WO2009141924A1 - Composition de résine durcissable colorante, filtre coloré, affichage à cristaux liquides et affichage el organique - Google Patents

Composition de résine durcissable colorante, filtre coloré, affichage à cristaux liquides et affichage el organique Download PDF

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Publication number
WO2009141924A1
WO2009141924A1 PCT/JP2008/066885 JP2008066885W WO2009141924A1 WO 2009141924 A1 WO2009141924 A1 WO 2009141924A1 JP 2008066885 W JP2008066885 W JP 2008066885W WO 2009141924 A1 WO2009141924 A1 WO 2009141924A1
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Prior art keywords
group
resin composition
curable resin
meth
colored curable
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PCT/JP2008/066885
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English (en)
Japanese (ja)
Inventor
康嗣 山内
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三菱化学株式会社
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Priority claimed from JP2008135900A external-priority patent/JP2009007560A/ja
Application filed by 三菱化学株式会社 filed Critical 三菱化学株式会社
Priority to CN2008801287444A priority Critical patent/CN102015904A/zh
Priority to KR1020107022440A priority patent/KR20110018292A/ko
Publication of WO2009141924A1 publication Critical patent/WO2009141924A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

  • 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 flatness and wettability of a coating film suitable for pixel formation by an inkjet method, and a color formed using this colored curable resin composition The present invention relates to a filter, a liquid crystal display device including the color filter, and an organic EL display.
  • a pixel forming method by using a coloring material (ink) in a pixel bank that is, a substantially rectangular recessed region surrounded by a black matrix by an inkjet method has been put into practical use.
  • the basic quality required for the color filter is that the flatness of the coating film serving as a pixel is good, that is, there is no color unevenness due to unevenness or bias, and there are no coating film defects such as wrinkles or cracks. .
  • the ink droplets that have landed inside the liquid-repellent bank have good wetting and spreading, that is, there is no color mixing between pixels, and the pixel bank It is important that the required amount of ink can be filled therein.
  • Patent Document 1 discloses a method for preventing unevenness of a colored layer by adding a surfactant to suppress the temperature change of the ink surface tension.
  • the surfactant described in this document greatly reduces the surface tension of the ink itself, which may impair the ejection stability of the ink jet.
  • the ink described in this document has a problem of reducing the wet-spreading property of the fine droplets landed by the inkjet method.
  • An object of the present invention is to solve the above-described problems in the prior art, and in particular, when forming color filter pixels by the inkjet method, the flatness of the pixels, which has often been a trade-off relationship in the past. It is another object of the present invention to provide a colored curable resin composition (ink) satisfying both wet spreading properties. Another object of the present invention is to provide a high-quality color filter formed using such a colored curable resin composition, and a liquid crystal display device and an organic EL display provided with the color filter.
  • the present inventors have unclear the detailed mechanism of action, but are colored and cured whose surface tension is moderately low and the interfacial tension with the substrate is not too high. It was found that both the flatness and wettability of the pixel are satisfied by using the conductive resin composition. By reducing the surface tension of the colored curable resin composition, the flatness of the pixels is improved. However, if the surface tension is too low, the ejection stability of the composition from the inkjet nozzle tends to be impaired. In addition, by not increasing the interfacial tension with the base material too high, wetting and spreading properties within the pixel bank can be improved.
  • a specific surfactant is effective for obtaining such a colored curable resin composition. Specifically, it has been found that when a dilute solution of a surfactant prepared under certain conditions has a contact angle and surface tension within a specific range, the use of the surfactant is effective. Moreover, in order to obtain such a colored curable resin composition, it is effective to contain a fluorosurfactant including a polyether polymer having a specific structure having a short pendant alkyl fluoride group. I found. It has been found that by using such a surfactant, wetting spreadability in the pixel bank and surface flatness of the resulting pixel can be improved without significantly reducing the surface tension of the composition. Reached.
  • the effect of the present invention becomes even more remarkable when a dispersant containing a block copolymer having a specific structure is used in combination. That is, the gist of the present invention is as follows. [1] In a colored curable resin composition containing at least (a) a color material, (b) a binder resin, (c) an organic solvent, and (g) a surfactant, (C) 80% by weight or more of the organic solvent is occupied by the solvent (c-1) having a boiling point of 180 ° C.
  • a colored curable resin characterized in that a 0.02% by weight solution of (g) surfactant prepared using the solvent (c-1) satisfies the following conditions (1) and (2): Composition.
  • the contact angle with respect to the glass substrate is 10 ° or less.
  • the surface tension ⁇ satisfies ( ⁇ 0 ⁇ 2) ⁇ ⁇ ⁇ 0 with respect to the surface tension ⁇ 0 of the solvent (c-1).
  • R 1 represents an alkylene group having 2 to 6 carbon atoms
  • R 2 represents an alkylene group having 2 to 3 carbon atoms
  • R 3 represents a hydroxyl group or a hydrogen atom
  • G represents 1 to 4 carbon atoms
  • v, w and u each independently represents an integer of 0 to 2
  • x and t each independently represents 1 or 2
  • s represents an integer of 0 to 10
  • n represents 2 Represents an integer of ⁇ 100.
  • a plurality of the following side chains in one molecule May be the same or different groups.
  • the surface tension ⁇ is 28 mN / m or more and less than 30 mN / m.
  • the colored curable resin composition according to any one of [1] to [5], wherein, in the condition (1), a contact angle with respect to the glass substrate is less than 5 °.
  • a contact angle with respect to the glass substrate is less than 5 °.
  • a surfactant In a colored curable resin composition containing at least (a) a color material, (b) a binder resin, (c) an organic solvent, and (g) a surfactant, (C) 80% by weight or more of the organic solvent is occupied by the solvent (c-1) having a boiling point of 180 ° C.
  • a colored curable resin composition wherein the surfactant contains a compound represented by the following general formula (10).
  • R 1 represents an alkylene group having 2 to 6 carbon atoms
  • R 2 represents an alkylene group having 2 to 3 carbon atoms
  • R 3 represents a hydroxyl group or a hydrogen atom
  • G represents 1 to 4 carbon atoms
  • v, w and u each independently represents an integer of 0 to 2
  • x and t each independently represents 1 or 2
  • s represents an integer of 0 to 10
  • n represents 2 Represents an integer of ⁇ 100.
  • the content of (a) the coloring material is 10 to 90% by weight, (b) the content of the binder resin is 1 to 80% by weight, and (c) the content of the organic solvent is 50 to 99% based on the total solid content.
  • AB block copolymer and / or BAB block in which (e) the dispersant is an A block having an amino group in the side chain and a B block having no amino group in the side chain The colored curable resin composition according to [13] above, which contains a copolymer and has an amine value of 10 mg KOH / g (in terms of effective solid content) or more.
  • the solvent (c-1) having a boiling point of 180 ° C.
  • a colored curable resin composition having both excellent pixel flatness and wet spreadability can be provided, so that the color filter can be provided with high quality and high yield.
  • the liquid crystal display device can be manufactured at low cost in large quantities.
  • 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 (g) a surfactant. c) 80% by weight or more of the organic solvent is occupied by the solvent (c-1) having a boiling point of 180 ° C. or higher (boiling point under pressure of 101.25 [hPa]), and the solvent (c-1) is used.
  • the prepared 0.02 wt% solution of the surfactant (g) satisfies the following conditions (1) and (2).
  • the contact angle with respect to the glass substrate is 10 ° or less.
  • the colored curable resin composition of the present invention contains at least (a) a coloring material, (b) a binder resin, (c) an organic solvent, and (g) a surfactant, and (c) 80% by weight of the organic solvent.
  • the solvent (c-1) having a boiling point of 180 ° C. or higher (boiling point under a pressure of 1013.15 [hPa]) accounts for the above, and (g) the surfactant is represented by the following general formula (10). It is characterized by containing a compound.
  • R 1 represents an alkylene group having 2 to 6 carbon atoms
  • R 2 represents an alkylene group having 2 to 3 carbon atoms
  • R 3 represents a hydroxyl group or a hydrogen atom
  • G represents 1 to 4 carbon atoms
  • v, w and u each independently represents an integer of 0 to 2
  • x and t each independently represents 1 or 2
  • s represents an integer of 0 to 10
  • n represents 2 Represents an integer of ⁇ 100.
  • a plurality of molecules per molecule May be the same or different groups.
  • (Meth) acryl”, “(meth) acrylate” and the like are “acryl and / or methacryl”, “acrylate and / or methacrylate”.
  • (co) polymer means “single polymer (homopolymer) and / or copolymer (copolymer)”.
  • Total solid content refers to all components in the curable resin composition of the present invention other than the solvent components described later.
  • the weight average molecular weight (Mw) of the resin ((co) polymer) is a value in terms of polystyrene measured by GPC (gel permeation chromatography).
  • the “amine value” represents an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the weight of KOH equivalent to the amount of base per 1 g of the solid content of the dispersant.
  • the measuring method will be described later.
  • the colored curable resin composition may be simply referred to as “ink”.
  • the (g) surfactant in the present invention is a 0.02% by weight solution of (g) a surfactant prepared using the solvent (c-1) described above. The following conditions (1) and (2) are satisfied. (1) The contact angle with respect to the glass substrate is 10 ° or less. (2) The surface tension ⁇ satisfies ( ⁇ 0 ⁇ 2) ⁇ ⁇ ⁇ 0 with respect to the surface tension ⁇ 0 of the solvent (c-1). By using the surfactant (g) that satisfies the above conditions (1) and (2), it becomes possible to control the interfacial tension and surface tension of the colored curable resin composition with the base material within an appropriate range.
  • the surfactant used in the composition for forming a pixel for a color filter can improve the coating property of the composition by reducing the surface tension of the composition containing the surfactant, or the coating film obtained. It worked to improve surface smoothness.
  • most of them have the function of increasing the interfacial tension with the base material. An increase in the interfacial tension of the composition with the substrate causes a decrease in wet spreadability in the pixel bank of the composition.
  • the colored curable resin composition of the present invention is “(g) 0.02 wt% solution of surfactant prepared using solvent (c-1)” (hereinafter referred to as “(g) surfactant solution”).
  • the wetting and spreading property in the pixel bank is remarkably improved by containing a surfactant having a contact angle of 10 ° or less to the glass substrate.
  • the contact angle of the surfactant solution with respect to the glass substrate is more preferably less than 5 °.
  • the surface tension ⁇ of the surfactant solution is ( ⁇ 0 ⁇ 2) ⁇ ⁇ ⁇ 0 with respect to the surface tension ⁇ 0 of the solvent (c-1).
  • the surface tension ⁇ of the surfactant solution is lower than the surface tension ⁇ 0 of the solvent (c-1) as the solvent. Especially, the case where surface tension (sigma) is 28 mN / m or more and less than 30 mN / m is more preferable.
  • the (g) surfactant in the colored curable resin composition of the present invention is preferably a compound represented by the following general formula (10).
  • R 1 represents an alkylene group having 2 to 6 carbon atoms
  • R 2 represents an alkylene group having 2 to 3 carbon atoms
  • R 3 represents a hydroxyl group or a hydrogen atom
  • G represents a fluorine group having 1 to 4 carbon atoms.
  • v, w and u each independently represents an integer of 0 to 2
  • x and t each independently represents 1 or 2
  • s represents an integer of 0 to 10.
  • n represents an integer of 2 to 100.
  • a plurality of molecules per molecule May be the same or different groups.
  • R 1 is an alkylene group having 2 to 6 carbon atoms.
  • R 1 is preferably an alkylene group having 2 to 4 carbon atoms.
  • R 3 represents a hydroxyl group or a hydrogen atom. When the value of s described later is 0, R 3 is preferably a hydrogen atom, and when s is an integer of 1 to 10, R 3 is preferably a hydroxyl group.
  • v, w and u each independently represent an integer of 0 to 2
  • x and t are each independently 1 or 2
  • s represents an integer of 0 to 10.
  • t and u are both 2 or less, but if these values are 3 or more, steric hindrance may occur, and the desired performance may not be obtained.
  • n represents an integer of 2 to 100, preferably an integer of 5 to 30.
  • n exceeds 100, the molecular weight becomes too large and the solubility may be impaired.
  • n is less than 2, the molecular weight becomes too small, and the stability in the solution may be impaired.
  • a compound represented by the following general formula (0) is particularly preferable.
  • the substituent G represents a fluorinated alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 100.
  • the substituent G represents a fluorinated alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms.
  • the number of carbon atoms is 5 or more, the substituent portion becomes too bulky, and the orientation to the interface may be impaired.
  • a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms is preferred.
  • the number of fluorine-substituted carbon atoms is preferably 1 to 3, more preferably 1 or 2.
  • N in the general formula (0) represents an integer of 2 to 100, preferably an integer of 5 to 30.
  • n exceeds 100, the molecular weight becomes too large and the solubility may be impaired.
  • n is less than 2, the molecular weight becomes too small, and the stability in the solution may be impaired.
  • the most preferable compounds are, for example, the following compounds.
  • the compound represented by the general formula (0) is commercially available, for example, “PF-636”, “PF-656”, “PF-6320”, “PF-6520” (all of which are manufactured by OMNOVA) Name.) Etc. can be used.
  • the colored curable resin composition preferably has a small contact angle with the transparent substrate of the color filter described later.
  • the contact angle with respect to a glass substrate (clean glass) is preferably less than 5 °. In terms of easily achieving such a contact angle, for example, (ii), (iii) and (iv) are particularly preferable among the above four compounds.
  • the compound represented by general formula (0) may be used individually by 1 type, or may use 2 or more types together.
  • the content of the surfactant (g) in the colored curable resin composition of the present invention is usually from 0.005 to 5% by weight, preferably from 0.02 to 1% by weight, more preferably from 0. 05 to 0.5% by weight.
  • the surfactant content is too high, it may be precipitated or the surface tension may be excessively lowered. If it is too low, the pixel flatness may be poor.
  • the surfactant may contain a surfactant other than the above as long as the effects of the present invention are not impaired. In this case, it is preferable to use in the form of replacing a part of the content of the compound represented by the general formula (0). Specific examples of the surfactant that can be used in combination will be described later.
  • the (a) coloring material of the present invention refers to a material that colors the colored curable resin composition of the present invention.
  • a dye or pigment can be used, but a pigment is preferable from the viewpoint of heat resistance, light resistance, and the like.
  • 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.
  • 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.
  • CI described below means a color index (CI).
  • C.I. I. Pigment Red 48 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.
  • C.I. I. Pigment Blue 1 As blue pigment, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.
  • Green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58. Of these, C.I. I. Pigment Green 7, 36, 58.
  • ⁇ As yellow pigment 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,
  • C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.
  • 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.
  • 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. Of these, C.I. I. Pigment violet 19, 23, 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 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 particle size of these pigments is usually 1 ⁇ m, preferably 0.5 ⁇ m or less, more preferably 0.25 ⁇ m or less.
  • the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering DLS.
  • a sufficiently diluted colored curable resin composition usually diluted to a pigment concentration of about 0.005 to 0.2% by weight, provided that there is a concentration recommended by the measuring instrument, According to the concentration
  • dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • azo dyes 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.
  • anthraquinone dyes examples 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.
  • a pigment for the color material (a) it is preferable to use a pigment for the color material (a) in that the 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.
  • 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.
  • Binder resin The colored curable resin composition of the present invention comprises (b) a binder resin as an essential component.
  • binder resins include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, and JP-A-2000-56118.
  • 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.
  • 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”). Can be mentioned.
  • epoxy group-containing (meth) acrylate examples 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.
  • R 1 to R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 7 and R 8 each independently represent a hydrogen atom or carbon number. 1 to 3 alkyl groups, and R 7 and R 8 may be linked to each other to form a ring.
  • 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.
  • the structure represented by following formula (1a), (1b), or (1c) is preferable.
  • the colored curable resin composition of the present invention when 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 the pixel formed using the colored curable resin composition.
  • 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.
  • 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. .
  • R 9 represents a hydrogen atom or a methyl group
  • R 10 represents the structure of the general formula (1).
  • the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (1) is: Among the repeating units derived from “other radical polymerizable monomers”, those containing 5 to 90 mol% are preferred, those containing 10 to 70 mol% are more preferred, and those containing 15 to 50 mol% are particularly preferred 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, or vinyl aromatics such as alkyl, nitro, cyano, amide, or ester derivatives in the ⁇ -, o-, m-, or p-position of styrene; butadiene, 2,3- Dienes such as dimethylbutadiene, isoprene, chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid -N-butyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid
  • (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) acrylic acid such as (meth) acrylic acid N, N-di-iso-propylamide and (meth) acrylic acid anthracenylamide (Meth) acrylic acid anilide, (meth) acryloyl nitrile, 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, diethyl itaconate; mono-such as N-phenylmaleimide, N-cyclohexylmaleimi
  • “other radical polymerizable monomers” in order to impart excellent heat resistance and strength to the colored curable resin composition, from the group consisting of styrene, benzyl (meth) acrylate, and monomaleimide It is effective to use at least one selected.
  • the content ratio of the repeating unit derived from at least one selected from the group consisting of styrene, benzyl (meth) acrylate, and monomaleimide is 1
  • the content is preferably -70 mol%, more preferably 3-50 mol%.
  • a known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the “other radical polymerizable monomer”.
  • the solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
  • the solvent include ethyl acetate; isopropyl acetate; ethylene glycol monoalkyl ether acetates such as cellosolve acetate and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; Propylene glycol monoalkyl ether acetates; Acetic esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, and butyl carbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl ether Dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran;
  • 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, based on 100 parts by weight of the copolymer obtained. 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 for 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.
  • organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.
  • the azo compound catalyst examples include azobisisobutyronitrile and azobiscarbonamide.
  • one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature.
  • the amount of the radical polymerization initiator used is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total monomers used for the copolymerization reaction.
  • 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, a radical polymerization initiator may be added to the solvent, and the monomer may be dropped while the temperature is raised.
  • the reaction conditions can be freely changed according to the target molecular weight.
  • the copolymer of the epoxy group-containing (meth) acrylate and the “other radical polymerizable monomer” may be 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate. , Preferably containing 10 to 95 mol% of repeating units derived from other radical polymerizable monomers, more preferably containing 20 to 80 mol% of the former and 80 to 20 mol% of the latter, Those containing 30 to 70 mol% and the latter 70 to 30 mol% are particularly preferred.
  • an unsaturated monobasic acid (polymerizable component) and, if necessary, a polybasic acid on the epoxy group portion of a copolymer of an epoxy resin-containing (meth) acrylate and another radical polymerizable monomer React with anhydride.
  • 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.
  • (meth) acrylic acid crotonic acid, o-, m-, or p-vinylbenzoic acid
  • the ⁇ -position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group.
  • monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred.
  • These 1 type may be used independently and may use 2 or more types together. By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
  • These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of the unsaturated monobasic acid is too small, the temporal stability of the colored curable resin composition may be lowered.
  • a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.
  • 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.
  • 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.
  • tetrahydrophthalic anhydride and 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 possible to expect improvement in wettability in the pixel bank of the colored curable resin composition of the present invention.
  • 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 in this range is considered effective for controlling the wettability of the composition. However, if the addition ratio is too small, the above-described effect cannot be expected so much.
  • a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.
  • the polybasic acid anhydride was added to improve the photosensitivity, and then generated.
  • a glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to a part of the carboxyl group.
  • the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group.
  • a glycidyl ether compound 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. Incidentally, the structure of such a resin is described in, for example, JP-A-8-297366 and JP-A-2001-89533, and is already known.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the above-mentioned (b-1) resin is preferably from 3000 to 100,000, particularly preferably from 5000 to 50,000. When the weight average molecular weight is less than 3000, heat resistance and film strength may be inferior. When it exceeds 100000, the viscosity of the resin increases, and the discharge properties from the nozzle of a composition using the resin tend to decrease. is there. As a measure of the 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 referred to as “(b-2) resin”) is not particularly limited as long as it has a carboxyl group, and usually a polymerizable monomer containing a carboxyl group is used. Obtained by polymerization.
  • 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 acryloyloxybutyladipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybut
  • the above carboxyl group-containing polymerizable monomer may be copolymerized 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, glyce
  • 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.
  • the resin may further have a hydroxyl group.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, etc. Is mentioned.
  • 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).
  • a polymerizable monomer containing no hydroxyl group such as acrylate and cyclohexylmaleimide, and a hydroxyl group-containing monomer 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 ⁇ - methylstyrene; a copolymer of (meth) acrylic acid and cyclohexyl maleimide.
  • 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 KOH mg / g, preferably 40 to 350 KOH mg / g, more preferably 50 to 300 KOH mg / g.
  • the polystyrene-equivalent weight average molecular weight measured by GPC is usually 2000 to 80000, preferably 3000 to 50000, and more preferably 4000 to 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 ejection properties from the nozzle of the composition using this tend to decrease. There is.
  • a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the (b-2) resin (hereinafter 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.
  • glycidyl (meth) acrylate allyl glycidyl ether, glycidyl- ⁇ -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 viewpoint of heat resistance and dispersibility of the pigment described later, alicyclic epoxy group-containing unsaturated compounds are used. preferable.
  • the alicyclic epoxy group-containing unsaturated compound 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.
  • 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.
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents an alkylene group
  • R 13 represents a divalent hydrocarbon group
  • n is an integer of 1 to 10.
  • 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.
  • the hydrocarbon group for R 13 is preferably one having 1 to 10 carbon atoms, and examples thereof include an alkylene group and a phenylene group.
  • alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
  • a compound represented by the general formula (3c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
  • a known method can be used.
  • a carboxyl group-containing linear 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, benzyl Quaternary ammonium salts such as triethylammonium chloride; epoxy reaction to the carboxyl group of the resin by reaction in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours in the presence of a catalyst such as pyridine and triphenylphosphine.
  • a catalyst such as pyridine and triphenylphosphine.
  • Group-containing unsaturated compounds can be introduced.
  • the acid value of the resin is usually 10 to 200 KOH mg / g, preferably 20 to 150 KOH mg / g, more preferably 30 to 150 KOH mg / g.
  • the polystyrene-reduced weight average molecular weight measured by GPC is usually 2000 to 100,000, preferably 4000 to 50000, and more preferably 5000 to 30000.
  • (B-4) “(Meth) acrylic resin” (B-4) (Meth) acrylic resin (hereinafter referred to as “(b-4) resin”) is a polymer obtained by polymerizing acrylic acid and / or acrylic acid ester as monomer components.
  • Preferred (b-4) resins include, for example, (b-4-1): a polymer obtained 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.
  • 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.
  • 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
  • X is represented by the following formula (6). A group or an adamantyl group which may be substituted
  • 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
  • L 1 and L 2 each independently represent a divalent linking group.
  • L 3 in the formula (5) may form a ring with R 3b or R 4b.
  • L 1 , L 2 and two or more of L 3 in the formula (5) may be bonded to each other to form a ring.
  • (B-4-1) “Polymer formed by polymerizing monomer components including (meth) acrylic acid and benzyl (meth) acrylate”
  • a polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate (hereinafter referred to as “(b-4-1) resin”) has a high affinity with a pigment.
  • the ratio of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component is not particularly limited, but (b-4-1) (meth) acrylic acid in all monomer components of the resin is usually It is 10 to 90% by weight, preferably 15 to 80% by weight, and more preferably 20 to 70% by weight.
  • the benzyl (meth) acrylate is generally 5 to 90% by weight, preferably 15 to 80% by weight, and more preferably 20 to 70% by weight, based on all monomer components. If the amount of (meth) acrylic acid is too large or too small, dispersion tends to be difficult.
  • (B-4-2) “Polymer obtained by polymerizing monomer components essentially comprising the compound represented by the general formula (4) and / or (5)”
  • a polymer obtained by polymerizing a monomer component essentially containing the compound represented by the general formula (4) and / or (5) is referred to as “(b-4-2) resin”.
  • the compound of the general formula (4) will be described.
  • 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.
  • R 1a and R 2a may be the same type of substituent or different substituents.
  • ether dimer examples include 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-propenoate, di (t-amyl) -2,2'-
  • dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.
  • These ether dimers may be used alone or in combination of two or more.
  • the ratio of the ether dimer in the monomer component in obtaining the (b-4-2) resin is not particularly limited, but it is usually 2 in the total monomer component of the (b-4-2) resin. It is ⁇ 60% by weight, preferably 5 to 55% by weight, and more preferably 5 to 50% by weight. If the amount of the ether dimer is too large, it may become difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, transparency, heat resistance, etc. There is a possibility that the performance of the coating film becomes insufficient.
  • 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.
  • 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.
  • An alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms is preferable.
  • 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 each independently a divalent linking group
  • L 3 is not particularly limited as long as it is a divalent linking group or a direct bond
  • At least either L 1 or L 2 is preferably a linking group having 1 or more carbon atoms.
  • L 1 , L 2 and L 3 are each independently a direct bond, an alkylene group having 1 to 15 carbon atoms, —O—, —S—, —C ( ⁇ O) —, and an alkenylene having 1 to 15 carbon atoms.
  • a group, a phenylene group, or a combination thereof is preferred.
  • 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 each independently an alkylene group having 1 to 5 carbon atoms.
  • General formula (6) the compound shown by following General formula (7) can be mentioned.
  • 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 or a halogen atom.
  • examples of the organic group represented by R 5b and R 6b include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, and an acyloxy group.
  • it is 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, or an alkoxy having 1 to 15 carbon atoms.
  • a cycloalkyl group having 3 to 15 carbon atoms is 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, or an alkoxy having 1
  • R 5b and R 6b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
  • 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 include the following substituents.
  • 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
  • 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 (M-1) to (M-22).
  • the proportion of the general formula (5) is not particularly limited, but is usually (b-4-2) the total monomer of the resin.
  • the content is 0.5 to 60% by weight, preferably 1 to 55% by weight, and more preferably 5 to 50% by weight. If the amount is too large, the dispersion stability may decrease when used as a dispersant.
  • the (b-4) acrylic resin in the present invention preferably contains an acid group, including the (b-4-1) resin and the (b-4-2) resin.
  • an acid group 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 referred to as “monomer for introducing an acid group”) May be used as a monomer component.
  • a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” hereinafter referred to as “monomer for introducing an acid group”
  • the process for providing an acid group as mentioned later is required after superposition
  • Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride.
  • monomers having a 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 are mentioned, Among these, (meth) acrylic acid is especially preferable.
  • Examples of the monomer capable of imparting an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; a monomer having an epoxy group such as glycidyl (meth) acrylate; And monomers having an isocyanate group such as acrylate. Only one type of monomer for introducing these acid groups may be used, or two or more types may be used.
  • the content ratio is not particularly limited. It is 5 to 70% by weight, preferably 10 to 60% by weight, based on all monomer components. Further, the (b-4) resin may have a radical polymerizable double bond.
  • (B-4) In order to introduce a radical polymerizable double bond into a resin, for example, “a monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter referred to as “single monomer for introducing a radical polymerizable double bond”). After polymerization as a monomer component, a treatment for imparting a radical polymerizable double bond as described later may be performed.
  • Examples of the monomer capable of imparting a radically 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.
  • the content ratio is not particularly limited, but usually (b- 4) 5 to 70% by weight, preferably 10 to 60% by weight, based on the total monomer components of the resin.
  • the (b-4) resin of the present invention is a polymer having the compound of the general formula (4) as an essential monomer component described in the section of (b-4-2) resin, an epoxy group It is preferable to have.
  • a monomer having an epoxy group hereinafter also referred to as “monomer for introducing an epoxy group” may be polymerized as a monomer component.
  • Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types. (B-4) When the monomer component in obtaining the resin also includes the monomer for introducing the epoxy group, the content ratio is not particularly limited, but usually (b-4) It is 5 to 70% by weight, preferably 10 to 60% by weight, based on all monomer components.
  • the monomer component for obtaining the resin may contain other copolymerizable monomers, if necessary, in addition to the above essential monomer components.
  • examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate.
  • acrylic acid esters such as: aromatic vinyl compounds such as styrene, vinyltoluene and ⁇ -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.
  • 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.
  • benzyl (meth) acrylate when a part or all of the (b-4) resin is used as a dispersant as described later, it is preferable to use benzyl (meth) acrylate, and the content thereof is usually (b-4) It is 1 to 70% by weight, preferably 5 to 60% by weight, based on all monomer components of the resin.
  • the content ratio is not particularly limited, but (b-4) the total monomer component of the resin The content is preferably 95% by weight or less, and more preferably 85% by weight or less. Further, the content ratio is 1% by mass or more, more preferably 5% by mass or more in the total monomer component of (b-4) resin.
  • (b-4) resin production method (polymerization method) will be described.
  • the polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C.
  • the polymerization concentration is preferably 5 to 50%, more preferably 10 to 40%.
  • a solvent used in a normal radical polymerization reaction may be used.
  • 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.
  • a polymerization initiator When the monomer component is polymerized, a polymerization initiator may be used as necessary.
  • the polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amyl.
  • Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane Carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) and the like.
  • These polymerization initiators may be used alone or in combination of two or more.
  • the amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight without gelation. In terms of being able to obtain several thousand to several tens of thousands of polymers, it is usually 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer component of (b-4) resin. It is.
  • a chain transfer agent may be added for adjusting the molecular weight.
  • the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and ⁇ -methylstyrene dimer.
  • mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and ⁇ -methylstyrene dimer.
  • n-dodecyl mercaptan and mercaptoacetic acid are preferable because they have a high chain transfer effect, can reduce residual monomers, and are easily available.
  • 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 In terms of being able to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, usually (b-4) 0.1 to 15% by weight, more preferably 0.5%, based on all monomer components of the resin. ⁇ 10% by weight.
  • the cyclization reaction of an ether dimer advances simultaneously,
  • the cyclization rate is not necessarily 100 mol%.
  • the acrylic 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. .
  • the treatment varies depending on the type of monomer used.
  • a monomer having an epoxy group such as glycidyl (meth) acrylate 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.
  • an isocyanate group such as 2-isocyanatoethyl (meth) acrylate
  • a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.
  • radical polymerizable double bond is introduced by using the monomer capable of imparting the radical polymerizable double bond described above as the monomer component when obtaining the resin (b-4), radical polymerization is performed after the polymerization. It is necessary to perform a process for imparting a sex double bond. The treatment varies depending on the type of monomer used.
  • a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid
  • 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-) vinylbenzylglycidyl ether may be added.
  • a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride
  • a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate is added. Just do it.
  • a compound having an acid group such as acrylic acid and a radical polymerizable double bond may be added.
  • the weight average molecular weight of the (b-4) resin of the present invention is not particularly limited, but preferably the polystyrene equivalent weight average molecular weight measured by GPC is 2,000 to 200,000, more preferably 4,000 to 100,000.
  • the weight average molecular weight exceeds 200,000, the viscosity becomes high, and the discharge property from the nozzle of the composition containing the same may decrease.
  • the weight average molecular weight is less than 2,000, the film strength tends to be insufficient.
  • a preferable acid value is 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g.
  • the polymer having the compound represented by the general formula (4) as an essential monomer component is a compound known per se, for example, JP-A-2004-300203. And compounds described in JP-A-2004-300204.
  • the epoxy acrylate resin having a carboxyl group is hereinafter referred to as “(b-5) resin”.
  • the (b-5) resin of the present invention is obtained by adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and further adding a polybasic acid It is synthesized by reacting an anhydride.
  • 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.
  • epoxy resin used as a raw material for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc., manufactured by Japan Epoxy Resin Co., Ltd.), Epoxy resin obtained by 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, manufactured by Japan Epoxy Resin Co., Ltd.) "Epicoat 807", "EP-4001”, “EP-4002", “EP-4004 etc.”), epoxy resins obtained by reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (eg Nippon Kayaku) “N” R-7406 ”(epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, bipheny
  • the epoxy resin is a copolymer type epoxy resin.
  • the copolymerization type epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “first component of copolymerization type epoxy resin”), and the like.
  • Second component of copolymerization type epoxy resin Monofunctional ethylenically unsaturated group-containing compound
  • second component of copolymerization type epoxy resin for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- Hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, ⁇ -methylstyrene, glycerol mono (meth) acrylate, and the following general formula Compound represented by (8)
  • the at least one element selected from the group consisting of include the obtained copolymer is reacted.
  • R 61 represents hydrogen or an ethyl group
  • R 62 represents hydrogen or an alkyl group having 1 to 6 carbon atoms
  • 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.
  • the copolymer type epoxy resin preferably has a molecular weight of about 1,000 to 200,000.
  • 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.
  • Specific examples of such a copolymer type epoxy resin include “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 of the 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 may be a problem in the film forming property. Conversely, if the resin exceeds the above range, gelation tends to occur during the addition reaction of ⁇ , ⁇ -unsaturated monocarboxylic acid. In some cases, manufacturing may be difficult.
  • Examples of the ⁇ , ⁇ -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 the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety include 2-succinoyloxyethyl acrylate, 2-malenoyloxyethyl acrylate, 2-phthaloyloxyethyl acrylate, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like.
  • 2-maleoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate and in particular, 2-maleic acrylate.
  • Noyloxyethyl is preferred. These may be used alone or in combination of two or more.
  • the addition reaction of an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group at the ester portion with an epoxy resin can be carried out using a known method, for example, an esterification catalyst The reaction can be carried out at a temperature of 50 to 150 ° C. in the presence.
  • 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 ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety is 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. A range is preferable, and a range of 0.7 to 1.1 equivalents is more preferable. If the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid anhydride The reaction is also insufficient.
  • Polybasic acid anhydrides to be further added to an epoxy resin in which an ⁇ , ⁇ -unsaturated carboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is added to the ester moiety include maleic anhydride and succinic anhydride.
  • a known method can also be used for the addition reaction of polybasic acid anhydride, similar to the addition reaction of ⁇ , ⁇ -unsaturated carboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety. Can be carried out by continuing the reaction under various conditions.
  • 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. From the viewpoint of the storage stability of the composition, it is preferable that the acid value is low.
  • epoxy acrylate resin having a carboxyl group examples include naphthalene-containing resins described in JP-A-6-49174; JP-A 2003-89716, JP-A 2003-165830, JP-A 2005-325331, JP Examples include fluorene-containing resins described in JP-A-2001-354735 and the like; JP-A-2005-126684, JP-A-2005-55814, JP-A-2004-295084, and the like. Also, commercially available epoxy acrylate resins having a carboxyl group can be used, and examples of commercially available products include “ACA-200M” manufactured by Daicel Corporation.
  • the binder resin acrylic resins described in, for example, JP-A-2005-154708 can also be used.
  • (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.
  • the molecular weight is particularly preferably about 5000 to 20000 as a weight average molecular weight in terms of polystyrene measured by GPC.
  • the colored curable resin composition of the present invention may be photocurable, thermosetting, or cured by both actions.
  • the binder resin is (b-1): “the copolymer of epoxy group-containing (meth) acrylate and other radical polymerizable monomer.
  • the following (b-6) resins having an epoxy group are most preferable.
  • thermosetting colored curable resin composition when forming a pixel for a color filter by the ink jet method, it does not require a photopolymerization initiator that may reduce luminance, and from the point that productivity can be increased by omitting the photocuring process, It is preferable to use a thermosetting colored curable resin composition.
  • (B-6) “Resin having an epoxy group”
  • the resin having a (b-6) epoxy group (hereinafter referred to as “(b-6) resin”) according to the present invention is not particularly limited as long as it has an epoxy group in the resin.
  • alicyclic polyether compounds having an epoxy group in the side chain polyglycidyl ether compounds, polyglycidyl ester compounds, polyglycidylamine compounds, and (meth) acrylates having an epoxy group are used alone or in combination.
  • a polymer obtained by polymerization as described above or a copolymer of an epoxy group-containing (meth) acrylate and another monomer can be used.
  • Specific examples of (b-6) resin are listed below, but are not limited thereto.
  • (b-6-1) “Alicyclic polyether compound having an epoxy group in the side chain”
  • 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, and the like.
  • Examples include polycyclohexyl ether having an epoxy group in the side chain.
  • EHPE3150 made by Daicel Chemical Industries Ltd.) etc. are mentioned, for example.
  • polyglycidyl ether compound examples include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), diglycidyl ether type of bis (3,5-dimethyl-4-hydroxyphenyl).
  • These (poly) glycidyl ether compounds may be those obtained by reacting a remaining hydroxyl group with an acid anhydride, a divalent acid compound or the like
  • polyglycidyl ester compound examples include a diglycidyl ester type epoxy of hexahydrophthalic acid, a diglycidyl ester type epoxy of phthalic acid, and the like.
  • polyglycidylamine compound examples include diglycidylamine type epoxy of bis (4-aminophenyl) methane, triglycidylamine type epoxy of isocyanuric acid, and the like.
  • (b-6-5) a polymer obtained by polymerizing one or more (meth) acrylates having an epoxy group such as the above compound (hereinafter referred to as “(b-6-5)”. ) Resin ”).
  • Examples of the (meth) acrylate having an epoxy group, which is a raw material for the resin include glycidyl (meth) acrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, ⁇ - n-butyl glycidyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, ⁇ -ethylacrylic And acid-6,7-epoxyheptyl. Particularly preferred is glycidyl (meth) acrylate.
  • the copolymer is referred to as “(b-6-6) resin”.
  • the content of other monomers is usually 10 to 70 mol%, preferably 15 to 60 mol%, of all monomers constituting the (b-6-6) resin.
  • monomers include, for example, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid esters such as phenyl acid, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate; and styrene And vinyl aromatic compounds such as ⁇ -methylstyrene, p-methylstyrene, and vinylnaphthalene.
  • Particularly preferred as the (meth) acrylate having an epoxy group is glycidyl (meth) acrylate.
  • Other monomers are particularly preferably dicyclopentanyl (meth) acrylate and ⁇ -methylstyrene.
  • the epoxy group used in the resin (b-6) in the present invention is usually a 1,2-epoxy group, but 1,3-epoxy is used for the purpose of improving stability over time or imparting flexibility.
  • a group (oxetane) or a 4,3-epoxycyclohexyl group can also be used.
  • (b-6) resins that do not contain an aromatic ring or that contain no phenyl group or a phenyl group having a substituent at the p (para) position are preferred because discoloration due to heat treatment can be suppressed. is there.
  • 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 mol%, 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 tends to be insufficient. If the amount is too large, the storage stability may be insufficient.
  • Mw 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 heat resistance and the film strength tend to be inferior.
  • 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.
  • the proportion of the resin is preferably 0.5% by weight or more, more preferably 1% by weight or more, and usually 50% by weight or less, based on the total solid content in the colored curable resin composition of the present invention. Preferably it is 40 weight% or less, More preferably, it is 35 weight% or less. (B-6) If the proportion of the resin is too small, the effect of improving the chemical resistance cannot be expected so much, and if it is too large, the storage stability tends to be insufficient.
  • the various binder resins described above may be used alone or in combination of two or more.
  • 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.
  • the colored curable resin composition of the present invention comprises (c) an organic solvent as an essential component.
  • the organic solvent has a function of adjusting the viscosity by dissolving or dispersing the respective components.
  • the (c) organic solvent may be any organic solvent that can dissolve or disperse each component constituting the colored curable resin composition.
  • (C) 80% by weight or more of the organic solvent has a boiling point of 180 ° C.
  • organic solvent examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl- 3-methoxybutanol, triethylene glycol monomer 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;
  • Ketones Monovalent 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, methyl 3-methoxypropionate, ethyl
  • Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Examples thereof include nitriles such as acetonitrile and benzonitrile.
  • solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like. These solvents may be used alone or in combination of two or more.
  • the colored curable resin composition of the present invention comprises (c) 80% by weight or more of the organic solvent having a boiling point of 180 ° C. or higher (boiling point under a pressure of 101.25 [hPa]). It is essential that (c-1) occupies.
  • the boiling point of the solvent (c-1) is preferably 200 ° C. or higher, particularly preferably 220 ° C. or higher.
  • the solvent (c-1) is preferably 80% by weight or more, more preferably 90% by weight or more in the (c) organic solvent.
  • Examples of the solvent (c-1) include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6 among the above organic solvents. -Hexanol diacetate, triacetin and the like. Of these, diethylene glycol mono-n-butyl ether acetate is particularly preferred.
  • a solvent having a boiling point lower than 180 ° C 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.
  • the organic solvent contains an alcohol, the ejection stability in the ink jet method may decrease.
  • 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 vapor pressure of the organic solvent is usually 10 mmHg or less, more preferably 5 mmHg or less, and further preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.
  • 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 95% by weight or less. (C) If the organic solvent is too much, the solid content concentration becomes too low and it becomes unsuitable for forming a coating film, or the viscosity of the ink becomes too high. Problems such as disturbing stability arise. In addition, when the colored curable resin composition is applied to an ink jet method, there is a possibility that the discharge stability is lowered.
  • the colored curable resin composition of the present invention preferably further contains (e) a dispersant.
  • a dispersant is not particularly limited as long as the effects of the present invention are not impaired, but (e-1): a graft copolymer containing a nitrogen atom, (e-2): containing a nitrogen atom It is preferable to contain an acrylic block copolymer and (e-3): one or more dispersants selected from the group consisting of urethane resin dispersants.
  • the nitrogen atom contained therein has an affinity for the pigment surface, and the portion other than the nitrogen atom increases the affinity for the medium. It is estimated that it contributes to the improvement of sex.
  • 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 Richrads, “Polymers at Surfaces and Interfaces”, 1999 edition, p281).
  • 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.
  • 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.
  • a portion suitable for it can be arranged in the portion requiring solvent affinity.
  • a graft copolymer containing a nitrogen atom (hereinafter sometimes referred to as “(e-1) copolymer”) is preferred because (g) the pigment can be dispersed extremely efficiently. The reason for this is not clear, but it has a structure that can actively eliminate the disposition of molecules (molecules) that interfere with the adsorption of the pigment and the dispersant around the adsorbing part to the pigment. It is guessed.
  • the graft copolymer containing a nitrogen atom those having a repeating unit containing a nitrogen atom in the main chain are preferred. Especially, it is preferable to have a repeating unit represented by Formula (I) and / or a repeating unit represented by Formula (II).
  • R 51 represents an alkylene group having 1 to 5 carbon atoms
  • A represents a hydrogen atom or any one of the following formulas (III) to (V).
  • R 51 represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably an ethylene group. It is.
  • A represents a hydrogen atom or any one of the following formulas (III) to (V), preferably formula (III).
  • R 51 and A have the same meanings as R 51 and A in formula (I).
  • 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 butylene, pentylene, hexylene and the like is preferable.
  • p represents an integer of 1 to 20, preferably an integer of 5 to 10.
  • Y 1 represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene, or an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy.
  • W 2 represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene and butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene and propylene 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 ethyl, propyl, butyl, pentyl, hexyl, etc., among which carbon number 2 such as ethyl, propyl, butyl, pentyl, etc. To 5 alkyl groups are preferred).
  • q represents an integer of 1 to 20, preferably an integer of 5 to 10.
  • W 3 represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, among which an alkyl group having 10 to 20 carbon atoms such as stearyl, A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as monohydroxystearyl is preferred.
  • the content of the repeating unit represented by the formula (I) or (II) in the graft copolymer (e) of the present invention is preferably as high as possible, usually 50 mol% or more, preferably 70. More than mol%.
  • the repeating unit represented by formula (I) and the repeating unit represented by formula (II) may both be present, and the content ratio is not particularly limited, but the repeating unit represented by formula (I) It is preferable to contain a large amount of.
  • the total number of repeating units represented by the formula (I) or the formula (II) is usually 1 to 100, preferably 10 to 70, more preferably 20 to 50 in one molecule.
  • the graft copolymer (e) as a dispersant of the present invention is preferably a graft copolymer having —NH 2 and —R 51 —NH 2 (R 51 is as defined above for R 51 ).
  • R 51 is as defined above for R 51 .
  • the main chain may be linear or branched.
  • the amine value of the (e-1) copolymer is usually 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g, and more preferably 15 to 40 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 and titrated with an acetic acid solution of 0.1 mol / L perchloric acid (HCLO 4 ) using an automatic titrator equipped with a pH electrode.
  • HCLO 4 0.1 mol / L perchloric acid
  • 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]
  • S represents the solid content concentration [wt%] of the dispersant sample.)
  • the polystyrene-equivalent weight average molecular weight of the above (e-1) copolymer measured by GPC is preferably from 3,000 to 50,000, particularly preferably from 5,000 to 20,000.
  • the weight average molecular weight is less than 3000, (a) aggregation of the coloring material cannot be prevented and the viscosity or gelation may occur. If it exceeds 50000, the viscosity itself becomes high, and (c) the solubility in an organic solvent may be insufficient. Further, due to the steric hindrance of the dispersant molecule itself, (a) adsorption to the coloring material may be hindered and the dispersibility may be lowered.
  • a known method can be adopted, and for example, a method described in JP-B-63-30057 can be used.
  • a commercially available graft copolymer having the same structure as described above can also be applied.
  • An acrylic block copolymer containing nitrogen atoms (hereinafter sometimes referred to as “(e-2) copolymer”) is preferred in that (a) the colorant can be dispersed very efficiently. The reason is not clear, but it is presumed that (a) there are few structures that become obstacles when adsorbing to the coloring material because the molecular arrangement is controlled.
  • the copolymer includes an A block having a quaternary ammonium base and / or amino group in the side chain and a B block having no quaternary ammonium base and / or amino group. B block copolymers and / or BAB block copolymers are preferred.
  • the A block constituting the block copolymer of the acrylic block copolymer containing a nitrogen atom has a quaternary ammonium base and / or an amino group.
  • the quaternary ammonium base is preferably —N + R 31 R 32 R 33 ⁇ Z ⁇ (wherein R 31 , R 32 and R 33 each independently represents 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.
  • Z ⁇ represents a counter anion).
  • 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.
  • 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. Specifically, the following are mentioned, for example.
  • R represents any group of R 31 , R 32 , and R 33 . These cyclic structures may further have a substituent.
  • R 31, R 32, R 33 in -N + R 31 R 32 R 33 has more preferably each independently, alkyl group having 1 carbon atoms which may 3 have a substituent, a substituent It may be a phenyl group which may be substituted, or a benzyl group which may have a substituent.
  • a block having a quaternary ammonium base those containing a partial structure represented by the following general formula (VI) are preferable.
  • R 31 , R 32 , and R 33 each independently represent 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.
  • 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. Groups are preferred.
  • Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, or a benzyl group is preferable.
  • Examples of the divalent linking group X 1 in the general formula (VI) 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 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 an alkylene group; Group))) and the like, and —COO—R 36 — is preferable.
  • Examples of the counter anion Z ⁇ include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ , and PF 6 ⁇ .
  • 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. It represents a good allyl group or an aralkyl group which may have a substituent.), More preferably, an amino group represented by the following formula is exemplified.
  • R 41 and R 42, R 41 and R 42 as defined above amino group, R 43 represents an alkylene group having 1 or more carbon atoms, R 44 represents a hydrogen atom or a methyl group.
  • R 41 and R 42 are preferably a methyl group
  • R 43 is preferably a methylene group or an ethylene group
  • R 44 is preferably a hydrogen atom. Examples of such a compound include a substituent represented by the following formula.
  • Two or more kinds of the partial structures containing the specific quaternary ammonium base and / or amino group as described above may be contained in one A block.
  • two or more quaternary ammonium bases and / or amino group-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization.
  • a partial structure containing neither the quaternary ammonium base nor the amino group may be contained in the A block.
  • Examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later.
  • the content of the partial structure containing neither a quaternary ammonium base nor an amino group in the A block 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 A block.
  • examples of the B block constituting the (e-2) copolymer include styrene monomers such as styrene and ⁇ -methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic.
  • the B block is particularly preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (VII).
  • R 39 represents a hydrogen atom or a methyl group.
  • R 40 represents a cyclic or chain alkyl group which may have a substituent, an allyl group which may have a substituent, or an aralkyl group which may have a substituent.
  • Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block.
  • the B block may further contain a partial structure other than these.
  • each partial structure may be contained in the B block in any form of random copolymerization or block copolymerization.
  • the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 99% by weight, more preferably 0 to 85% by weight.
  • the (e-2) copolymer in the present invention is an AB block or a BAB block copolymer composed of such an A block and a B block. It is prepared by a polymerization method.
  • the living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method.
  • the polymerization active species is an anion, for example, shown in the following scheme.
  • the polymerization active species is a radical, and is represented by the following scheme, for example.
  • the amine value (in terms of effective solid content) in 1 g of the (e-2) copolymer according to the present invention is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 50 mgKOH / g or more, Particularly preferably, it is 80 mgKOH / g or more, and usually 300 mgKOH / g or less.
  • the acid value of the (e-2) copolymer depends on the presence and type of an acidic group serving as the acid value group, but is generally preferably lower and is usually 100 mgKOH / g or less.
  • the molecular weight of the copolymer is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-equivalent weight average molecular weight (Mw) measured by GPC. If the weight average molecular weight of the block copolymer is too small, the dispersion stability decreases, and if it is too large, the steric hindrance of the dispersant molecule itself causes (a) the adsorption to the colorant to be inhibited and the dispersibility tends to decrease. It is in. In the present invention, a commercially available acrylic block copolymer having the same structure as described above can also be applied.
  • Urethane resin dispersants are polyisocyanate compounds, compounds 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.
  • polyisocyanate compound examples include fragrances such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate.
  • fragrances such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate.
  • Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ⁇ , ⁇ ' -Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane; xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetrame Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate; lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicyclohept
  • 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.
  • an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like.
  • 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. An alkoxylated one or a mixture of two or more of these may be mentioned.
  • Examples of the polyether glycol include polyether diol, polyether ester diol, or a mixture of two or more of these.
  • polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides, such as 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.
  • 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.
  • 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.
  • polyester glycol examples 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.
  • 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- , 4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octa Aliphatic glycols such as methylene glycol
  • the diol Or a polylactone diol or polylactone monool obtained by using a monohydric alcohol having 1 to 25 carbon atoms as an initiator, such as polycaprolactone glycol, polymethylvalerolactone, or a mixture of two or more thereof.
  • a monohydric alcohol having 1 to 25 carbon atoms such as polycaprolactone glycol, polymethylvalerolactone, or a mixture of two or more thereof.
  • the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ⁇ -caprolactone to a monool. is there.
  • polycarbonate glycol examples include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
  • polyolefin glycol examples include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Of these compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred.
  • 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.
  • 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, and a thiol group.
  • a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, and n-butyl
  • the dialkylamino group is 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.
  • 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
  • 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.
  • 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. Can be mentioned.
  • compounds 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-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like can be mentioned.
  • 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 the raw material of the dispersant is usually 10 to 200 parts by weight, preferably 20 to 20 parts by weight of the 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 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.
  • the (e-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, isopropanol, sec-butanol and tert-butanol; halogenated hydrocarbons such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide, N- Aprotic polar solvents such as methyl pyrrolidone and dimethyl sulfoxide are used.
  • a normal urethanization reaction catalyst is used as a catalyst at the time of manufacture.
  • tin system such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate
  • iron system such as iron acetylacetonate and ferric chloride
  • tertiary amine system such as triethylamine and triethylenediamine It is done.
  • the amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled within the range of 1 to 100 mgKOH / g in terms of the amine value of the (e-3) dispersant resin after the reaction.
  • the dispersion ability tends to be lowered.
  • the isocyanate group remains in the dispersant molecule (e-3) by the above reaction, if the alcohol or amino compound is further reacted with the isocyanate group, (e-3) the temporal stability of the dispersant is improved. Since it becomes high, it is preferable.
  • the weight average molecular weight in terms of polystyrene measured by GPC of these urethane resin dispersants is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. Range. When the weight average molecular weight is 1,000 or less, dispersibility and dispersion stability tend to be inferior. When the weight average molecular weight is 200,000 or more, the solubility is lowered and the dispersibility is inferior, and at the same time, the reaction control may be difficult.
  • the (e) dispersant used in the colored curable resin composition of the present invention may contain other dispersants in addition to the dispersants (e-1) to (e-3) described above.
  • Other dispersants include, for example, polyallylamine-based dispersants, dispersants containing monomers and macromonomers having amino groups, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, Examples thereof include polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • EFKA EFKA Chemicals Beebuy
  • Disperbyk manufactured by Big Chemie
  • Disparon manufactured by Enomoto Kasei
  • SOLPERSE manufactured by Lubrizol
  • KP manufactured by Shinetsu
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • ajisper manufactured by Ajinomoto Fine-Techno Co., Ltd.
  • other series names can be mentioned.
  • the content ratio of (e) the dispersant is usually 95% by weight or less, preferably 65% by weight or less, more preferably 50% by weight or less based on (a) the colorant. Moreover, it is 5 weight% or more normally, Preferably it is 7 weight% or more, Most preferably, it is 10 weight% or more.
  • the amount is too large, the ratio of the coloring material (a) is relatively reduced, so that the coloring power is lowered. For this reason, the film thickness becomes too thick with respect to the color density, and when used in a color filter, a cell gap control defect may occur in the liquid crystal cell forming step.
  • the colored curable resin composition of the present invention particularly when (e-2): an acrylic block copolymer is included among the above-mentioned dispersants, the effect is remarkably exhibited.
  • it includes an AB block copolymer and / or a BAB block copolymer comprising an A block having an amino group in the side chain and a B block having no amino group in the side chain.
  • the dispersing agent whose amine value of this block copolymer is 10 mgKOH / g (in terms of effective solid content) or more is mentioned.
  • 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 colored curable resin composition of the present invention uses a part of the above-mentioned (b) binder resin together with the above (e) dispersant in the dispersion treatment step to be described later, and both serve as a dispersant. You may let them. In this way, a resin that performs the same function as the dispersant may be referred to as a “dispersion resin”.
  • the colored curable resin composition of the present invention preferably contains (f) a monomer.
  • 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).
  • ethylenic compound an addition-polymerizable compound having at least one ethylenic double bond
  • the ethylenic compound undergoes addition polymerization by the action of a photopolymerization initiation system described later or by the action of a thermal polymerization initiator described later by heating.
  • 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.
  • the ethylenic compound examples 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.
  • 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
  • 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 , Isopropy
  • (meth) acrylic acid ester (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, and pyrogallol tri (meth) acrylate.
  • 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.
  • 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
  • condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin 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 condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol
  • 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
  • aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate
  • (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane
  • 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.
  • the preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g.
  • the acid groups as the entire polyfunctional monomer are within the above range. It is preferable to adjust so that it may enter.
  • 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.
  • the monomer (f) 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.), and the like.
  • the content ratio of these (f) 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. Further, the ratio to (a) the color material is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably It is 100 weight% or less, More preferably, it is 80 weight% or less.
  • (h) Photopolymerization Initiation System and / or Thermal Polymerization Initiator The curable resin composition of the present invention has the purpose of (h) photopolymerization initiation system and / or thermal polymerization initiation for the purpose of curing the coating film. It is preferable to contain an agent (hereinafter sometimes referred to as “component (h)”), but the curing method may be other than the method using the initiator.
  • the curable resin composition of the present invention includes (b) a resin having an ethylenic double bond as a binder resin component, or (f) includes an ethylenic compound as a monomer component
  • a thermal polymerization initiator that directly absorbs or photosensitizes to cause a decomposition reaction or a hydrogen abstraction reaction and has a function of generating a polymerization active radical and / or a polymerization active radical by heat, It is preferable to mix
  • the component (h) as the photopolymerization initiation system is sometimes referred to as an accelerator (hereinafter referred to as the (h2) component) to a photopolymerization initiator (hereinafter sometimes referred to as the (h1) component).
  • an additive such as a sensitizing dye (hereinafter sometimes referred to as (h3) component).
  • the colored curable resin composition of the present invention may contain a photopolymerization initiating system as the component (h).
  • the photopolymerization initiation system as the component (h) is usually a mixture of (h1) a photopolymerization initiator, and (h2) a polymerization accelerator and (h3) an additive such as a sensitizing dye, which are added as necessary.
  • an additive such as a sensitizing dye, which are added as necessary.
  • Examples of the photopolymerization initiator constituting the photopolymerization initiation system (h1) include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; Biimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl- radical activators such as s-triazine derivatives, N-aryl- ⁇ -amino acids such as N-phenylglycine, N-aryl- ⁇ -amino acid salts, N-aryl- ⁇ -amino acid esters, ⁇ - aminoalkylphenones Derivatives; oxime ester derivatives described in JP 2000-80068 A and the like.
  • titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phenyl-1yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny) 1-yl), dicyclopentadienyltitanium di (2,6-difluorophen-1-yl), dicyclopentadienyltitanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylsilane) Lopentadienyl) titanium bis (2,6-difluorophen-1-yl),
  • Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazolol 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′-methoxy) Phenyl) -4,5-diphenylimidazole dimer and the like.
  • halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2′-benzofuryl) Vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2 ′-(6 ′′ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2- And trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl). ) -S-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s -Triazine and the like.
  • Examples of ⁇ -aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylamino) Benzoyl) coumarin, 4- (diethylamino) chalcone, etc.
  • oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime) and the like.
  • 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, 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, ⁇ -hydroxy-2-methyl Phenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropy
  • Examples of the (h2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; or mercapto compounds such as aliphatic polyfunctional mercapto compounds.
  • Each of these (h1) photopolymerization initiator and (h2) polymerization accelerator may be used alone or in combination of two or more.
  • the total content of these (h1) photopolymerization initiator and (h2) 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 reduced, while if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.
  • a sensitizing dye is used for the purpose of increasing the sensitivity as required.
  • an appropriate dye is used depending on 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 as described in JP-A-3-239703, JP-A-5-289335, etc .; JP-A-3-239703, JP-A-5-289335, etc.
  • amino group-containing 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, (
  • the content ratio of (h3) sensitizing dye is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight in the total solid content.
  • the range is usually 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less.
  • thermal polymerization initiator examples include azo compounds, organic peroxides, and hydrogen peroxide. . Of these, azo compounds are preferably used.
  • 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-ethy
  • organic peroxide examples include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like.
  • thermopolymerization initiators there are those that also function as thermal polymerization initiators, such as ⁇ -aminoalkylphenone compounds. Therefore, as the thermal polymerization initiator, a compound selected from (h1) examples given as examples of the photopolymerization initiator may be used.
  • thermal polymerization initiators may be used alone or in combination of two or more.
  • the content of the thermal polymerization initiator in the colored curable resin composition of the present invention is preferably selected in the range of 0 to 30% by weight, particularly 0 to 20% by weight based on the total solid content.
  • the colored curable resin composition of the present invention is not limited to the compounds described in the section of (g) surfactant, as long as the effects of the invention are not impaired.
  • Other surfactants may be contained.
  • various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but various properties such as voltage holding ratio and compatibility with (c) organic solvents are available. It is preferable to use a nonionic surfactant because it is less likely to adversely affect the surface.
  • anionic surfactant examples 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.
  • cationic surfactant examples 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.
  • 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.
  • TSF4460 manufactured by GE Toshiba Silicone / “DFX-18” manufactured by Neos
  • BYK-300 manufactured by Big 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
  • FC4430 manufactured by Sumitomo 3M The combination of is mentioned.
  • the colored curable resin composition of the present invention includes, in addition to the above components, a dispersion aid, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a plasticizer, a dye, and a thermal polymerization inhibitor. Further, it may contain a storage stabilizer, a surface protective agent, an adhesion improver, a development improver and the like.
  • the dispersion aid is used for improving the dispersibility of the pigment in the color material (a), improving the dispersion stability, and the like.
  • dispersing aids include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole. And pigment derivatives such as dioxazines.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the content ratio of these dispersion aids is usually 0.1% by weight or more, and usually 300% by weight or less, preferably with respect to the color material (a). Is 200% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. If the added amount is small, the effect is not exhibited. Conversely, if the added amount is too large, the dispersibility and dispersion stability tend to be deteriorated.
  • An organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride may be contained. These are preferably contained when the colored curable resin composition contains (e-3) a urethane resin dispersant as the (e) dispersant.
  • Specific examples of the organic carboxylic acid include aliphatic carboxylic acids and aromatic carboxylic acids.
  • Aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, (meth) acrylic acid and other monocarboxylic acids; oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, cyclohexane dicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and other dicarboxylic acids; tricarbaric acid, aconitic acid and other tricarboxylic acids, and the like.
  • aromatic carboxylic acid examples 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.
  • those having a molecular weight of 600 or less are preferable, and those having a molecular weight of 50 to 500 are particularly preferable.
  • maleic acid, malonic acid, succinic acid, and itaconic acid are preferable.
  • the organic carboxylic acid anhydride include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides.
  • aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.
  • those having a molecular weight of 600 or less are preferable, and those having a molecular weight of 50 to 500 are particularly preferable.
  • maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred.
  • the content ratio of these organic carboxylic acids and / or organic carboxylic anhydrides is usually 0.01% by weight or more, preferably 0.03% by weight or more in the total solid content. More preferably, it is 0.05% by weight or more, and 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 in the total solid content of the colored curable resin composition.
  • the colored curable resin composition of the present invention may contain a thermal polymerization inhibitor.
  • the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t -Butyl-p-cresol, ⁇ -naphthol and the like.
  • the content of these thermal polymerization inhibitors is preferably in the range of 3% by weight or less in the total solid content of the colored curable resin composition.
  • the colored curable resin composition of the present invention may be prepared by preparing a pigment dispersion in advance and mixing other components thereto, or may mix all the components together. Below, the case where it prepares according to the former method is demonstrated to an example, However, It is not limited to this.
  • a color material (c) an organic solvent, and (a) when the color material contains a pigment, (e) a dispersant, which is an optional component, are weighed in predetermined amounts, and in the dispersion treatment step, (a) color
  • the pigment in the material is dispersed to obtain a pigment dispersion.
  • 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.
  • the pigment is made into fine particles, so that the application characteristics of the colored curable resin composition are improved, and the light transmittance of the pixels of the color filter produced using this is improved.
  • the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm.
  • the temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower.
  • the dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the pigment dispersion, the size of the sand grinder apparatus, and the like.
  • a colored curable resin composition is obtained by mixing a photopolymerization initiation system and / or a thermal polymerization initiator and other components to obtain a uniform dispersion solution.
  • the obtained pigment dispersion is preferably filtered with a filter or the like.
  • the colored curable resin composition of the present invention is usually in a state in which all components are dissolved or dispersed in a solvent. This is supplied onto the substrate to form the color filter and the constituent members of the liquid crystal display device.
  • a method for producing a color filter using the colored curable resin composition of the present invention and a liquid crystal display device (panel) using the same will be described.
  • 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
  • the film thickness is thicker than that of a color filter by lithography (usually a film thickness of 1.5 ⁇ m or more, preferably about 1.8 to 2.5 ⁇ m, more preferably about 2.0 to 2.3 ⁇ m).
  • liquid repellent treatment is often applied to the upper surface of the black matrix.
  • a photosensitive material including a black color material from a conventionally used chromium compound such as chromium, chromium oxide, chromium nitride, or a black matrix formed of a light shielding metal material such as nickel and tungsten alloy.
  • the resin black matrix (BM) is more preferable.
  • the resin black matrix (BM) may be formed by a general photolithography method.
  • the obtained resin BM is subjected to hydrophilic treatment on the surface of the transparent substrate and liquid repellency of the black matrix (BM) pattern by chemical treatment or physical treatment, respectively.
  • the colored curable resin composition of the present invention is used to draw with an inkjet device, and drying, photocuring and / or heat curing are performed.
  • the composition is completely cured to form a pixel by forming pixels.
  • 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.
  • polyester such as polyethylene terephthalate; polyolefin such as polypropylene and polyethylene; thermoplastic plastic such as polycarbonate, polymethyl methacrylate, and polysulfone.
  • Sheet Thermosetting plastic sheet such as epoxy resin, polyester resin, poly (meth) acrylic resin; various glass plates and the like.
  • a glass plate and a heat-resistant plastic plate are preferably used from the viewpoint of heat resistance.
  • heat drying such as a hot plate, IR (infrared) oven, convection oven or the like can be used.
  • Preferred drying conditions are 40 to 150 ° C., and drying time is 10 seconds to The range is 60 minutes.
  • 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.
  • both can be used together and can also be performed sequentially or simultaneously.
  • 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.
  • 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.
  • an optical filter can also be used.
  • the liquid crystal display device (panel) 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.
  • 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 the gap (gap) with the counter substrate is used, and a spacer of 2 to 8 ⁇ m 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 ⁇ m.
  • 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.
  • the degree of decompression in the liquid crystal cell is usually 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 7 Pa, preferably 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 6 Pa.
  • the liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 to 100 ° C., preferably 50 to 90 ° C.
  • the warming at the time of decompression is usually in the range of 10 to 60 minutes, and then the liquid crystal inlet is immersed in the liquid crystal.
  • 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.
  • thermotropic liquid crystal nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of these may be used.
  • an organic EL element can be produced by laminating the organic light-emitting body 500 on the color filter via the organic protective layer 30 and the inorganic oxide film 40.
  • 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.
  • a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used.
  • organic EL display A method described in, for example, “Organic EL display” (Ohm, published on August 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 thus manufactured, etc.
  • 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.
  • the weight average molecular weight Mw of the obtained copolymer was 9000, the amine value was 121 mgKOH / g, and the acid value was 0 mgKOH / g.
  • the amine value was expressed by the following method in terms of the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent, and was measured by the following method.
  • a 100 mL beaker 0.5 to 1.5 g of the dispersant obtained by the above synthesis was precisely weighed and dissolved in 50 mL of acetic acid. This solution was neutralized with a 0.1 mol / L HCLO 4 acetic acid solution using an automatic titrator equipped with a pH electrode. With the inflection point of the titration pH curve as the end point of titration, the amine value was determined by the following formula.
  • the dropping of each charged solution was started from the monomer tank and the chain transfer agent tank to initiate polymerization.
  • the dropwise addition was performed over 135 minutes while maintaining the temperature of the reaction vessel at 90 ° C., and the temperature was raised to 110 ° C. 60 minutes after the completion of the dropwise addition.
  • 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.
  • Example 1 (A) 8.6 g of Pigment Green 36 and 8.6 g of Pigment Yellow 150 as a coloring material (pigment), 5.8 g of the compound obtained in Synthesis Example 1 as a dispersant, (b) Binder As a resin, 5.8 g of the resin obtained in Synthesis Example 2 and (c) 115.2 g of diethylene glycol mono-n-butyl ether acetate (DEGBEA) as an organic solvent were mixed and stirred and homogenized. 300 g of zirconia beads were added and dispersed by shaking for 5 hours with a paint conditioner to prepare a pigment dispersion. Separately, (b) 10.5 g of an epoxy resin EHPE3150 manufactured by Daicel Chemical Co., Ltd.
  • EHPE3150 an epoxy resin manufactured by Daicel Chemical Co., Ltd.
  • Example 2 Coloring and curing were carried out in the same manner as in Example 1 except that (g) the surfactant to be added to the clear base was changed to a compound represented by the following structural formula (iv) (PF-6520 manufactured by OMNOVA). A functional resin composition was obtained. In the same manner as in Example 1, the surface tension ⁇ and the contact angle ⁇ with respect to the glass substrate of the 0.02 wt% DEGBEA solution of the compound represented by the following structural formula (iv) were measured. The results are shown in Table 1. The surface tension of this colored curable resin composition was 28.0 mN / m. Table 1 shows the results of evaluation of wet spreadability and pixel flatness.
  • Example 3 (G) Coloring curability in exactly the same procedure as in Example 1 except that (g) the surfactant to be added to the clear base was changed to the compound represented by the following structural formula (ii) (OMNOVA PF-656).
  • a resin composition was obtained.
  • the surface tension ⁇ and the contact angle ⁇ with respect to the glass substrate were measured in the same manner as in Example 1. The results are shown in Table 1.
  • the surface tension of this colored curable resin composition was 29.8 mN / m. Table 1 shows the results of evaluation of wet spreadability and pixel flatness.
  • Example 1 A colored curable resin composition was obtained in the same procedure as in Example 1 except that the surfactant was not added to the clear base. Moreover, the surface tension of this colored curable resin composition was 30.0 mN / m. Table 1 shows the results of evaluation of wet spreadability and pixel flatness.
  • Comparative Example 2 Add to the clear base (g) Color and cure in exactly the same way as in Example 1 except that the surfactant is Surflon “S-393” (nonionic; fluorine surfactant) manufactured by Seimi Chemical Co., Ltd. A functional resin composition was obtained.
  • the surfactant is Surflon “S-393” (nonionic; fluorine surfactant) manufactured by Seimi Chemical Co., Ltd.
  • a functional resin composition was obtained.
  • Example 3 For the 0.02 wt% DEGBEA solution of “S-393”, the surface tension ⁇ and the contact angle ⁇ with respect to the glass substrate were measured in the same manner as in Example 1. The results are shown in Table 1.
  • the colored curable resin composition had a surface tension of 24.0 mN / m.
  • Table 1 shows the results of evaluation of wet spreadability and pixel flatness.
  • (Comparative Example 3) (G) The same procedure as in Example 1 except that the surfactant is “F-475” (non-ionic; silicone-containing fluorine-based surfactant) manufactured by Dainippon Ink and Chemicals, Inc. A colored curable resin composition was obtained.
  • Example 1 For the 0.02 wt% DEGBEA solution of “F-475”, as in Example 1, the surface tension ⁇ and the contact angle ⁇ with respect to the glass substrate were measured. The results are shown in Table 1. Moreover, the surface tension of this colored curable resin composition was 27.0 mN / m. Table 1 shows the results of evaluation of wet spreadability and pixel flatness.
  • alkali-free glass substrate “AN635” 10 cm square is coated with a photosensitive resin composition containing a black color material so as to have a film thickness of 0.7 mm, and a line width of 20 ⁇ m and opening width by photolithography.
  • a black matrix pattern of 220 ⁇ m ⁇ 700 ⁇ m and a thickness of 2.0 ⁇ m was formed.
  • the central portion of each pixel bank formed by a black matrix pattern was obtained by the inkjet method in each example and comparative example. About 200 pL of the colored curable resin composition was applied.
  • the coated substrate was dried by a decompression process to form pixels.
  • the surface shape of the obtained pixel was measured with a three-dimensional laser microscope, and the area ratio (%) of the flat portion to the pixel area was evaluated.
  • Area ratio (%) of flat portion [(area of flat portion in pixel) / (pixel area)] ⁇ 100
  • the colored cured resin compositions of Examples and Comparative Examples shown in Table-1 were evaluated as follows.
  • the wet spread was defined as x when the area ratio of wet spread was less than 40%, ⁇ when 40% or more and less than 60%, and ⁇ when 60% or more.
  • the pixel flatness the case where the area ratio of the flat portion to the pixel area is less than 60% is evaluated as x, the ratio between 60% and less than 80% is ⁇ , and the area ratio is 80% or more.
  • the surface tension of less than 25 mN / m was evaluated as x, the value of 25 mN / m or more and less than 28 mN / m as ⁇ , and the value of 28 mN / m or more and 31 mN / m or less as ⁇ . From the evaluation results shown in Table 1, the colored curable resin composition of the present invention has a wet spread and a pixel without excessive reduction in surface tension due to the addition of the compound represented by the general formula (0). It was found that a colored curable resin composition having good flatness can be obtained.
  • a colored curable resin composition exhibiting excellent performance in both surface smoothness of pixels and wettability in a pixel bank in color filter production by an inkjet method. be able to. Further, by using such an ink, a high-quality color filter can be manufactured with a high yield, and a large-scale and inexpensive supply of a liquid crystal display device can be realized. It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2008-135900 filed on May 23, 2008 is cited here as the disclosure of the specification of the present invention. Incorporated.

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Abstract

L'invention porte sur une composition de résine durcissable colorante (encre) qui, lorsqu'elle est utilisée dans la fabrication d'un filtre coloré par le procédé de jet d'encre, peut concilier un caractère lisse de surface de pixel avec des propriétés de mouillage et une aptitude à l'étalement à l'intérieur de rangs de pixels. La composition de résine durcissable colorante comprend (a) un colorant, (b) une résine liante, (c) un solvant organique et (g) un tensioactif, au moins 80 % en poids du solvant organique (c) étant constitué par un solvant (c-1) ayant un point d'ébullition supérieur ou égal à 180°C (point d'ébullition mesuré à une pression de 1,01325 hPa). Une solution à 0,02 % en poids du tensioactif (g) dans le solvant (c-1) a une tension de surface dans une plage spécifique et un angle de contact dans une plage spécifique avec un substrat en verre.
PCT/JP2008/066885 2007-05-28 2008-09-18 Composition de résine durcissable colorante, filtre coloré, affichage à cristaux liquides et affichage el organique WO2009141924A1 (fr)

Priority Applications (2)

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CN2008801287444A CN102015904A (zh) 2007-05-28 2008-09-18 着色固化性树脂组合物、滤色器、液晶显示装置和有机电致发光显示屏
KR1020107022440A KR20110018292A (ko) 2008-05-23 2008-09-18 착색 경화성 수지 조성물, 컬러 필터, 액정 표시 장치 및 유기 ｅｌ 디스플레이

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JP2008-135900 2008-05-23
JP2008135900A JP2009007560A (ja) 2007-05-28 2008-05-23 着色硬化性樹脂組成物、カラーフィルタ、液晶表示装置及び有機ｅｌディスプレイ

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WO2012132755A1 (fr) * 2011-03-31 2012-10-04 旭硝子株式会社 Composition de résine photosensible négative et film de revêtement
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JP2011232709A (ja) * 2010-04-30 2011-11-17 Taiyo Holdings Co Ltd 硬化性樹脂組成物
WO2012132755A1 (fr) * 2011-03-31 2012-10-04 旭硝子株式会社 Composition de résine photosensible négative et film de revêtement
JP2016108374A (ja) * 2014-12-02 2016-06-20 セイコーエプソン株式会社 成膜用インク、成膜方法、膜付きデバイスおよび電子機器
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WO2016208518A1 (fr) * 2015-06-22 2016-12-29 Jsr株式会社 Composition pour former un film sous-couche de réserve, film sous-couche de réserve et procédé de production de substrat à motifs

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