cured by photocuring, examples of the light source used for exposure include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and a medium pressure mercury lamp. And lamp light sources such as low-pressure mercury lamps and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, and the like. In the case where only the wavelength of specific irradiation light is used, an optical filter can also be used.

[3-2] Liquid crystal display device
Next, the liquid crystal display device (panel) of the present invention will be described.
The liquid crystal display device of the present invention is manufactured by making the above-described color filter of the present invention and a liquid crystal driving substrate face each other and enclosing a liquid crystal therebetween. More specifically, for example, it is manufactured as follows.
First, an alignment film is formed on the color filter, a spacer is disposed on the alignment film, and then a liquid crystal cell is formed by bonding to a counter substrate for driving liquid crystal. Next, liquid crystal is injected into the formed liquid crystal 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 or a flexographic printing method is usually employed, and the thickness of the alignment film is usually 10 to 100 nm. After the alignment film is cured by thermal baking, it is surface-treated by ultraviolet (UV) irradiation or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.
A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film 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 to 8 μm. After bonding 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 the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. To do. The degree of vacuum in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, Preferably it is 50-90 degreeC. The warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. In the liquid crystal cell into which the liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

The type of the liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of a lyotropic liquid crystal, a 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 these may be used.
[2-4] Organic EL Display When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. A part of the color is formed using the colored resin composition of the present invention), and a color of the present invention in which a resin black matrix (not shown) provided between adjacent pixels 20 is formed. An organic EL element can be manufactured by preparing a filter and laminating the organic light-emitting body 500 on the color filter via the organic protective layer 30 and the inorganic oxide film 40.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. 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.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In addition, the weight average molecular weight of the polymer obtained in the following synthesis examples is a value obtained by measurement by gel permeation chromatography (GPC) under the following conditions and in terms of polystyrene.
Separation column Tosoh GMHxl x 2 Standard sample Polystyrene Flow rate 1.0ml / min
Column temperature 40 ° C
Calibration curve 5th

[Synthesis Example 1]
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2,2′-azobis-2 -8.47 weight part of methylbutyronitrile was dripped over 3 hours, and also it stirred at 90 degreeC for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 28.5 parts by weight of succinic acid and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the binder resin 1 thus obtained was about 9000, and the acid value was 38 mgKOH / g.

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

[Synthesis Example 3]
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. To this, 95.1 parts by weight of glycidyl methacrylate and 72.6 parts by weight of a monoacrylate having a tricyclodecane skeleton (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and 2,2′-azobis-2-methylbutyrate was further added. 8.47 parts by weight of nitrile was added dropwise over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours to obtain a binder resin 3 having a weight average molecular weight Mw of about 6100.

[Synthesis Example 4]
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, 10 parts by weight of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 15 parts by weight of methacrylic acid, 20 parts by weight of methyl methacrylate, 55 parts by weight of benzyl methacrylate, t- 2.6 parts by weight of butyl peroxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate were charged, and 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate were added to the chain transfer agent tank. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization.

  While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a 30 wt% polymer solution having a weight average molecular weight of 9200 and an acid value of 107 mg KOH / g.

[Synthesis Example 5]
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.
On the other hand, 10 parts by weight of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 15 parts by weight of methacrylic acid, 20 parts by weight of methyl methacrylate, 55 parts by weight of benzyl methacrylate, t- 2.6 parts by weight of butyl peroxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate were charged, and 4.0 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate were added to the chain transfer agent tank. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a 30 wt% polymer solution having a weight average molecular weight of 12300 and an acid value of 107 mgKOH / g.

[Synthesis Example 6]
50 parts by weight of polyethyleneimine having a weight average molecular weight of about 5000, 40 parts by weight of polycaprolactone with n = 5, and 6 parts by weight of stearic acid are mixed with 300 parts by weight of propylene glycol monomethyl ether acetate, and a nitrogen atmosphere at 150 ° C. for 3 hours. Stir below. Dispersant C thus synthesized had an amine value of 54 mgKOH / g and an acid value of 10 mgKOH / g.

[Example 1]
8.6 g of Pigment Green 36 as a pigment, 8.6 g of Pigment Yellow 150, 5.8 g of Dispersant A described later as a dispersant, and 5.8 g of the resin obtained in Synthesis Example 4 as a dispersion resin (effective solids) After mixing 115.2 g of diethylene glycol mono-n-butyl ether acetate as a solvent and stirring and homogenizing, 300 g of zirconia beads having a particle diameter of 0.5 mm were added, and the mixture was shaken for 5 hours with a paint conditioner to be dispersed. Thus, a pigment dispersion A was prepared.

Separately, 4.1 g of the binder resin 1 obtained in Synthesis Example 1, 1.4 g of Irgacure 907 manufactured by Ciba Geigy Co. as a polymerization initiator, and 16.1 g of diethylene glycol mono-n-butyl ether acetate as a solvent were mixed. A clear base was produced.
While stirring 78.4 g of the above pigment dispersion A, 21.6 g of the above clear base was dropped and mixed, and then filtered through a 5 μm membrane filter to obtain a uniform colored curable resin composition.

<Dispersant A: BYK-LPN6919 manufactured by Big Chemie>
A methacrylic AB block copolymer having a tertiary amino group.
The weight average molecular weight Mw is 9000, the amine value is 121 mgKOH / g, the acid value is almost 0 mgKOH / g, and the “repeating unit having an amino group in the side chain” in the B-block is represented by the following formula (i). Yes, the proportion of the repeating unit represented by the following formula (ii) in the B block is 11 mol%.

The amine value was measured by the following method.
<Measurement of amine value>
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: Dispersant sample weighed [g], V: Titration amount at the end of titration [mL], S: Dispersant sample solid content concentration [wt%].)
Next, non-alkali glass substrate (trade name “AN635”) manufactured by Asahi Glass Co., Ltd. 10 cm square 0.7 mm
A photosensitive resin composition containing a black pigment was applied to the thickness, and predetermined exposure, development, and post-baking treatments were performed to produce a black matrix pattern having a rectangular opening with a film thickness of 2 μm and 700 μm × 220 μm.

After the substrate is subjected to a liquid repellent treatment by fluorine-based gas plasma treatment, the amount of the colored curable resin composition corresponding to 1800 pl by an inkjet method is applied to the center of each pixel bank formed by the black matrix pattern. Was applied. The wetting and spreading of the colored curable resin composition in the pixel bank was good and spread uniformly throughout.
Thereafter, drying under reduced pressure was performed at 50 Pa for 10 minutes. When the surface of the coating film after drying was observed, slight wrinkles were observed, but there were no cracks and a good coating film was obtained. An optical micrograph of the obtained dried coating film is shown in FIG.

[Example 2]
4.5 g of binder resin 2 obtained in Synthesis Example 2, 0.6 g of binder resin 3 obtained in Synthesis Example 3, 1.5 g of DPHA (dipentaerythritol hexaacrylate), manufactured by Ciba Geigy as a polymerization initiator A clear base was prepared by mixing 1.7 g of Irgacure 907 and 34.6 g of diethylene glycol mono-n-butyl ether acetate as a solvent.

Pigment dispersion A prepared in the same manner as in Example 1: While stirring 57.1 g, 42.9 g of the above clear base was dropped and mixed, and then filtered through a 5 μm membrane filter to obtain a uniform colored curable resin composition. A substrate was prepared in the same manner as in Example 1, and the colored curable resin composition was applied and dried under reduced pressure in the pixel bank. The wetting and spreading within the pixel bank of the colored curable resin composition was good and spread uniformly throughout, but when the coating film surface after drying was observed, neither wrinkles nor cracks were observed, and a good coating film was gotten. An optical micrograph of the obtained dried coating film is shown in FIG.

[Comparative Example 1]
6.5 g of epoxy resin EHPE3150 (weight average molecular weight: 2400, acid value: 0) manufactured by Daicel Chemical Industries, 1.7 g of Irgacure 907 manufactured by Ciba Geigy Corp. as a polymerization initiator, and diethylene glycol mono-n-butyl ether acetate 34. 6g was mixed and the clear base was produced.

Pigment dispersion A prepared in the same manner as in Example 1: 42.8 g of the above clear base was dropped and mixed while stirring 57.2 g, and then filtered through a 5 μm membrane filter to obtain a uniform colored curable resin composition. Got.
A substrate was prepared in the same manner as in Example 1, and the colored curable resin composition was applied and dried under reduced pressure in the pixel bank. The wetting and spreading of the colored curable resin composition in the pixel bank was good and spread uniformly throughout.
When the coating film surface after drying was observed, cracks were observed on the front surface of the coating film. An optical micrograph of the obtained dry coating film is shown in FIG.

[Comparative Example 2]
8.6 g of Pigment Green 36 as a pigment, 8.6 g of Pigment Yellow 150, 3.4 g of the dispersant obtained in Synthesis Example 6 as a dispersant, and 6 of the resin obtained in Synthesis Example 5 as a dispersion resin. .9 g, 117.3 g of diethylene glycol mono-n-butyl ether acetate as a solvent were mixed, and after stirring and homogenizing, 300 g of zirconia beads having a particle diameter of 0.5 mm were added, and the mixture was dispersed by shaking for 5 hours in a paint conditioner. Pigment dispersion B was prepared.

Separately, 7.5 g of the binder resin 1 obtained in Synthesis Example 1, 1.6 g of Irgacure 907 manufactured by Ciba Geigy Co., Ltd. as a polymerization initiator, and 13.9 g of butyl carbitol acetate as a solvent are mixed to form a clear base. Produced.
While stirring 77.0 g of the pigment dispersion B, 23.0 g of the clear base was dropped and mixed, and then filtered through a 5 μm membrane filter to obtain a uniform colored curable resin composition.
A substrate was prepared in the same manner as in Example 1, and the colored curable resin composition was applied and dried under reduced pressure in the pixel bank. The wetting and spreading of the colored curable resin composition in the pixel bank was bad, and the entire pixel did not spread. An optical micrograph of the obtained dried coating film is shown in FIG.

[Reference example]
A solution was prepared by dissolving 4 g of dipentaerythritol hexaacrylate (DPHA) in 16 g of diethylene glycol mono-n-butyl ether acetate.
A substrate was prepared in the same manner as in Example 1, and the obtained solution was applied and dried under reduced pressure in the pixel bank. The wet spread of the solution in the pixel bank was bad, and the entire pixel did not spread. FIG. 5 shows an optical micrograph showing the state of wetting and spreading.

  According to the present invention, when forming a pixel of a color filter by an ink jet method, coloring that satisfies both the wet spread of colored ink and the reduction of coating film defects of the pixel, which has often been in a trade-off relationship in the past. A curable resin composition can be provided.

2 is a photograph of the surface of a coating film produced in Example 1. 4 is a photograph of the surface of a coating film produced in Example 2. 2 is a photograph of the surface of a coating film produced in Comparative Example 1. 6 is a photograph of the surface of a coating film produced in Comparative Example 2. It is a photograph which shows the mode of the wet spreading of the solution in a reference example. 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 (15)

At least (A) a pigment, (B) a dispersant, (C) a binder resin and (D) an organic solvent,
(B) A AB block having a B-block having an amino group in the side chain and an A-block having no amino group and having an amine value of 20 mgKOH / g or more in terms of effective solid content. A polymer and / or an ABA block copolymer,
(C) The binder resin contains a resin (C1) having a polystyrene-equivalent weight average molecular weight measured by GPC of 4,000 or more and 50,000 or less and an acid value of 150 mgKOH / g or less. A colored curable resin composition for an ink jet color filter.   The colored curable resin composition according to claim 1, wherein the (C1) resin has an epoxy group and / or a carboxyl group. The ethylene in which the (C1) resin contains (a) mono (meth) acrylate having a structure represented by the following general formula (1), and (b) epoxy group-containing (meth) acrylate or (meth) acrylic acid The colored curable resin composition according to claim 1 or 2, which is a (meth) acrylic copolymer obtained by reacting a polymerizable unsaturated group-containing monomer.

(In formula (1), R ^{1 to} R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ and R ⁸ each independently represent a hydrogen atom or 1 to carbon atoms. 3 represents an alkyl group or is linked to each other to form a ring.)   The (C1) resin contains (a) a mono (meth) acrylate having a structure represented by the general formula (1), and (b1) an epoxy group-containing (meth) acrylate. The colored curable resin composition according to claim 3, which is a (meth) acrylic copolymer obtained by polymerizing a monomer.   The (C1) resin contains (a) a mono (meth) acrylate having a structure represented by the general formula (1), and (b1) an epoxy group-containing (meth) acrylate. Polymers are obtained to obtain a trunk resin, and (c) an unsaturated monobasic acid is reacted with at least part of the epoxy group derived from (b1) in the trunk resin, and (d) at least part of the resulting hydroxyl group. The colored curable resin composition according to claim 3, which is a (meth) acrylic copolymer obtained by reacting a polybasic acid or an anhydride thereof.   The backbone resin of the (C1) resin is (a) a mono (meth) acrylate having a structure represented by the general formula (1), (b1) an epoxy group-containing (meth) acrylate, and (e1) aromatic carbonization. The colored curable resin composition according to claim 5, which is obtained by polymerizing an ethylenically unsaturated monomer having a hydrogen group.   Ethylenically unsaturated group-containing monomer in which the (C1) resin contains (a) mono (meth) acrylate having the structure represented by the general formula (1) and (b2) (meth) acrylic acid The colored curable resin composition of Claim 3 which is a (meth) acrylic-type copolymer obtained by making this react.   The (C1) resin is (a) mono (meth) acrylate having the structure represented by the general formula (1), (b2) (meth) acrylic acid, and (e1) ethylene having an aromatic hydrocarbon group. The colored curable resin composition according to claim 7, which is a (meth) acrylic copolymer obtained by reacting a polymerizable unsaturated monomer.   The organic solvent (D) contains a solvent having a boiling point of 180 ° C. or higher (boiling point under a pressure of 101.25 [hPa] condition), according to any one of claims 1 to 8. Colored curable resin composition.   10. The colored curable resin according to claim 9, wherein the organic solvent contains 50% by weight or more of a solvent having a boiling point of 180 ° C. or higher (boiling point under a pressure of 101.25 [hPa]). Composition.   The colored curable resin composition according to any one of claims 1 to 10, further comprising (E) a monomer.   The colored curable resin composition according to any one of claims 1 to 11, further comprising (F) a polymerization initiator.   The color filter which has a pixel formed using the colored curable resin composition as described in any one of Claims 1 thru | or 12.   14. A liquid crystal display device comprising: the color filter according to claim 13 and a liquid crystal driving substrate facing each other, and liquid crystal sealed therein.   An organic EL display comprising the color filter according to claim 13.