JP2009052031A - Coloring curable resin composition, color filter, liquid crystal display, and organic el display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring curable resin composition satisfying both flatness and wetting spreadability of a pixel which are brought conventionally into a trade-off relation in many cases, when forming the pixel for a color filter by an ink-jet method. <P>SOLUTION: This coloring curable resin composition is a coloring material used for forming the color filter by the ink-jet method, contains at least (a) a color material, (b) a binder resin, (c) an organic solvent and (d) a dispersant, and has 0.4 wt.% or more to 5 wt.% or less of water content. An amino value of the (d) dispersant in term of an effective solid content is 10 mg KOH/g or more, in the coloring curable resin composition, and the (d)dispersant is an A-B block copolymer and/or an A-B-A block copolymer comprising B-blocks having an amino group in its side chain, and A-blocks having no amino group in its side chain. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored curable resin composition, a color filter, a liquid crystal display device, and an organic EL display. Specifically, in the production of a color filter, a colored curable resin composition having long-term ejection stability suitable for pixel formation by an inkjet method, and a color filter having pixels formed using the colored curable resin composition, The present invention relates to a liquid crystal display device and an organic EL display provided with this color filter.

A color filter manufacturing technique in which a coloring material is driven into a pixel bank, that is, a substantially rectangular recessed area surrounded by a black matrix, by an inkjet method has been put into practical use. The basic quality required for color filters is that the flatness of the coating film in the pixel is good, that is, there is no unevenness or uneven color, and there are no coating defects such as wrinkles or cracks. It is important in ensuring. In addition, to stabilize the manufacturing process and improve yield, wetting and spreading of droplets that land in a liquid-repellent bank is good, that is, the required droplet volume can be filled while avoiding color mixing between pixels. is important.
However, the mechanism of drying of fine droplets landed by the ink jet method has not been sufficiently elucidated theoretically yet. Therefore, the process conditions and ink composition (coloring material, dispersant, binder resin, organic solvent, etc.) for obtaining a dry coating film with good flatness without causing the coating film defects as described above are empirical. And there was no choice but to adjust by trial and error.
Similarly, the mechanism of the wetting and spreading of minute droplets landed by the ink jet method has not yet been fully theoretically elucidated. In other words, wetting and spreading behavior of macro droplets of about 1 μL can be described almost accurately by macro liquid properties such as contact angle and viscosity, but wetting and spreading behavior of micro droplets of several to several tens of pL by the inkjet method. Are not necessarily correlated with them. For this reason, when the fluidity of the ink is increased, the spreadability of the wettability is often in a trade-off relationship with the flatness of the pixel.
For example, Patent Document 1 discloses a method for preventing the unevenness of the colored layer by adding a surfactant to suppress the temperature change of the surface tension. However, since the surfactant described in the document significantly lowers the surface tension of the ink itself, there is a possibility that the ejection stability by the ink jet method may be impaired. Furthermore, although it is difficult to predict with general common sense, the ink described in the document has a problem of reducing the wet-spreading property of the fine droplets landed by the ink jet method.
Japanese Patent Laid-Open No. 7-216276

As described above, even if the ink is prepared so that it spreads well as the behavior of macro droplets, the desired characteristics can be obtained because the factors that inhibit the wetting and spreading act when micro droplets are formed. Often not. In addition, since it is extremely difficult to identify the above-mentioned inhibition factors themselves, the wetting and spreading properties of microdroplets are adjusted by trial and error depending on the combination of ink constituent materials (coloring material, dispersant, binder resin, organic solvent, etc.) However, it has been difficult to eliminate the relationship between the flatness of the pixel and the trade-off described above.
An object of the present invention is to solve the above-described problems in the prior art, and in particular, when forming a pixel of a color filter by an ink jet method, the flatness of the pixel, which has often been in a trade-off relationship in the past, and An object of the present invention is to provide a colored curable resin composition satisfying both wet spreading properties.
Another object of the present invention is to provide a high-quality color filter and a liquid crystal display device having pixels formed using such a colored curable resin composition.

  In the present invention, an earnest analysis of the inhibition factors for the wettability of the fine droplets, the detailed mechanism is unknown, but the influence of the amount of moisture in the colored curable resin composition is large, the amount of moisture It has been found that by adjusting the height relatively high, the wet spreading property is improved and the flatness of the pixel is also improved. In particular, as a dispersant component, an A- having an amine value of 10 mgKOH / g or more (in terms of effective solid content) composed of a B-block having an amino group in the side chain and an A-block having no amino group in the side chain. When a dispersant that is a B block copolymer and / or an ABA block copolymer or a dispersant that is a graft copolymer containing a nitrogen atom is used, the effect is particularly remarkable. I found it.

  By providing a colored curable resin composition having good wettability and pixel flatness in an inkjet method, and manufacturing a color filter with a high quality yield, a liquid crystal display device can be provided in a large amount at a low cost.

  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 does not exceed the gist thereof. It is not limited to the contents of.

[1] Colored curable resin composition
The colored curable resin composition of the present invention contains at least (a) a color material, (b) a binder resin, (c) an organic solvent, and (d) a dispersant, and has a water content of 0.4% by weight or more. It is characterized by being not more than% by weight.
In addition, although each structural component of the colored curable resin composition of this invention is demonstrated below, "(meth) acryl", "(meth) acrylate", etc. are "acryl and / or methacryl", "acrylate and / or Or “methacrylate”, for example, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”. In addition, “(co) polymer” means “single polymer (homopolymer) and / or copolymer (copolymer)”.
In the following, “total solid content” refers to all components in the curable resin composition of the present invention other than the solvent components described later.
Moreover, below, the weight average molecular weight (Mw) of resin ((co) polymer) is the value of polystyrene conversion measured by GPC (gel permeation chromatography).
In the following, the colored curable resin composition may be simply referred to as “ink”.

[1-1] (a) Color material
(A) A coloring material means what colors the coloring curable resin composition of this invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. 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. Note that “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, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 254, and the like.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Of these, C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 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, and the like. Of these, C.I. I. Pigment Green 7, 36 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-described various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

The average primary particle size of these pigments is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less.
The primary particle diameter of the pigment was determined by the following method. That is, the pigment was ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment was obtained by observation with a transmission electron microscope (TEM). The primary particle size was measured from this image, the number average value was calculated, and the average primary particle size was determined.
Examples of the dye that can be used as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

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

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
Among these, it is preferable to use a pigment for the colorant (a) mainly in that light resistance and / or weather resistance and fastness of the coating film finally obtained are excellent. Further, in terms of color tone adjustment, pigments and dyes may be used in combination as necessary.

  In the colored curable resin composition of the present invention, the proportion of the color material (a) relative 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%. It is 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 color material is too small, the coloring power is lowered, the film thickness becomes too thick with respect to the color density, and there is a case where the gap control at the time of forming a liquid crystal cell is adversely affected. On the other hand, if the content ratio of (a) the coloring material is too large, the dispersion stability deteriorates and there is a risk that problems such as re-aggregation and thickening occur.

[1-2] (b) Binder resin
The colored curable resin composition of the present invention comprises (b) a binder resin as an essential component. (B) The binder resin may be, for example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118. Known polymer compounds described in JP-A-2003-233179 and the like can be used, and (b) a particularly preferable binder resin will be described below.

(B-1): “Unsaturated monobasic acid in at least part of the epoxy group of the copolymer with respect to the copolymer of epoxy group-containing (meth) acrylate and other radical polymerizable monomer Or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction "
As one of particularly preferred resins, “with respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, at least a part of the epoxy group of the copolymer is unsaturated. A resin obtained by adding a basic acid, or a resin obtained by adding a polybasic acid anhydride to at least a part of hydroxyl groups generated by the addition reaction (hereinafter referred to as “(b-1)” resin. There is). More specifically, “an epoxy group contained in the copolymer with respect to a copolymer of 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radical polymerizable monomer. Resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the compound, and adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl group generated by the addition reaction.

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

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

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 C carbon atoms. 3 may be 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 has 5 to 6 carbon atoms. Is preferred.
Especially, as a structure represented by General formula (1), the structure represented by following formula (1a), (1b), or (1c) is preferable.
By introducing these structures into the binder resin, when the colored curable resin composition of the present invention is used for a color filter or a liquid crystal display element, the heat resistance of the colored curable resin composition is improved, It is possible to increase the strength of pixels formed using the colored curable resin composition.
In addition, the mono (meth) acrylate which has a structure represented by General formula (1) may be used individually by 1 type, and may use 2 or more types together.

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

In the formula (2), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents a structure represented by the general formula (1).
In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (1) is: Among repeating units derived from “other radical polymerizable monomers”, those containing 5 to 90 mol% are preferable, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable. preferable.

  The “other radical polymerizable monomer” other than the mono (meth) acrylate having the structure represented by the general formula (1) is not particularly limited. Specifically, for example, styrene, vinyl aromatics in which the α-, o-, m-, or p-position of styrene is substituted with an alkyl group, nitro group, cyano group, amide group, ester group, or the like; butadiene , Dienes such as 2,3-dimethylbutadiene, isoprene, chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (n) propyl (meth) acrylate, (iso) propyl (meth) acrylate, (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 , Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid Decyl, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, (meta ) Propargyl acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, ( (Meth) acrylic acid furyl, (meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl, ( (Meth) acrylic acid-1 , 1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenyl (meth) acrylate Such as methyl, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. (Meth) acrylic acid esters; (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (Meth) acrylates such as (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenylamide, etc. (Meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl compounds such as N-vinylpyrrolidone, vinylpyridine, vinyl acetate; Unsaturated dicarboxylic acid diesters such as diethyl acid, diethyl maleate, diethyl fumarate and diethyl itaconate; monoesters such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide Maleimides; N- (meth) acryloylphthalimide and the like.

Among these “other radical polymerizable monomers”, in order to impart excellent heat resistance and strength to the colored curable resin composition, it was selected from styrene, benzyl (meth) acrylate, and monomaleimide. It is effective to use at least one kind. In particular, in the repeating unit derived from “another radical polymerizable monomer”, the content of the repeating unit derived from at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 70 mol. % Is preferable, and 3 to 50 mol% is more preferable.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.

  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 carried out 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 performed dropwise in a solvent that has been heated and stirred. Further, the monomer may be added dropwise while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.
If the epoxy group-containing (meth) acrylate is too small, the amount of unsaturated monobasic acid or polybasic acid anhydride described below may be insufficient, while the epoxy group-containing (meth) acrylate is too much. If the amount of the other radical polymerizable monomer is too small, heat resistance and strength may be insufficient.

Subsequently, an unsaturated monobasic acid (polymerizable component) and, if necessary, a polybasic acid on the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radical polymerizable monomer React with anhydride.
As the unsaturated monobasic acid to be added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples include (meth) acrylic acid; crotonic acid; o-, m- or p-vinylbenzoic acid; the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These 1 type may be used independently and may use 2 or more types together.
By adding such a component, it is possible to impart polymerizability to the (b-1) resin.

  These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. When the addition ratio of the unsaturated monobasic acid is too small, there is a concern that the residual epoxy group may adversely affect the temporal stability of the colored curable resin composition. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.
By adding such a component, it is expected that the composition of the present invention is improved in wettability in the pixel bank.

  These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%. Adjustment of the addition ratio within this range is considered to be effective for controlling the wettability of the composition. However, if the addition ratio is too small, the above effect cannot be expected. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be.
A glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl group.
Both of these may be added.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. As commercial products, for example, trade names “Denacol EX-111”, “Denacol EX-121”, “Denacol EX-141”, “Denacol EX-145”, “Denacol EX-146”, “Denacol EX-146” manufactured by Nagase Chemical Industries, Ltd. Denacol EX-171 "," Denacol EX-192 "and the like.
The resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

  (B-1) The polystyrene-converted weight average molecular weight (Mw) of the resin measured by GPC is preferably from 3,000 to 100,000, particularly preferably from 5,000 to 50,000. When the molecular weight is less than 3000, the film strength may be inferior, and when it exceeds 100000, the viscosity of the resin increases, and the inkjet dischargeability of the composition using the resin tends to deteriorate. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

(B-2): Carboxyl group-containing linear resin
The carboxyl group-containing linear resin (hereinafter sometimes referred to as “(b-2) resin”) is not particularly limited as long as it has a carboxyl group, and is usually a polymerizable monomer containing a carboxyl group. It is obtained by polymerizing a monomer.
Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Adipic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2 -(Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyl Oxybutyl succinic acid, 2- (meta Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; Monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone; hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid, or Examples thereof include monomers added with acids or anhydrides such as anhydrides thereof. A plurality of these may be used.
Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.

The (b-2) resin may be a copolymer obtained by copolymerizing the above carboxyl group-containing polymerizable monomer with another polymerizable monomer having no carboxyl group.
Other polymerizable monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate , Benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy (Meth) acrylic esters such as ethyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; vinyl aromatics such as styrene and its derivatives Vinyl compounds such as N-vinylpyrrolidone; N-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide; polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl Examples thereof include macromonomers such as (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, and polycaprolactone macromonomer. These may be used in combination.

Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, They are butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide.
(B-2) The resin may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like. Is mentioned. By copolymerizing these with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.

(B-2) Specific examples of the resin include (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and cyclohexyl (meth). Polymeric monomers not containing hydroxyl groups such as acrylate and cyclohexylmaleimide, and hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate Copolymer; (meth) acrylic acid and (meth) acrylic acid ester such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. Copolymer; (meth) acrylic Copolymers of acid and styrene; a copolymer of (meth) acrylic acid and styrene and α- methylstyrene; a copolymer of (meth) acrylic acid and cyclohexyl maleimide.
From the viewpoint of excellent pigment dispersibility, a copolymer resin containing benzyl (meth) acrylate is particularly preferable.

The acid value of the (b-2) resin in the present invention is usually 30 to 500 mgKOH / g, preferably 40 to 350 mgKOH / g, more preferably 50 to 300 mgKOH / g. In addition, from the viewpoint of storage stability of the composition, a lower acid value is preferable.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-20000 normally, Preferably it is 3000-50000, More preferably, it is 4000-30000. If the weight average molecular weight is too small, the stability of the colored curable resin composition tends to be inferior. If it is too large, the viscosity of the resin increases, and the inkjet dischargeability of the composition tends to deteriorate.

(B-3): (b-2) Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin
A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the (b-2) resin (hereinafter sometimes referred to as “(b-3) resin”) is also particularly preferable.
The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.
For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- Acyclic epoxy group-containing unsaturated compounds such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but from the viewpoints of heat resistance and dispersibility of the pigment described later, alicyclic epoxy group-containing unsaturated compounds are used. preferable.

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

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

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

The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 mgKOH / g, preferably 20 to 150 mgKOH / g, more preferably 30 to 150 mgKOH / g.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-100000 normally, Preferably it is 4000-50000, More preferably, it is 5000-30000.

(B-4): (Meth) acrylic resin
(B-4) (Meth) acrylic resin (hereinafter sometimes referred to as “(b-4) resin”), (meth) acrylic acid and / or (meth) acrylic acid ester as monomer components And a polymer obtained by polymerizing these. Preferred (meth) acrylic resins include, for example, (b-4-1): a polymer formed by polymerizing monomer components containing (meth) acrylic acid and benzyl (meth) acrylate, and (b-4- 2): A polymer obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (4) and / or (5) can be mentioned.

In 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 formula (5), R ^1b represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X is represented by the following formula (6). A group or an adamantyl group which may be substituted;

In Formula (6), R ^2b , R ^3b , and R ^4b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, and L ¹ and L ² represent a divalent linking group. L ³ in formula (5) may be bonded to R ^3b or R ^4b in formula (6) to form a ring. Further, two or more of L ¹ and L ² in formula (6) and L ³ in formula (5) may be bonded to each other to form a ring.

(B-4-1): a polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate (hereinafter sometimes referred to as “(b-4-1) resin”)
(B-4-1) The resin is preferably used in that it has a high affinity with the pigment.
The ratio of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component is not particularly limited, but (meth) acrylic acid in the total monomer component is usually 10 to 90% by weight, preferably 15%. -80% by weight, more preferably 20-70% by weight. Moreover, benzyl (meth) acrylate is 5 to 90 weight% normally in all the monomer components, Preferably it is 15 to 80 weight%, More preferably, it is 20 to 70 weight%. If the amount of (meth) acrylic acid is too much or too little, dispersion tends to be difficult.

(B-4-2): a polymer (hereinafter referred to as “(b-4-2) resin”) obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (4) and / or (5). Sometimes called)
First, the compound of General formula (4) is demonstrated.
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 from the viewpoint of heat resistance. R ^1a and R ^2a may be the same type of substituent or different substituents.

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

  (B-4-2) The ratio of the ether dimer in the monomer component in obtaining the resin is not particularly limited, but is usually 2 to 60% by weight, preferably 5 to 55% in the total monomer components. % By weight, more preferably 5 to 50% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, the transparency, heat resistance, etc. There is a possibility that the performance of the coating film becomes insufficient.

Then, the compound of General formula (5) is demonstrated.
In General Formula (5), R ^1b preferably represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
In the general formula (6), the organic groups represented by R ^2b , R ^3b and R ^4b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, or an acyl group. Carboxyl group or acyloxy group, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkenyl group having 3 to 18 carbon atoms. Group, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, or an acyloxy group having 1 to 15 carbon atoms, and more preferably. Is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms.

Preferred substituents among R ^2b , R ^3b and R ^4b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
L ¹ and L ² are divalent linking groups, L ³ is not particularly limited as long as it is a divalent linking group or a direct bond, but at least either L ¹ or L ² is a linking group having 1 or more carbon atoms. Is preferred. L ¹ , L ² and L ³ are each independently a direct bond, alkylene having 1 to 15 carbon atoms, —O—
, -S-, -C (= O)-, alkenylene having 1 to 15 carbon atoms, phenylene, or a combination thereof is preferable.
As a preferable combination of L ¹ , L ² and L ³ , L ³ is a direct bond, alkylene having 1 to 5 carbon atoms, or a ring formed by combining with R ^3b or R ^4b, and L ¹ and L ² are C1-C5 alkylene.
Moreover, as a preferable thing of General formula (6), the compound shown by following General formula (7) can be mentioned.

In the formula (7), R ^2b , R ^3b , R ^4b , L ¹ and L ² have the same meaning as in the formula (6), and R ^5b and R ^6b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, Represents an amino group or an organic group.
In the general formula (7), the organic groups represented by R ^5b and R ^6b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, or An acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, and 1 carbon atom. -15 alkoxy group, C1-C15 alkylthio group, C1-C15 acyl group, C1-carboxyl group, or C1-C15 acyloxy group, more preferably C1-C15. Or an alkyl group having 10 to 10 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms.
Preferred substituents among R ^5b and R ^6b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
In addition, the alkyl group of R ^1b , the organic groups of R ^2b , R ^3b and R ^4b , the divalent linking group of L ¹ , L ² and L ³ , and the adamantyl group of X are each independently a substituent. Specific examples thereof may include the following substituents.

Halogen atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group A linear or branched alkyl group having 1 to 18 carbon atoms such as n-heptyl group, n-octyl group and t-octyl group; carbon number such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and adamantyl group A cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyl A linear or branched alkoxy group having 1 to 18 carbon atoms such as a xyl group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octyloxy group; methylthio group, Ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, a linear or branched alkylthio group having 1 to 18 carbon atoms such as t-octylthio group; an aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; carbon such as benzyl group and phenethyl group Aralkyl group having 7 to 18 carbon atoms; straight chain or branched chain having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group, hexenyloxy group Alkenyloxy group; represented by -OCOR ^18; carboxyl group; an acyl group represented by -COR ^17; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group An acyloxy group represented by —NR ¹⁹ R ²⁰ ; an acylamino group represented by —NHCOR ²¹ ; a carbamate group represented by —NHCOOR ²² ; a carbamoyl group represented by —CONR ²³ R ²⁴ ; Carboxylic acid ester group represented by ²⁵ ; sulfamoyl group represented by —SO ₃ NR ²⁶ R ²⁷ ; sulfonic acid ester group represented by —SO ₃ R ²⁸ ; 2-thienyl group, 2-pyridyl group, furyl group , Oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide A saturated or unsaturated heterocyclic group such as a side group; a trialkylsilyl group such as a trimethylsilyl group;

R ^{17 to} R ²⁸ are each a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or An aralkyl group which may have a substituent is represented.
Moreover, the positional relationship of the said substituent is not specifically limited, When it has a some substituent, it may be same or different.
Specific examples of the compound represented by the general formula (5) include the following.

  In the monomer component constituting the (b-4-2) resin according to the present invention, the ratio of the general formula (5) is not particularly limited, but usually 0.5 to 60% by weight in the total monomer components. The amount is preferably 1 to 55% by weight, more preferably 5 to 50% by weight.

(B-4-3) (b-4) Resin
The (b-4) resin in the present invention preferably has an acid group, including the (b-4-1) resin and the (b-4-2) resin. By having an acid group, the resulting colored curable resin composition can be cured by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter abbreviated as acid-epoxy curing). It can be set as a curable resin composition. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more.

  (B-4) In order to introduce an acid group into the resin, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter “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, Among these, (meth) acrylic acid is especially preferable.
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 And 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.

(B-4) When the monomer component for obtaining the resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited. It is -70 weight%, Preferably it is 10-60 weight%.
Moreover, (b-4) resin may have a radically polymerizable double bond.

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

(B-4) When the monomer component for obtaining the resin also includes the monomer for introducing the radical polymerizable double bond, the content ratio is not particularly limited, but usually the total amount It is 5-70 weight% in a body component, Preferably it is 10-60 weight%.
When (b-4) resin of this invention is (b-4-2) resin, it is preferable to have an epoxy group.
In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one kind or two or more kinds.
(B-4) When the monomer component for obtaining the resin also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but usually 5% of all monomer components. It should be ˜70% by weight, preferably 10 to 60% by weight.

(B-4) The monomer component for obtaining the resin may contain other copolymerizable monomers, if necessary, in addition to the essential monomer component.
Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene; Substituted butadiene compounds; ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like.
Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.
Further, in particular, when a part or all of the resin (b-4) is used as a dispersant as described later, it is preferable to use benzyl (meth) acrylate, and the content thereof is usually all monomer components. The content is 1 to 70% by weight, preferably 5 to 60% by weight.

  (B-4) When the monomer component in obtaining the resin also includes the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by weight or less, and 85% by weight or less. More preferred.

Next, (b-4) resin production method (polymerization method) will be described.
There is no particular limitation on the method for polymerizing the monomer component, and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. , Depending on the molecular weight of the target polymer. The polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C. Regarding the polymerization concentration, the polymerization concentration is preferably 5 to 50%, more preferably 10 to 40%.

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

When the monomer component is polymerized, a polymerization initiator may be used as necessary. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amyl. Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane Carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) and the like. These polymerization initiators may be used alone or in combination of two or more.
The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is not gelled. It is usually 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer components, in that thousands to tens of thousands of polymers can be obtained.

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

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

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

Although the weight average molecular weight of (b-4) resin of this invention is not restrict | limited in particular, Preferably the weight average molecular weight of polystyrene conversion measured by GPC is 2000-200000, More preferably, it is 4000-100000. When the weight average molecular weight exceeds 200,000, the viscosity becomes high and the ink jet discharge property may be deteriorated. On the other hand, when the weight average molecular weight is less than 2000, the film strength tends to be insufficient.
(B-4) When resin has an acid group, a preferable acid value is 30-500 mgKOH / g, More preferably, it is 50-400 mgKOH / g.

  Of the resin components (b-4), examples of the (b-4-2) resin include the compounds described in JP-A-2004-300203 and JP-A-2004-300204.

(B-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “(b-5) resin”)
The epoxy acrylate resin is obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester portion to the epoxy resin, and further reacting with a polybasic acid anhydride. Is synthesized. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc., manufactured by Yuka Shell Epoxy Co., Ltd.), bisphenol A type epoxy resin Epoxy resin obtained by the reaction of alcoholic hydroxyl group and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F-type resin (for example, oily shell epoxy) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc.") manufactured by the company, epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin and epichlorohydrin (for example, Japan “NER-74” manufactured by Kayaku Co., Ltd. 6 ”(epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg“ YX-4000 ”manufactured by Yuka Shell Epoxy), phenol novolac type epoxy resin (eg Nippon Kayaku) “EPPN-201” manufactured by Yakuhin, “EP-152”, “EP-154” manufactured by Yuka Shell Epoxy, “DEN-438” manufactured by Dow Chemical Co.), (o, m, p-) cresol Novolac-type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), Tris Phenolmethane type epoxy resin (for example, “EPPN-501”, “EPN-502”, “Nippon Kayaku Co., Ltd.” PPN-503 ”), fluorene epoxy resin (for example, cardo epoxy resin“ ESF-300 ”manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (“ Celoxide 2021P ”,“ Celoxide EHPE ”manufactured by Daicel Chemical Industries, Ltd.) ), Dicyclopentadiene type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example, “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “EXA-7200” manufactured by Dainippon Ink, Japan “NC-3000” and “NC-7300” manufactured by Kayaku Co., Ltd.) and epoxy resins represented by the following structural formula (see JP-A-4-355450) can be suitably used.

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

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

  As for the molecular weight of the said copolymerization type epoxy resin, about 1000-200000 is preferable. The amount of the first component of the copolymerization type epoxy resin used is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably 70% by weight based on the second component of the copolymerization type epoxy resin. % By weight or less, particularly preferably 50% by weight or less.

As such a copolymer type epoxy resin, specifically, “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, “CP-50S”, “CP-50M”, “CP-20MA” and the like are exemplified.
The molecular weight of the raw material epoxy resin is usually in the range of 200 to 200,000, preferably 300 to 100,000, as the weight average molecular weight in terms of polystyrene measured by GPC. If the weight average molecular weight is less than the above range, there are many cases where problems occur in the film-forming property. May become difficult.

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

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

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

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

A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be carried out by continuing the reaction under the same conditions as the addition reaction of α, β-unsaturated carboxylic acid or ester thereof.
The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mgKOH / g, more preferably in the range of 20 to 140 mgKOH / g. In addition, from the viewpoint of storage stability of the composition, a lower acid value is preferable.

In addition, as the (b-5) resin in the present invention, for example, a naphthalene-containing resin described in JP-A-6-49174; JP-A-2003-89716, JP-A-2003-165830, JP-A-2005-325331 Examples thereof include fluorene-containing resins described in JP-A No. 2001-354735, JP-A Nos. 2005-126684, 2005-55814, and 2004-295084.
Moreover, the commercially available epoxy acrylate resin which has a carboxyl group can also be used, and "ACA-200M" by Daicel Corporation etc. can be mentioned as a commercial item, for example.

As the binder resin, for example, an acrylic binder described in JP-A-2005-154708 can also be used.
Among the various resins described above, as the binder resin (b) in the present invention, (b-1): “for a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, Resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the copolymer, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction Is particularly preferred. Further, the molecular weight is particularly preferably about 5000 to 20000 as a polystyrene-reduced weight average molecular weight measured by GPC.
In addition, the various resins described above can form a high-density color pixel having excellent adhesion to the substrate when used in combination with (d) a dispersant described later.
Specifically, part of (b) the binder resin is used in the dispersion treatment step described later together with the above-mentioned (d) dispersant. At this time, the binder resin (b) is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the color material (a).
Thus, as the (b) binder resin used in the dispersion treatment step, various resins described in the section of (b) binder resin can be used, and in particular, (b-4) (meth) acrylic resin. Among them, a polymer ((b-4-2) resin) obtained by polymerizing a monomer component essentially containing the compound represented by the general formula (4) is most preferable.
(D) When used in a dispersion treatment step together with a dispersant, the acid value of the (b) binder resin is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, most preferably 150 mgKOH / g or more, and 500 mgKOH / g g or less is preferable, 300 mgKOH / g or less is more preferable, and 200 mgKOH / g or more is most preferable. In addition, from the viewpoint of the storage stability of the composition, it is preferable that the acid value is low.
When used in the dispersion treatment step together with (d) the dispersant, the weight average molecular weight in terms of polystyrene measured by GPC of the (b) binder resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more. It is preferably 200000 or less, more preferably 50000 or less, and most preferably 30000 or less. If the molecular weight is too large, the viscosity of the resin increases, and the inkjet dischargeability of the composition may be deteriorated. If the molecular weight is too small, the dispersion stability may decrease.

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, the binder resin is (b-1): “the copolymer of epoxy group-containing (meth) acrylate and other radical polymerizable monomer. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the polymer, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, The following (b-6) epoxy group-containing resins are preferably used in combination.
In addition, when manufacturing a color filter by the inkjet method, it is not always necessary to include a photopolymerization initiator, which will be described later. It is preferable to use an ink having a thermosetting property (colored curable resin composition) from the viewpoint of increasing the color temperature.

(B-6) Resin having an epoxy group
The resin having a (b-6) epoxy group (hereinafter sometimes referred to as “(b-6) resin”) according to the present invention is not particularly limited in its structure as long as it has an epoxy group in the resin. Among them, among them, preferred are alicyclic polyether compounds having an epoxy group in the side chain, polyglycidyl ether compounds, polyglycidyl ester compounds, polyglycidyl amine compounds (meth) acrylates having an epoxy group alone or A polymer obtained by combining two or more kinds, or a polymer containing an epoxy group-containing (meth) acrylate constituent unit usually containing other monomers in an amount of 10 to 70 mol%, preferably 15 to 60 mol%. Can be mentioned.
Specific examples of the resin containing an epoxy group include the following compounds.

(b-6-1) An alicyclic polyether compound having an epoxy group in the side chain
Examples of the alicyclic polyether compound having an epoxy group in the side chain include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, Examples include polycyclohexyl ether having an epoxy group in the side chain. As a commercial item of such a compound, EHPE3150 (made by Daicel Chemical Industries Ltd.) etc. are mentioned, for example.

(B-6-2) Polyglycidyl ether compound
Examples of the polyglycidyl ether compound include polyethylene glycol diglycidyl ether type epoxy, bis (4-hydroxyphenyl) diglycidyl ether type epoxy, and bis (3,5-dimethyl-4-hydroxyphenyl) diglycidyl ether type. Epoxy, diglycidyl ether type epoxy of bisphenol F, diglycidyl ether type epoxy of bisphenol A, diglycidyl ether type epoxy of tetramethylbisphenol A, diglycidyl ether type epoxy of ethylene oxide-added bisphenol A, dihydroxy fluorene type epoxy, di Hydroxyalkyleneoxylfluorene type epoxy, bisphenol A / aldehyde novolac type epoxy, phenol novolac type epoxy, crezo Lunovolak type epoxy and polyglycidyl ether resins include bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, polymerized epoxy resin of phenol and naphthalene. And phenol resin type epoxy resin.
These (poly) glycidyl ether compounds may be those obtained by reacting the remaining hydroxyl group with an acid anhydride or dibasic acid to introduce a carboxyl group.

(B-6-3) Polyglycidyl ester compound
Examples of the polyglycidyl ester compound include a diglycidyl ester type epoxy of hexahydrophthalic acid, a diglycidyl ester type epoxy of phthalic acid, and the like.

(B-6-4) Polyglycidylamine compound
Examples of the polyglycidylamine compound include diglycidylamine type epoxy of bis (4-aminophenyl) methane, triglycidylamine type epoxy of isocyanuric acid, and the like.

(B-6-5) Other monomers
Other examples include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth) acrylic acid-3,4- (Meth) having an epoxy group such as epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl A polymer containing one acrylate alone or a combination of two or more, or a (meth) acrylate structural unit having an epoxy group usually contains 10 to 70 mol%, preferably 15 to 60 mol% of another comonomer. The polymer made into is mentioned. Among these, as the copolymer, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, (meth) acrylic Esters of (meth) acrylic acid such as phenyl acid, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and styrene And vinyl aromatic compounds such as α-methylstyrene, p-methylstyrene, and vinylnaphthalene. A preferred (meth) acrylate having an epoxy group is glycidyl (meth) acrylate. Preferred copolymers include dicyclopentanyl (meth) acrylate and α-styrene.

The epoxy group used in the (b-6) resin used in the present invention is usually a 1,2-epoxy group, but for the purpose of improving stability over time or imparting flexibility, A 3-epoxy group (oxetane) or a 4,3-epoxycyclohexyl group can also be used.
In addition, in the resin (b-6) according to the present invention, those that do not contain an aromatic ring or those that are unsubstituted or contain a phenyl group having a substituent at the p (para) position suppresses discoloration due to heat treatment. Therefore, it is preferable. Examples of such an epoxy compound include a bisphenol A type epoxy resin, an epoxy resin having a fluorene skeleton which may have a substituent, and a copolymer of glycidyl (meth) acrylate.

The content of the (b-6) resin is usually 0.5 mol% or more, preferably 1.0 mol% or more, and usually 70 mol% or less, preferably 65, based on the entire resin (b-1). It is less than mol%. (B-6) If the amount of the resin is too small, the chemical resistance improving effect may be insufficient. If the amount is too large, the storage stability may be insufficient.
(B-6) The weight average molecular weight (Mw) of the resin is usually 300 or more, preferably 500 or more, and usually 100,000 or less, preferably 50,000 or less. If the molecular weight is too small, the film strength tends to be inferior, and if it is too large, the liquid properties as a coating solution may become non-Newtonian. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2.0 or more and 5.0 or less.

(B-6) The ratio of the resin is generally 0% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, based on the total solid content in the curable resin composition of the present invention. The amount is usually 50% by weight or less, preferably 40% by weight or less, and more preferably 35% by weight or less. (B-6) If the proportion of the resin is too small, the chemical resistance improving effect may be insufficient, and if it is too large, the storage stability may be insufficient.
The above-mentioned various binder resins may be used alone or in combination of two or more.
In the colored curable resin composition of the present invention, the content of the (b) 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. When the content of the binder resin is less than this range, the film becomes brittle and the adhesion to the substrate may be lowered. On the other hand, if it exceeds this range, the film hardness may be insufficient or the coloring power may be insufficient.

[1-3] (c) Organic solvent
The colored curable resin composition of the present invention contains (c) an organic solvent as an essential component. (C) The organic solvent has a function of adjusting the viscosity by dissolving or dispersing the respective components.
Such (c) organic solvent may be any one that can dissolve or disperse each component constituting the colored curable resin composition.
Specifically, 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-methoxy Butanol, triethylene glycol monomethyl ether Triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;

  Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, glycol alkyl ether acetates such as ethylene glycol diacetate;
Glycol diacetates such as 1,3-butylene glycol diacetate, propylene glycol diacetate, 1,6-hexanediol diacetate;
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, and 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. Also, if the boiling point is too high, the effect of inhibiting drying of the curable resin composition is high as described later, but there are many residual solvents in the coating film even after heat firing, which may cause quality problems. 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, from several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable that (c) the organic solvent 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 (c) 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-hexanol diester. Examples include acetate and triacetin.

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

  The proportion of the organic solvent (c) 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 Is 95% by weight or less. (C) If there is too much organic solvent, the solid concentration becomes too low and it becomes unsuitable for forming a coating film, or the viscosity of the ink becomes too high, which hinders the stability of the composition. In some cases, the discharge stability may be lowered when the ink jet method is applied.

[1-4] (d) Dispersant
The colored curable resin composition of the present invention contains (d) a dispersant as an essential component. (D) The type of the dispersant is not particularly limited, but (d-1): a graft copolymer containing a nitrogen atom, (d-2): an acrylic block copolymer containing a nitrogen atom, (d -3): It is preferable to contain one or more dispersants selected from urethane resin dispersants.

(D-1): a graft copolymer containing a nitrogen atom, and (d-2): an acrylic block copolymer containing a nitrogen atom, the nitrogen atom contained therein has an affinity for the pigment surface Thus, it is presumed that the portion other than the nitrogen atom increases the affinity for the medium, thereby contributing to the improvement of the dispersion stability as a whole.
The performance of the dispersant is greatly influenced by its adsorption behavior on the solid surface. Regarding the relationship between the molecular architecture and the adsorption behavior, it is known that when the same unit is used, the adsorption behavior is excellent in the order of random copolymerization <graft copolymer <block copolymer. (For example, Jones and Richards, “Polymers at Surfaces and Interfaces” p281).

Although the detailed mechanism is unknown, the following can be inferred.
That is, in the case of a normal random copolymer, the monomer constituting the copolymer has a high probability of being stably arranged in the copolymer sterically and / or electrically during the formation of the polymer. . Since the portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, it may be an obstacle when adsorbed on the pigment. In contrast, for resins with a controlled molecular arrangement such as graft copolymers or block copolymers, the part that prevents the adsorption of the dispersant should be placed at a position away from the adsorption part of the pigment and the dispersant. Can do. That is, an optimum portion for adsorption can be arranged in the adsorption portion between the pigment and the dispersant, and a portion suitable for it can be arranged in the portion requiring solvent affinity. In particular, for the dispersion of a colorant containing a pigment having a small crystallite size, it is presumed that this molecular arrangement affects good dispersibility.

(D-1): Graft copolymer containing nitrogen atom
A graft copolymer containing nitrogen atoms (hereinafter sometimes referred to as “(d-1) copolymer”) is preferable in that (a) the colorant can be dispersed very efficiently. The reason is not clear, but it has a structure that can positively eliminate the part (molecule) that obstructs the adsorption of the pigment and the dispersant around the adsorption part to the pigment. It is guessed. (D-1) As a copolymer, what has a repeating unit containing a nitrogen atom in a principal chain is preferable. Especially, it is preferable to have a repeating unit represented by Formula (II) or / and a repeating unit represented by Formula (III).

^{Wherein, R 51} represents an alkylene group having 1 to 5 carbon atoms, A represents either a hydrogen atom or the following formula (IV) ~ (VI).
In the formula (II), R ⁵¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, or a propylene group, preferably 2 to 3 carbon atoms, and more preferably Is an ethylene group. A represents a hydrogen atom or any one of the following formulas (IV) to (VI), preferably formula (IV).

Wherein ^{(III), R 51} and A have the same meanings as ^{R 51} and A in the formula (II).

In Formula (IV), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as a butylene group, a pentylene group, and a hexylene group is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In formula (V), Y ₁ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as an ethylene group or a propylene group, or an alkylene group having 1 to 4 carbon atoms such as an ethyleneoxy group or a propyleneoxy group. An alkyleneoxy group is preferred. W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as an ethylene group, a propylene group or a butylene group, and among them, an alkylene group having 2 to 3 carbon atoms such as an ethylene group or a propylene group is preferable. Y ₂ represents a hydrogen atom or —CO—R ⁵² (R ⁵² represents an alkyl group having 1 to 10 carbon atoms such as an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Group, a C2-C5 alkyl group such as a pentyl group is preferred.). q represents an integer of 1 to 20, preferably an integer of 5 to 10.

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

Moreover, repeating units other than Formula (II) and Formula (III) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. The graft copolymer of the present invention preferably has a terminal of —NH ₂ or —R ⁵¹ —NH ₂ (R ⁵¹ is synonymous with R ⁵¹ ).
The (d-1) copolymer may have a branched main chain or a branched chain.
(D-1) The amine value of the copolymer is usually 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g, and more preferably 15 to 40 mgKOH / g. If the amine value is too high or too low, the dispersion stability may be lowered and the viscosity may become unstable, and if it is too high, the electrical characteristics after the liquid crystal panel is formed may be lowered.

  (D-1) The polystyrene-converted weight average molecular weight measured by GPC of the copolymer is preferably 3000 to 50000, and particularly preferably 5000 to 20000. If the weight average molecular weight is less than 3000, aggregation of the coloring material cannot be prevented and the viscosity or gelation may occur. When the weight average molecular weight exceeds 50,000, the viscosity itself becomes high, and (c) the solubility in an organic solvent may be insufficient. In addition, due to the steric hindrance of the molecule itself, (a) adsorption to the coloring material is hindered, so that dispersibility may be reduced.

(D-1) As a method for synthesizing the copolymer, a known method can be employed. For example, a method described in JP-B-63-30057 can be used.
In the present invention, a commercially available graft copolymer having the same structure as described above can also be applied.

(D-2): (meth) acrylic block copolymer having nitrogen atom
A (meth) acrylic block copolymer having a nitrogen atom (hereinafter sometimes referred to as “(d-2) copolymer”) is preferable in that (a) the colorant can be dispersed very efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed on the pigment.
(D-2) As a copolymer, an A- block comprising a B-block having a quaternary ammonium base and / or amino group in the side chain and an A-block having no quaternary ammonium base and amino group. B block copolymers and / or ABA block copolymers are preferred.

(D-2) The B-block constituting the copolymer has a quaternary ammonium base and / or an amino group.
The quaternary ammonium base is preferably —N ⁺ R ³¹ R ³² R ³³ · Z ⁻ (where R ³¹ , R ³² and R ³³ are each independently a hydrogen atom, or an optionally substituted cyclic or chain) Or two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure, and Z ⁻ represents a counter anion). With the quaternary ammonium base represented. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

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

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

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

In the general formula (VII), R ³¹ , R ³² and R ³³ each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R ³¹ , R ³² , and R ³³ may be bonded to each other to form a cyclic structure. R ³⁴ represents a hydrogen atom or a methyl group. X ¹ represents a divalent linking group, and Z ⁻ represents a counter anion.
In the general formula (VII), the hydrocarbon groups of R ³¹ , R ³² and R ³³ are each independently a substituent having an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms. preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.
In the general formula (VII), examples of the divalent linking group X ¹ include an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ³⁵ —, —COO—R ³⁶ — (provided that R ³⁵ and R ³⁶ is each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ³⁷ —O—R ³⁸ —: R ³⁷ and R ³⁸ are each independently Represents an alkylene group), etc., and is preferably —COO—R ³⁶ —.

Examples of the counter anion Z ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .
As the B-block, those having an amino group are particularly preferred. 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 preferable allyl group or an aralkyl group which may have a substituent is represented by the following formula.

(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. An example of such a partial structure is a structure represented by the following formula.

  Two or more kinds of partial structures containing the specific quaternary ammonium base and / or amino group as described above may be contained in one B-block. In that case, the two or more quaternary ammonium bases and / or amino group-containing partial structures may be contained in the B-block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base and an amino group may be contained in B-block, As an example of this partial structure, the part derived from the below-mentioned (meth) acrylic acid ester monomer Examples include the structure. The content in the B-block of the quaternary ammonium base and the partial structure not containing an amino group is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the amino group-free partial structure is not contained in the B-block.

On the other hand, (d-2) the A-block constituting the copolymer can be copolymerized with the monomer constituting the B-block, and has both a quaternary ammonium base and an amino group. There is no particular limitation as long as it is composed of no monomer.
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 ) (Meth) acrylate monomers such as octyl acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate; And (meth) acrylate monomers such as acrylic acid chloride; vinyl acetate monomers; and polymer structures obtained by copolymerizing comonomers such as glycidyl ether monomers such as allyl glycidyl ether and crotonic acid glycidyl ether.
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 (I) is preferable.

(In the formula, n represents an integer of 1 to 5, and R ¹ represents a hydrogen atom or a methyl group.)
The partial structure represented by the above formula (I) 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.
In addition, from the viewpoint of improving the familiarity to the non-polar part of the solvent by imparting appropriate hydrophobicity, the (meth) acrylic acid ester system in which the A-block is represented by the following general formula (VIII) It preferably contains a monomer-derived partial structure.

(In General Formula (VIII), R ³⁹ represents a hydrogen atom or a methyl group. R ⁴⁰ may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents an allyl group or an aralkyl group which may have a substituent.)
R ⁴⁰ is preferably a cyclic group from the viewpoint of high affinity with the pigment and easy compatibility.
Two or more partial structures derived from the (meth) acrylic acid ester monomer may be contained in one A-block. Of course, the A-block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in an A-block that does not contain a quaternary ammonium base, each partial structure is contained in the A-block in any form of random copolymerization or block copolymerization. May be. When the A-block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the A-block of the partial structure other than the (meth) acrylate monomer is , Preferably 0 to 99% by weight, more preferably 0 to 85% by weight.

The (d-2) copolymer used in the present invention is an AB block or ABA block copolymer type polymer compound composed of such B-block and A-block. Such a block copolymer is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. 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 Papers, 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, 101, 2921-2990, etc. can be employed.

  The amine value (effective solid content conversion) in 1 g of the AB block copolymer and the ABA block copolymer according to the present invention is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more. More preferably, it is 50 mgKOH / g or more, particularly preferably 80 mgKOH / g or more, and usually 300 mgKOH / g or less.

The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably lower, usually 100 mgKOH / g or less, 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. If the molecular weight of the block copolymer is too small, the dispersion stability tends to decrease. is there.
In the present invention, a commercially available acrylic block copolymer having the same structure as described above can also be applied.

(D-3): Urethane resin dispersant
The urethane resin dispersant (hereinafter sometimes referred to as “(d-3) dispersant”) includes a polyisocyanate compound, a compound having one or two hydroxyl groups in the same molecule, and active in the same molecule. A urethane resin obtained by reacting hydrogen with a compound having a tertiary amino group is particularly preferred.

  Examples of the polyisocyanate compound include aroma such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω ' -Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane; xylylene diisocyanate, α, α, α ', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate; lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate And triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane) and tris (isocyanatephenyl) thiophosphate; and their trimers, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination of two or more. .

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, or one terminal hydroxyl group of these compounds is an alkyl group having 1 to 25 carbon atoms and alkoxy. Or a mixture of two or more of these.
Examples of the polyether glycol include polyether diol, polyether ester diol, or a mixture of two or more of these. As the polyether diol, those obtained by homopolymerizing or copolymerizing alkylene oxide, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, Or the mixture of 2 or more types of those is mentioned. Examples of the polyether ester diol include those obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or an anhydride thereof, or by reacting polyester glycol with an alkylene oxide. And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

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

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like.
Of these compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred. In addition, the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

  In the compound having an active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom includes a hydroxyl group, an amino group, a thiol group, etc. Among these, a hydrogen atom in the functional group is mentioned, and an amino group, particularly a primary amino group hydrogen atom is preferable. As the tertiary amino group, for example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, or the like, and the dialkylamino group are linked to form a heterocyclic structure. More specifically, an imidazole ring or a triazole ring can be mentioned. Among them, a dimethylamino group and an imidazole ring are preferable because of excellent dispersion stability.

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

  As the tertiary amino group is a nitrogen-containing heterocycle, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include nitrogen-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring; nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. It is done. Further, specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H. -1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino Examples include -1,4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4- Triazole and the like are preferable.

  The preferred use ratio of these (d-3) dispersant raw materials is usually 10 to 200 parts by weight, preferably 20 parts by weight of a compound having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. -190 parts by weight, more preferably 30-180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2-25 parts by weight, preferably 0.3-24 parts by weight. .

The (d-3) dispersant is produced according to a known method for producing a urethane resin. Solvents used in the production are usually ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone; esters such as ethyl acetate, butyl acetate and cellosolve; benzene, toluene, xylene and hexane Hydrocarbons such as diacetone alcohol, some alcohols such as isopropanol, sec-butanol and tert-butanol; halogenated hydrocarbons such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide An aprotic polar solvent such as N-methylpyrrolidone or dimethyl sulfoxide is used. Moreover, as a catalyst at the time of manufacture, a normal urethanization reaction catalyst is used. For example, tin systems such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate; iron systems such as iron acetylacetonate and ferric chloride; tertiary amine systems such as triethylamine and triethylenediamine Can be mentioned.
Further, the introduction amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g, more preferably 5 to 80 mgKOH in terms of the amine value of the dispersant after the reaction. / G, more preferably in the range of 10-60 mg KOH / g. When the amine value is out of the above range, the dispersion ability tends to be lowered. In addition, when an isocyanate group remains in a dispersing agent by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the temporal stability of the dispersing agent becomes high.

  The weight average molecular weight in terms of polystyrene measured by GPC of these (d-3) dispersants is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to It is in the range of 50,000. When the molecular weight is 1,000 or less, the dispersibility and dispersion stability tend to be inferior. When the molecular weight is 200,000 or more, the solubility is lowered and the dispersibility is inferior.

(D-4): Other dispersant
The dispersant used in the colored curable resin composition of the present invention may contain other dispersants in addition to the various dispersants described above.
Other dispersants include, for example, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate, polyester phosphate, sorbitan aliphatic ester dispersant, fat Group-modified polyester dispersants and the like.
Specific examples of such a dispersant include EFKA (manufactured by EFKA Chemicals Beebuy (eFKA)), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by Geneka), and KP (manufactured by Shin-Etsu Chemical). Kogyosha Chemical Co., Ltd., Polyflow (Kyoeisha Chemical Co., Ltd.), Ajispar (Ajinomoto Co., Inc.) and other series names can be selected from commercially available products. These polymer dispersants may be used alone or in combination of two or more.

In the colored curable resin composition of the present invention, the content ratio of the (d) dispersant is usually 95% by weight or less, preferably 65% by weight or less, more preferably, based on the pigment contained in the (a) color material. It is 50% by weight or less, usually 5% by weight or more, preferably 7% by weight or more, and particularly preferably 10% by weight or more. (D) When the content ratio of the dispersant is too small, (a) the adsorption to the coloring material is insufficient, aggregation cannot be prevented, and the viscosity may be increased or gelled. It may worsen and problems such as re-aggregation and thickening may occur. On the other hand, if the amount is too large, the ratio of the pigment is relatively reduced, so the coloring power is low, the film thickness is too thick for the color density, and when used in a color filter, the cell gap in the liquid crystal cell forming process. Poor control may occur.
In the colored curable resin composition of the present invention, among the various dispersants described above, (d-1): a graft copolymer containing a nitrogen atom, or (d-2): an acrylic block copolymer. When it contains, the effect is exhibited notably.
(D-2) Among the dispersants, an AB block copolymer and / or A- consisting of a B-block having an amino group in the side chain and an A-block having no amino group in the side chain. Examples thereof include a dispersant containing a B-A block copolymer and having an amine value of 10 mgK0H / g (in terms of effective solid content) or more. The amine value (in terms of effective solid content) of the dispersant is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 50 mgKOH / g or more, particularly preferably 80 mgKOH / g or more. Usually 300 mgKOH / g or less.
The amine value of the dispersant is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HCLO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. 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 represents the amount of the dispersant sample weighed [g], V represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
In addition, the colored curable resin composition of the present invention contains a part of the above-mentioned (b) binder resin together with the (d) dispersant in the dispersion treatment step when preparing the colored curable resin composition described later. Therefore, both of them may serve as a dispersant. In this way, a resin that performs the same function as the dispersant may be referred to as a “dispersion resin”.

[1-5] Water Content in Composition The colored curable resin composition of the present invention has a water content of 0.4% by weight or more, preferably 0.7% by weight or more, more preferably, in the composition. It is 1.0% by weight or more, 5.0% by weight or less, preferably 4.0% by weight or less, more preferably 3.0% by weight or less. If the water content is too small, sufficient effects cannot be obtained with respect to the improvement of wettability and pixel flatness of the colored curable resin composition, and if the water content is too high, the colored curable resin composition As a result, corrosion may occur in the nozzle head member or the like, or ejection stability may be reduced.
The water content in the colored curable resin composition can be measured and adjusted by known means. For example, the water content of the colored curable resin composition prepared by the method described later is measured by the Karl Fischer method, and the deficiency is compensated by dropping water into the colored curable resin composition, The molecular sieve (for example, “Molecular Sieves 3A 1/16” manufactured by Wako Pure Chemical Industries, Ltd.) previously vacuum-dried in an oven or the like can be dehydrated by adding to the colored curable resin composition and stirring.
Examples of other dehydration means include a method using a porous material such as silica gel and alumina, and a dehydrating agent such as sodium sulfite (Na ₂ SO ₃ ) and calcium chloride, but are not limited to these methods. Absent.

[1-6] (e) Monomer
The colored curable resin composition of the present invention preferably contains (e) a 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).
The ethylenic compound is, for example, a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system described later when the colored curable resin composition of the present invention is irradiated with actinic rays. It is. In addition, the monomer in this invention means the concept opposite to what is called a polymeric substance, and also contains a dimer, a trimer, and an oligomer other than a monomer in 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 and a (meth) acryloyl group-containing hydroxy compound.

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 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.

Other 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, more preferred polyfunctional monomers having an acid group are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate, which are 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.
When the colored curable resin composition of the present invention is used for producing an inkjet color filter, the monomer (e) is preferably a linear monomer or a monomer having a relatively small molecular weight, for example, ethoxylated trimethylol. Propane 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 color material (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. Hereinafter, it is preferably 100% by weight or less, more preferably 80% by weight or less.

[1-7] (f) Photopolymerization initiation system and / or thermal polymerization initiation system
The colored curable resin composition of the present invention preferably includes (f) a photopolymerization initiation system and / or a thermal polymerization initiation system for the purpose of curing the coating film. But you can.
In particular, when the colored curable resin composition of the present invention includes (b) a resin having an ethylenic C = C double bond as a binder resin, or (e) when an ethylenic compound is included as a monomer. , A photopolymerization initiating system that has a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical and / or a thermal polymerization initiation system that generates a polymerization active radical by heat Is preferably blended. In the present invention, the component (f) as the photopolymerization initiation system is a photopolymerization initiator (hereinafter arbitrarily referred to as (f1) component) to an accelerator (hereinafter arbitrarily referred to as (f2) component), It means a mixture in which an additive such as a sensitizing dye (hereinafter arbitrarily referred to as component (f3)) is used in combination.

[1-7-1] Photopolymerization initiation system
The colored curable resin composition of the present invention may contain (f) a photopolymerization initiation system. The (f) photopolymerization initiation system is usually used as a mixture of (f1) a photopolymerization initiator and an additive such as (f3) a sensitizing dye and (f2) a polymerization accelerator that are added as necessary. , A component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiation system (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-difluoro-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 halomethylated triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl). ) -S-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s -Triazine etc. are mentioned.

Examples of the α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like 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 derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 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; benzoic acid ester 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; anthrone derivatives such as benzanthrone and the like.

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.
These (f1) photopolymerization initiators and (f2) polymerization accelerators may be used alone or in combination of two or more.

  In the colored curable resin composition of the present invention, the total content of these (f1) photopolymerization initiator and (f2) polymerization accelerator is usually 0.1% by weight or more, preferably 0.8% in the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less. If this content is extremely low, the sensitivity to exposure light may be insufficient.

  Further, (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 and the like; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP-A 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP No. -107761, JP-A-5-210240, it may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

  Among these 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%.

[1-7-2] Thermal polymerization initiation system
Specific examples of the (f) thermal polymerization initiation system (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. 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 is not sufficiently cured, and the durability as a color filter may be insufficient. If the amount is too large, the degree of thermal shrinkage increases, and cracking and cracking may occur after thermosetting. In addition, storage stability may be reduced. Therefore, it is preferable to select in the range of 0 to 30% by weight, particularly 0 to 20% by weight, based on the total solid content of the colored curable resin composition of the present invention.

[1-8] Surfactant
The colored curable resin composition of the present invention may contain a surfactant as a surfactant as long as the effects of the invention are not impaired. 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, “SH8400” manufactured by Tore Silicone; silicone surfactants such as “KP341” manufactured by Silicone; “FC430” manufactured by Sumitomo 3M; Dainippon Ink and Chemicals, Inc. "F470" manufactured by KK; fluorine-based surfactants such as "DFX-18" manufactured by Neos; polyoxyethylene-based surfactants such as "Emulgen 104P" and "Emulgen A60" manufactured by Kao Corporation, etc. . Of these, silicone surfactants are preferable, and so-called polyether-modified or aralkyl-modified silicone surfactants having a structure in which a side chain of a polyether group or an aralkyl group is added to polydimethylsiloxane are more preferable.

Two or more 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. Of these, a combination of silicone surfactant / fluorine surfactant is preferable.
Examples of the silicone surfactant / fluorine surfactant combination include a polyether-modified silicone surfactant / oligomer-type fluorine surfactant combination. 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.

[1-9] Other components
In addition to the above components, the colored curable resin composition of the present invention includes a dispersion aid, an organic carboxylic acid or / and an organic carboxylic acid anhydride, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface protective agent, It may contain an adhesion improver, a development improver, and the like.
The dispersion aid is used for improving the dispersibility of the pigment in the colorant (a), improving the dispersion stability, and the like. For example, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, Examples thereof include derivatives of isoindolinone, dioxazine, 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, usually 30% by weight or less, based on the color material component (a). Preferably it is 200 weight% or less, More preferably, it is 10 weight% or less, Most preferably, it is 5 weight% or less. This is because if the addition amount is small, the effect may not be 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 contains an organic carboxylic acid or / and an organic carboxylic acid anhydride having a molecular weight of 1000 or less in order to improve pattern adhesion when used in a color filter as described later. Also good. These are preferably contained when the urethane resin dispersant is included as the above-mentioned (d) dispersant.
Specific examples of the organic carboxylic acid include aliphatic carboxylic acids and aromatic carboxylic acids.
Aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, (meth) acrylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid And dicarboxylic acids such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid; and tricarboxylic acids such as tricarbaric acid and aconitic acid. Examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and a carboxylic acid in which a carboxyl group is bonded to the phenyl group through a carbon bond.

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. Specifically, maleic acid, malonic acid, succinic acid, and itaconic acid are preferable.
Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specifically, acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, Aliphatic carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride Things. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.
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. Specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred.

In the colored curable resin composition of the present invention, the content of these organic carboxylic acids or / and organic carboxylic anhydrides is usually 0.01% by weight or more, preferably 0.03% by weight or more, based on the total solid content. More preferably, it is 0.05% by weight or more, and is usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less.
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 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.
First, (a) the color material, (c) the organic solvent, and (d) the dispersant are weighed in predetermined amounts, and in the dispersion treatment step, (a) the pigment in the color material is dispersed 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 performing this dispersion treatment, the pigment is made into fine particles, so that the coating characteristics of the colored curable resin composition are improved and the transmittance of the product color filter substrate and the like is improved.

  When dispersing the pigment, it is preferable to use (b) a part of the binder resin and a dispersion aid as appropriate. 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 to the pigment dispersion obtained by the above dispersion treatment, (b) a binder resin, (c) an organic solvent, and in some cases, an optional component (e) a monomer, and (f) initiation of photopolymerization. A colored curable resin composition is obtained by mixing the system and / or the thermal polymerization initiation system and 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 filtered 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 components are dissolved or dispersed in (c) an organic solvent. This is supplied onto the substrate to form the color filter and the constituent members of the liquid crystal display device.
Hereinafter, a method for producing a color filter using the colored curable resin composition of the present invention, a liquid crystal display device (panel) and an organic EL display using the same will be described.

[3-1] Color filter A method for producing a color filter by the ink jet method using the colored curable resin composition of the present invention will be described.
In the inkjet method, a partition pattern (black matrix) is first provided on a substrate, and pixel forming ink is directly applied in the pattern 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 wall for preventing RGB inks that are driven into the pixels from being mixed, so that the conventional photo 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 including a black color material from a conventionally used chromium compound such as chromium, chromium oxide and chromium nitride, and a black matrix made of a light-shielding metal material such as nickel and tungsten alloy. A resin black matrix (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 made hydrophilic on the surface of the transparent substrate and lyophobic on the BM pattern by chemical treatment or physical treatment, respectively.
Next, in a substantially rectangular recessed area surrounded by the resin BM pattern, the colored curable resin composition of the present invention is used to draw with an ink jet apparatus, and the composition is dried, photocured and / or thermally cured. A color filter is obtained by completely curing 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.

  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, for example, as follows using the above-described color filter of the present invention.
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 the counter substrate. 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.

[3-3] Organic EL Display When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1, a pattern formed from a colored resin composition on a transparent support substrate 10 ( That is, a color filter in which a pixel black and a resin black matrix (not shown) provided between adjacent pixels 20 are formed is produced, and the organic protective layer 30 and the inorganic oxide film 40 are formed on the color filter. The organic EL element 100 can be manufactured by stacking the organic light-emitting body 500 through the substrate. Note that at least one of the pixels 20 is manufactured using the colored resin composition of the present invention. As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, Inc., August 20, 2004, light emission, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 manufactured in this manner, etc. Thus, an organic EL display can be produced.
The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

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.
(Example)

(Synthesis Example 1: Synthesis of Binder Resin (b-4-2) (Polymer formed by Polymerizing Monomer Component Essentially with Compound Represented by Formula (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 2: Binder resin (b-1) (for a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, at least a part of the epoxy group of the copolymer) Synthesis of a resin obtained by adding an unsaturated monobasic acid to a resin, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction)
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2'-azobis-2-methyl 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours.
Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours.
The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 8400, acid value of 80 mgKOH / g.

(Example 1)
As a pigment, C.I. I. 8.6 g of CI Pigment Green 36, C.I. I. 8.6 g of Pigment Yellow 150, 5.8 g of the dispersant (A) described below in terms of solid content, 5.8 g of the binder resin obtained in Synthesis Example 1 in terms of solid content, and butyl carbitol acetate ( (Diethylene glycol mono-n-butyl ether acetate) 115.2 g was mixed and stirred and homogenized, then 300 g of zirconia beads having a particle diameter of 0.5 mm was added, and the mixture was shaken with a paint conditioner for 5 hours to disperse the pigment dispersion. Produced.
Separately, 3.0 g of the epoxy resin EHPE3150 manufactured by Daicel Chemical Co., Ltd. as the binder resin, 7.5 g of the binder resin obtained in Synthesis Example 2, 1.4 g of Irgacure 907 manufactured by Ciba Geigy Co., Ltd. as the polymerization initiator, and the solvent A clear base was prepared by mixing 16.2 g of butyl carbitol acetate.
While stirring 22.0 g of the pigment dispersion, 28.0 g of the clear base was dropped and mixed, and then filtered through a 5 μm membrane filter to obtain 90.0 g of a uniform colored curable resin composition.
Further, 0.8 g of pure water was added to the colored curable resin composition while stirring, and the water content was measured. As a result, the water content in the colored curable resin composition was 1.0% by weight.
The water content in the composition was measured by the method described later.

<Dispersant (A): BYK-LPN6919 manufactured by Big Chemie>
As the dispersant, a methacrylic AB block copolymer having a tertiary amino group was used. 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): The ratio of the repeating unit represented by the following formula (ii) in the A-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 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%].)

<Method for measuring moisture content>
About the coloring curable resin composition obtained in the Example and the comparative example, the moisture content was measured on the following conditions by the Karl Fischer method.
Apparatus: KF moisture meter CA-100 manufactured by Dia Instruments
・ Injection volume: 40-50 μL
・ Anode / catholyte: Aquamicron AS / CXU
・ End Sens. : 0.1 μg / sec

  Then, according to the following evaluation methods, the wet spreading property of the obtained colored curable resin composition was evaluated. The results are shown in Table-1. When an amount equivalent to 200 pl was applied to the central portion of the pixel bank by the ink jet method, it spreads to 70% of the pixel area after 3 minutes. Similarly, a coating equivalent to 2000 pl was applied and left for 5 minutes, and then the coated substrate was dried by a reduced pressure treatment. As a result, a flat color filter film surface having 90% of the pixel area was obtained.

(Comparative Example 1)
A colored curable resin composition was prepared in exactly the same procedure except that pure water was not added to the colored curable resin composition of Example 1. The water content of this colored curable resin composition was measured and found to be 0.1% by weight. This colored curable resin composition was also evaluated for wet spreadability according to the following evaluation method. The results are shown in Table-1.

(Evaluation methods)
Asahi Glass Co., Ltd. Alkali-free glass substrate (AN635) 10cm square 0.7mm thick coated with curable resin composition for black matrix, matrix with line width 20μm, opening width 220μm × 700μm, thickness 2.0μm by photolithography method A pattern was formed.
After the substrate is subjected to a liquid repellent treatment by a fluorine plasma treatment, an amount equivalent to 200 pl is applied to the central portion of each pixel of the black matrix pattern (that is, the central portion of the pixel bank) by an inkjet method for 3 minutes. The area ratio (%) of the wetting spread to the subsequent pixel area was evaluated. Similarly, a coating equivalent to 2000 pl was applied and left for 5 minutes, and then the coated substrate was dried by a decompression process. Then, the surface shape was measured with a three-dimensional laser microscope, and the area ratio (%) of the flat portion to the pixel area was calculated. evaluated.
The wetting spread was rated as x for less than 40%, ◯ for 40% or more and less than 60%, and ◎ for 60% or more.
The pixel flatness was evaluated as x for less than 60%, Δ for 60% or more and less than 80%, and ◯ for 80% or more.

(Synthesis Example 3: Synthesis of Dispersant (d-1) (Graft Copolymer Containing Nitrogen Atom))
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 2)
As a pigment, C.I. I. 8.6 g of CI Pigment Green 36, C.I. I. 5.7 g of Pigment Yellow 150, 3.8 g of the dispersant obtained in Synthesis Example 3 (as solid content), 3.8 g of the binder resin obtained in Synthesis Example 1 in terms of solid content, and 1,3 as the solvent -95.8 g of butylene glycol diacetate was mixed and stirred and homogenized, and then 300 g of zirconia beads having a particle size of 0.5 mm were added and dispersed by shaking for 5 hours with a paint conditioner to prepare a pigment dispersion.
Separately, 2.6 g of the epoxy resin EHPE3150 manufactured by Daicel Chemical Co., Ltd. as the binder resin, 1.1 g of the binder resin obtained in Synthesis Example 2, 0.5 g of Irgacure 907 manufactured by Ciba Geigy Co., Ltd. as the polymerization initiator, and the solvent A clear base was prepared by mixing 10.0 g of butyl carbitol acetate.
While stirring 53.5 g of the pigment dispersion, 46.5 g of the clear base was dropped and mixed, and then filtered through a 5 μm membrane filter to obtain 90.0 g of a uniform colored curable resin composition.
Furthermore, when 0.4 g of pure water was added to the colored curable resin composition while stirring, and the water content was measured, the water content in the colored curable resin composition was 0.5% by weight.

(Example 3)
In Example 2, a colored curable resin composition was prepared in exactly the same procedure except that 0.9 g of pure water added to the colored curable resin composition was used. When the water content of this colored curable resin composition was measured, it was 1.1% by weight.

Example 4
In Example 2, a colored curable resin composition was prepared in exactly the same procedure except that the amount of pure water added to the colored curable resin composition was 3.3 g. When the water content of this colored curable resin composition was measured, it was 3.7% by weight.

(Comparative Example 2)
In Example 2, a colored curable resin composition was prepared in exactly the same procedure except that pure water was not added to the colored curable resin composition. The water content of this colored curable resin composition was measured and found to be 0.1% by weight.

Using the colored curable resin compositions obtained in Examples 2 to 4 and Comparative Example 2, wetting spread and pixel flatness were evaluated in the same manner as in Example 1 and Comparative Example 1 described above. The results are shown in (Table 2).

   From the results of Tables 1 and 2, it is understood that a colored curable resin composition having good wet spread and pixel flatness can be obtained by adjusting the water content to be larger than that in the case of using a normal liquid preparation method. It was.

  According to the present invention, when forming a pixel of a color filter by an inkjet method, a colored curable resin composition satisfying both the flatness of the pixel and the wet spreading property, which has often been in a trade-off relationship in the past. Can be provided.

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

Explanation of symbols

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

Claims (10)

A coloring material used for forming a color filter by an inkjet method, comprising at least (a) a coloring material, (b) a binder resin, (c) an organic solvent, and (d) a dispersant, and having a water content of 0.4. A colored curable resin composition, characterized by being from 5% by weight to 5% by weight. (D) AB block copolymer and / or ABA block in which the dispersant comprises a B-block having an amino group in the side chain and an A-block having no amino group in the side chain. The colored curable resin composition according to claim 1, comprising a dispersant made of a copolymer, wherein the amine value in terms of effective solid content of the dispersant is 10 mg KOH / g or more. (D) The colored curable resin composition according to claim 2, wherein the A-block of the dispersant contains 5 to 40 mol% of a partial structure represented by the following formula (I) in the A-block.
(Here, n represents an integer of 1 to 5. R ¹ represents a hydrogen atom or a methyl group.) (D) The coloring curable resin composition of Claim 1 in which a dispersing agent contains the dispersing agent which consists of a graft copolymer containing a nitrogen atom. (C) The colored curable resin composition according to any one of claims 1 to 4, wherein the organic solvent contains a solvent having a boiling point of 180 ° C or higher (boiling point under a pressure of 101.25 [hPa]). object. The colored curability according to claim 5, wherein the content of the solvent having a boiling point of 180 ° C or higher (boiling point under a pressure of 1013.25 [hPa]) is 50% by weight or more based on the total amount of the organic solvent (c). Resin composition. (C) The colored curable resin composition according to any one of claims 1 to 6, wherein the content of the alcohol with respect to the total amount of the organic solvent is 20% by weight or less. The color filter which has a pixel formed using the colored curable resin composition as described in any one of Claims 1 thru | or 7. A liquid crystal display device comprising the color filter according to claim 8. An organic EL display comprising the color filter according to claim 8.