JP2008224982A - Colored curable composition for color filter, color filter, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition for a color filter having superior developability even under low exposure value, and to provide a color filter having high color purity and superior patterning properties, and to provide a liquid crystal display. <P>SOLUTION: The colored curable composition for a color filter comprises a colorant, a polymerizable compound, a photopolymerization initiator and a sensitizer. The sensitizer is at least one of the compounds represented by general formula (1), wherein R<SP>7</SP>represents a 6-15C alkyl group; and X<SP>1</SP>and X<SP>2</SP>, each independently represent a halogen atom, an alkyl group, an aryl group, an aralkyl group or an aromatic heterocyclic group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a colored curable composition for a color filter, a color filter, and a liquid crystal display device.

Conventionally, a pigment dispersion method has been most widely adopted in a method for producing a color filter used in a liquid crystal display device or the like.
In the pigment dispersion method, a colored curable composition (hereinafter sometimes referred to as “color resist”) in which a black matrix is formed on a transparent support such as a glass substrate and then a red pigment is dispersed, for example, is then spun. It is applied to the entire surface by a coating method or the like and exposed through a mask. When developed after exposure, red pixels are obtained. By forming the blue and green pixels in the same manner, three color pixels are formed.
In the manufacture of such a color filter, since the substrate has recently become larger, it is necessary to increase productivity, and development of a color resist with higher sensitivity is awaited.

On the other hand, color filters obtained from color resists are required to have wider color reproducibility and higher transmittance than before.
In order to improve the color reproducibility of the color filter, it is necessary to increase the colorant content of the colored layer to increase the color purity. For this reason, when it is going to improve the color reproducibility of a color filter, the pigment concentration in solid content of a colored curable composition will become high, and solid content of a photocurable material (initiator, polymeric material, or a crosslinkable material). The inside ratio becomes relatively small. As a result, the curability at the exposed portion is lowered and it becomes difficult to form a pattern in the development process.

Therefore, in order to obtain a color filter having high color reproducibility and excellent patternability, it is desirable to use a color resist that is sufficiently cured even if the content ratio of the photocurable material is low.
Here, in order to improve the sensitivity of the color resist, it is beneficial to add a sensitizing dye. Examples of sensitizing dyes used in color resists include xanthene dyes (for example, see Patent Document 1), coumarin dyes (for example, see Patent Document 2), ketocoumarin dyes (for example, see Patent Document 2 described above), and dialkyls. A dye having an aminobenzene skeleton (see, for example, Patent Document 3) is disclosed.
However, further improvement has been desired to improve the color reproducibility more than ever.
JP-A-4-221958 JP-A-5-289335 Japanese Patent Laid-Open No. 5-210240

An object of the present invention is to provide a colored curable composition for a color filter which is excellent in developability even at a low exposure amount.
It is another object of the present invention to provide a color filter and a liquid crystal display device having high color purity and excellent patternability.

  In order to obtain a colored curable composition excellent in developability even at a low exposure amount, the present inventors paid attention to an initiator system having sensitivity to g-line.

Usually, the exposure of the color resist for producing the color filter is proximity exposure using a high-pressure mercury lamp or mirror projection exposure. In these exposures, i-line (365 nm), h-line (405 nm), and g-line (436 nm) are main emission line spectra.
Therefore, in order to manufacture a color filter with these exposure machines, a color resist sensitive to i-line, h-line or g-line must be applied. However, since the initiator system sensitive to g-line is colored yellow, it is not preferable for color filter color design. So far, the initiator system that is sensitive to i-line and h-line is mainly used. It has been.

  On the other hand, in the case of a green resist, it absorbs i-line and h-line light, so the amount of exposure light reaching the lower layer of the green colored layer (the far side from the exposure side) is drastically reduced, and as a result, it hardens in the lower layer. It becomes difficult. The lower layer portion that is not sufficiently cured is eroded by the developing solution in the developing process to cause an undercut, and the patterning property is deteriorated. In severe cases, the pattern may be missing or the pattern may be washed away by the developer.

Accordingly, the present inventors have conducted earnest research on the idea that the sensitivity of the resist can be further increased by using g-line in addition to i-line and h-line in the photocuring reaction.
As a result, it has been found that the use of the specific pyromethene compound according to the present invention in a colored curable composition can increase the sensitivity, and the present invention has been achieved.
The compound according to the present invention absorbs at 450 to 540 nm and is colored slightly yellow, but there is almost no problem in the design of colored pixels such as red and green that absorb in the visible shortwave region, and the sensitivity is increased. This is particularly effective for green, which has a high degree of difficulty.

<1> A color containing a colorant, a polymerizable compound, a photopolymerization initiator, and a sensitizer, wherein the sensitizer is at least one selected from the following general formula (1). It is a coloring curable composition for filters.

In General Formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, a hydrocarbon ring group, a heterocyclic group, or —SO ₃ —R ⁰ ( R ⁰ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a quaternary ammonium group), R ⁷ represents an alkyl group having 6 to 15 carbon atoms, and X ¹ and X ² each independently represent a halogen atom. An atom, an alkyl group, an aryl group, an aralkyl group, or an aromatic heterocyclic group is represented. These groups may be further substituted.

<2> The colored curable composition for color filters according to <1>, wherein the polymerizable compound is a compound containing three or more (meth) acryloyl groups in one molecule.

<3> The color filter content according to <1> or <2>, wherein the content of the colorant with respect to the total solid content of the curable colored resin composition is 30% by mass or more and 70% by mass or less. It is a colored curable composition.

<4> The color filter according to any one of <1> to <3>, wherein one or more types from the following group A and one or more types from the following group B are used in combination as the colorant: It is a colored curable composition for use.
Group A: Color Index Pigment Green 7,36
Group B: Color Index Pigment Yellow 138, 139, 150, 185

<5> The above-mentioned polymerizable compound is at least one selected from dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and pentaerythritol tetra (meth) acrylate. The colored curable composition for a color filter according to any one of 1> to <4>.

<6> Further, an alkali-soluble resin is contained, and the alkali-soluble resin includes, as a monomer component, at least one selected from (meth) acrylic acid, maleic acid, maleic anhydride, and crotonic acid, and methyl (meth) Total solids of the curable colored resin composition comprising at least one copolymer having at least one selected from acrylate, butyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene The colored curable composition for a color filter according to any one of <1> to <5>, wherein the content of the alkali-soluble resin relative to the amount is 5% by mass or more and 30% by mass or less. It is.

<7> Furthermore, the content rate of the said surfactant with respect to the total solid of a curable coloring resin composition is 0.01 including the surfactant whose content of a fluorine atom is 5 mass% or more and 20 mass% or less. The colored curable composition for a color filter according to any one of <1> to <6>, wherein the color curable composition is for a color filter.

<8> A color filter produced using the colored curable composition for a color filter according to any one of <1> to <7>.

<9> A backlight, a polarizing plate, at least two substrates, a liquid crystal layer sandwiched between the substrates, a color filter layer according to <8> provided on at least a part of the substrate, A liquid crystal display device having

According to the present invention, it is possible to provide a colored curable composition for a color filter that is excellent in developability even at a low exposure amount.
In addition, a color filter and a liquid crystal display device having high color purity and excellent patternability can be provided.

  The colored curable composition for color filters of the present invention (hereinafter sometimes referred to as “colored curable composition of the present invention”) includes a colorant, a polymerizable compound, a photopolymerization initiator, and a sensitizer. contains. The sensitizer is at least one selected from the following general formula (1).

In General Formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, a hydrocarbon ring group, a heterocyclic group, or —SO ₃ —R ⁰ ( R ⁰ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a quaternary ammonium group), R ⁷ represents an alkyl group having 6 to 15 carbon atoms, and X ¹ and X ² each independently represent X ¹ and X ^{2 each} represents a halogen atom, an alkyl group, an aryl group, an aralkyl group, or an aromatic heterocyclic group. These groups may be further substituted.

  If the pyromethene compound represented by the general formula (1) is used in the colored curable composition, the color curable composition for color filters can be highly sensitive. This is particularly effective in the case of green, which is difficult to achieve high sensitivity.

The pyromethene compound is disclosed in the following patent documents.
For example, Japanese Patent Application Laid-Open No. 2002-244287 discloses that an initiator titanocene compound is used in combination with a lithographic printing plate, and exposure is performed with a 488 nm or 532 nm laser. However, the purpose of this patent document is to increase the adhesive strength with an aluminum substrate and improve the printing strength. When a pyromethene compound or the like is added to acryloyl phosphates, the adhesive strength with the aluminum substrate is increased, and the pyromethene compound is not used for the purpose of increasing the sensitivity.

  Moreover, in the said patent document regarding a lithographic printing plate, PB15: 6 as a pigment contains 3 mass% with respect to composition solid content. However, in the case of a colored curable composition for a color filter, the pigment is usually contained in the range of 30 to 50% by mass. In the disclosed lithographic printing plate, since the sensitivity is adjusted with a composition having a low pigment concentration, if this composition is applied to a colored curable composition for a color filter as it is, the sensitivity is insufficient. Not applicable.

Furthermore, JP-A-2006-79012 discloses that a metal chelate pyromethene compound is used as a colorant in a spectral adjustment filter. The spectral adjustment filter is used in combination with a color filter, but is not related to a color filter, and is not used as a sensitizer in this patent document.
Hereinafter, the composition of the colored curable composition for a color filter of the present invention will be described.

[Colored curable composition for color filter]
The colored curable composition for a color filter of the present invention contains (A) a colorant, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a sensitizer. E) It may contain other components.

<(A) Colorant>
(A) A coloring agent means what colors the coloring curable composition of this invention. As the colorant, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.
As the pigment, various color pigments 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. The structure is organic such as azo, anthraquinone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, diketopyrrolopyrrole, quinophthalone, etc. In addition to pigments, various inorganic pigments can also be used.
Specific examples of pigments that can be used are shown below by pigment numbers. In addition, “CI” described below means a color index (CI).

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276.
Of these, 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.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.
Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 3, 15: 6.

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

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

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

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.

Since the colored curable composition of the present invention contains a specific pyromethene compound, it absorbs at 450 to 540 nm and is slightly colored yellow. Even if it is colored yellow, it is particularly effective for a pixel whose color change is small. Such a pixel is a colored pixel having a color tone that absorbs a yellow wavelength region such as red or green, and is particularly useful for a green pixel. Among the green pixels, C.I. I. Pigment Green 7, 36 or more, C.I. I. It is preferable to use one or more of pigment yellows 138, 139, 150, and 185 in combination.
Even if these pigments are not used, the colored curable composition of the present invention is effective in designing colored pixels such as red and green that absorb in the visible short wave region (yellow wavelength region). In the color design of red and green pixels, the coloring with the specific pyromethene compound of the present invention hardly needs to be considered.

  Moreover, when the coloring composition for color filters of this invention is the coloring curable composition for resin black matrices of a color filter, a black coloring agent can be used as a coloring agent. The black colorant may be a black colorant alone, or may be a mixture of red, green, blue and the like. These colorants can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  Coloring agents that can be mixed to prepare a black colorant include Victoria Pure Blue (42595), Auramine O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK70: 100 (50240), Erioglaucine X (42080), N0.120 / Lionol Yellow (21090), Dionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D ( 21095), Shimla Fast Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Onol Blue ES (Pigment Blue 15: 6), Dionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), and the like (in addition, the numbers in parentheses above are the color index ( CI))).

  Further, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

Examples of the black colorant that can be used alone include carbon particles such as carbon black, acetylene black, lamp black, bone blutter, graphite, iron black, aniline black, cyanine black, titanium black, and silver, or particles containing metal. Can be mentioned.
Examples of preferable metals constituting these metal fine particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium. , Tantalum, bismuth, antimony, and alloys thereof. Further preferable metal is at least one selected from copper, silver, gold, platinum, palladium, tin, calcium, and alloys thereof, and particularly preferable metal is copper, silver, gold, platinum, tin, and alloys thereof. A compound with other elements other than metals is also preferable.
Examples of the compound of metal and other elements include metal oxides, sulfides, sulfates, carbonates, and the like, and these particles are preferable as the metal compound particles. Of these, sulfide particles are preferred because of their color tone and ease of fine particle formation.
Moreover, a metal, its alloy, and a metal compound may be used together, and 2 or more types may be sufficient as it. Among these, silver or an alloy thereof and a sulfide thereof are particularly preferable because of their high shielding effect. As an example of an alloy, a silver tin alloy is mentioned as a preferable example.

  Among these black colorants, alloys such as carbon black, titanium black, silver and silver tin, and sulfides thereof are preferable because of their high shielding effect. Examples of carbon black include the following carbon black.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31

  Degussa: PrintexS, Printex3OP, PrintexSO, Pril: itex30OP, Printex40, Printex45, Printex55, PrintexGO, Printex75, PrintexSO, Printex85, Printex9O, PrintexA, PrintexL, PrintexG, PrintexP, PrintexU, Printexv, PrintexG, SpecialBlack550, Specia1B1ack350, Specia1B1ack250, Special Black100, Special Black6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Col r Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

  Manufactured by Cabot: Monarch120, Monarch280, Monarch4, 60, Monarch800, Monarch880, Monarch900, MonarchGA, GAR6LRE, REGAL250, REGAL250, REGAL250, REGAL250, REGAL250 PEARlS480, PEARLS130, VULCAN XC72R, ELFTEX-8

  Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890, Raven1000, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVENS750, RAVEN7000

Examples of titanium black include the following.
As a method for producing titanium black, a mixture of titanium dioxide and titanium metal is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. It is not a thing.

Examples of commercially available titanium black include Mitsubishi Materials Titanium Black 10S, 12S, 13R, 13M, 13M-C, and the like.
As an example of another black pigment, aniline black, an iron oxide black pigment, and organic pigments of three colors of red, green, and blue can be mixed and used as a black pigment.
In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.

  The above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

The average primary particle size of these pigments is preferably 10 nm to 100 nm, more preferably 10 nm to 50 nm.
The content of the pigment is preferably 30% by mass or more and 70% by mass or less, more preferably 38% by mass or more and 60% by mass or less, and 42% by mass with respect to the total solid content of the colored curable composition. % To 60% by mass is more preferable.
In the present invention, the “total solid amount” means all components excluding the solvent component, that is, (A) a colorant, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) sensitization. It is meant to include components other than the solvent among the agent and (E) other components.

As described above, a pigment is preferable as the colorant from the viewpoint of heat resistance, light resistance, and the like, but a dye can also be used.
Examples of the dye 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.

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

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Examples include Day Sparse Blue 60.

  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.

<(B) Polymerizable compound>
The colored curable composition of the present invention contains a polymerizable compound.
The polymerizable compound used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and a compound having at least one, preferably three or more terminal ethylenically unsaturated bonds in one molecule. Chosen from. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention.

These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.
Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.

Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used.
Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (2) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

Formula ^{_{(2): CH 2 = C}} (R 4) COOCH 2 CH (R 5) OH
In general formula (2), R ⁴ and R ⁵ represent H or CH ₃ .

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; finger ring types such as cyclohexane diisocyanate and isophorone diisocyanate Diisocyanate; aromatic diisocyanate such as toluene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3-hydroxy (1, Reaction products with (meth) acryloyl group-containing hydroxy compounds such as 1,1-trimethacryloyloxymethyl) propane And the like.
In the present invention, the term “(meth) acryloyl group” means that both an acryloyl group and a methacryloyl group are included, and (meth) acrylate, (meth) acrylic acid and the like have the same meaning.

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, A highly sensitive photopolymerizable colored curable composition can be obtained.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  About these polymerizable compounds, the details of the usage method such as the structure, single use or combination, addition amount and the like can be arbitrarily set according to the performance design of the final colored curable composition.

The polymerizable compound is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Moreover, you may introduce | transduce an acid group by making a non-aromatic carboxylic anhydride react with the hydroxyl group of the above-mentioned ethylenic compound as needed.
In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

A preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. In the case of an acid value in this range, the development and dissolution characteristics are excellent, the production and handling are easy, and the photopolymerization performance is good, so that the curability such as the surface smoothness of the pixel is excellent.
Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer are adjusted to fall within the above range. It is desirable to do.

  In the present invention, more preferred polyfunctional monomers having an acid group are mainly dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate which are commercially available as T01382 manufactured by Toa Gosei Co., Ltd. It is a mixture as a component. Other polyfunctional monomers can be used in combination with this polyfunctional monomer.

  Further, in terms of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. In order to increase the strength of the image area, that is, the cured film, the polymerizable compound is preferably a tri- or higher functional compound, and particularly preferably a compound containing three or more (meth) acryloyl groups in one molecule. .

  Furthermore, it is also effective to adjust both sensitivity and strength by using different functional groups and different polymerizable groups (for example, acrylic ester, methacrylic ester, styrene compound, vinyl ether compound). .

  From the viewpoint of sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. . Moreover, it is preferable to contain an EO modified body from a viewpoint of a sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of a sensitivity and an exposure part intensity | strength.

  In addition, selection and use of addition polymerization compounds for compatibility and dispersibility with other components (eg, binder polymer, photopolymerization initiator, colorant (pigment, dye, etc.) in the colored curable composition The method is an important factor, and for example, compatibility may be improved by using a low-purity compound or a combination of two or more types, and also improve the adhesion of the support or the overcoat layer described later. A specific structure may be selected for the purpose.

From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D Le) isocyanurate, pentaerythritol tetraacrylate EO-modified product, dipentaerythritol hexaacrylate EO-modified products thereof as preferred.
Moreover, as a commercial item of a polymeric compound, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp Co., Ltd.), DPHA (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH -600, T-600 and AI-600 (manufactured by Kyoeisha) are preferred.

Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetra A modified acrylate EO, a modified dipentaerythritol hexaacrylate EO, and the like are preferable, and at least one selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and pentaerythritol tetraacrylate is more preferable.
As a commercial item, DPHA (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha) are more preferable.

  The content of the polymerizable compound is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and more preferably 10 to 35% by mass in the total solid content of the colored curable composition in the present invention. More preferably.

<(C) Photopolymerization initiator>
The colored curable composition of the present invention contains a photopolymerization initiator that directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

When a black photopolymerizable layer is formed with a colored curable composition, the photopolymerization initiator is sensitive to ultraviolet light to visible light because the image is exposed from the photopolymerizable layer through a pattern mask. It means a compound that exhibits, and it is preferable to use an exposure light source corresponding to the image exposure.
Also in the red, green, and blue photopolymerizable layers, red, green, and blue allo-image patterns are formed between the four black matrix patterns by exposure through a pattern mask for each color and other methods. Therefore, as in the case of the black matrix pattern, the photopolymerization initiator is preferably a compound that exhibits sensitivity to ultraviolet light to visible light, particularly a compound that exhibits spectral sensitivity at a wavelength of 450 nm or less, particularly 400 nm or less.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbiimidazoles described in JP-A-10-39503. Derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino-acids such as N-phenyl-glycine, N-aryl-α-amino-acid salts, N-aryl-α-amino-acid esters, etc. Examples include radical activators, α-amino-alkylphenone compounds, and oxime ester initiators described in JP-A No. 2000-80068.

  Furthermore, examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Examples include hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Halomethylated triazine derivatives such as ethoxynaphthyl) -4,6-bis (todichloromethyl) mono-s-triazine and 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 4- (o-bromo-pN) , N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (Tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, etc. It is done.

  2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2-benzofuryl) vinyl] -1,3,4-oxadi Azole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  2- (2′-chlorophenyl) -4,5-diphenyl-imidazolol dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (2 '-Fluorophenyl) -4,5-diphenyl-imidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenyl-imidazole dimer, (4'-methoxyphenyl) -4,5 -Imidazole derivatives such as diphenyl-imidazole dimer.

  Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl edel.

  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-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl (p-isopropylphenyl) ) Ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p -Acetophenone derivatives such as butylphenyl) ketone.

  Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone.

Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.
Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine.
Phenazine derivatives such as 9,10-dimethylbenzphenazine.
Anthrone derivatives such as benzanthrone.

  Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bisphenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di Cyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, dicyclopentadienyl-Ti-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis2,3 4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dicyclopen Dienyl -Ti-2,6-difluoro-3- (pyrr-1-yl) - titanocene derivatives such as phenyl-1-yl.

  2-Methyl-1 [4- (methyl-thio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 , 2-Benzyl-2-dimethyl-amino-1- (4-morpholinophenyl-) butanone-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopro Piophenone, 2-ethylhexynol-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. [Alpha] -aminoalkylphenone compounds.

  1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- Oxime ester compounds such as 3-yl]-, 1- (O-acetyloxime).

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-mol Forinophenyl) -butanone-1,2,4,6 trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4 -Acetophenone derivatives such as morpholinobyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, Examples thereof include benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl dimethyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dicyclopenta Dienyl-Ti-bis-2,4-di-fluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl- Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoro Enyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl Dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-penta Examples thereof include fluorophenyl-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like. Specific examples include Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As the photopolymerization initiator (D) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

  More preferably, they are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  Specific examples of the photopolymerization initiator component include dialkyl acetophenone compounds described on pages 16 to 26 of "Fine Chemical" (March 1, 1991, vo 1.20, N0.4). Benzoin, thioxanthone derivatives, and the like, as well as hexaarylbiimidazole series, S-trihalomethyltriazine series, and JP-A-4-221958 described in JP-A-58-403023 and JP-B-45-37377. And a combination of a titanocene and a xanthene dye, an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group, and the like described in JP-A-4-219756. .

A photoinitiator may be used individually by 1 type and may use 2 or more types together.
The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to 1% by mass with respect to the total solid content of the colored curable composition. 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

<(D) Sensitizer>
The colored curable composition of the present invention has a specific pyromethene compound represented by the following general formula (1). Sensitivity can be improved by adding a compound represented by the general formula (1).

In General Formula (1), R ^{1 to} R ⁶ are a hydrogen atom, an alkyl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, a hydrocarbon ring group, a heterocyclic group, or —SO ₃ —R ⁰ (R ⁰ is a hydrogen atom) Atom, alkyl group, aryl group, aralkyl group, quaternary ammonium group). R ⁷ represents an alkyl group having 6 to 15 carbon atoms, X ¹ and X ² are each independently X ¹ and X ² are each independently a halogen atom, an alkyl group, an aryl group, an aralkyl group, Represents an aromatic heterocyclic group. These groups may be further substituted.

In the present invention, in the general formula (1), at least one of R ^{1 to} R ⁶ has an alkyl group branched at the α-position or β-position, and in particular, R ² or R ⁵ has an α-position. Alternatively, it preferably has an alkyl group branched at the β-position. This branched alkyl group is preferably represented by the following general formula (3).

In General Formula (3), R ⁹ and R ¹⁰ represent an alkyl group having 1 to ¹⁰ carbon atoms, preferably 1 to 7 carbon atoms, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and q is 0. Or 1 is represented.
The branched alkyl group is more preferably an alkyl group having 3 to 20 carbon atoms having a secondary or tertiary carbon atom in the α-position or β-position, and more preferably 3 in the α-position or β-position. It is a C4-C7 alkyl group having a secondary carbon atom.

  In the pyromethene compound in which an alkyl group having a secondary or tertiary carbon atom is introduced at the α-position or β-position, the absorption wavelength peak is shifted to the longer wavelength side compared to the case where the corresponding alkyl group is linear. In addition, the sensitivity to the oscillation wavelength of a 488 nm argon ion laser or a 532 nm YAG laser is enhanced. Moreover, this pyromethene compound has favorable solubility with respect to various coating solvents.

  Specific examples of the alkyl group branched at the α-position or β-position include, for example, the following (in the following formula, q represents 0 or 1 as described above).

Furthermore, the following are mentioned as an example of the substituted or unsubstituted alkyl group used for R < ¹ > -R < ⁶ >.

Moreover, the following are mentioned as an example of the acyl group used for R < ¹ > -R < ⁶ >.

Moreover, the following are mentioned as an example of the alkoxycarbonyl group used for R < ¹ > -R < ⁶ >.

The substituted or unsubstituted hydrocarbon ring group used for R ^{1 to} R ⁶ is preferably a 1 to 3 ring aryl group or an aliphatic hydrocarbon ring group having 6 to 10 carbon atoms. Specific examples include the following.

In the present invention, R ⁷ is different from R ^{1 to} R ⁶ described above and represents an alkyl group having 6 to 15 carbon atoms. The carbon chain of the alkyl group is preferably linear, but can also be branched. Branching can be used in any of α-position, β-position, ω-position, and the like. In the present invention, the significance of this R ⁷ is extremely important. As is apparent from Comparative Examples described later, when the number of carbon atoms is 5 or less, it contributes to printing durability even though it has an effect as a sensitizer. I can't.

X ¹ and X ² each independently represent a halogen atom, an alkyl group, an aryl group, an aralkyl group, or an aromatic heterocyclic group. These groups may be further substituted.
. X ¹ and X ² are preferably each independently a halogen atom, and particularly preferably a fluorine atom.

The combinations of R ^{1 to} R ⁷ detailed above are diverse. Specific examples of the pyromethene compound suitable for the present invention are listed below, but are not limited to these exemplified compounds.

In the following exemplary compounds, X ¹ and X ² are both fluorine atoms.

From the viewpoint of sensitivity, the amount of the compound represented by the general formula (1) is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound in the photopolymerizable photosensitive layer. Preferably it is 0.05-20 mass parts.
The compound represented by General formula (1) can be used individually by 1 type or in combination of 2 or more types.

  Furthermore, sensitizing dyes having other structures can be used together if necessary. Specific examples thereof include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703, JP-A-5-289335 and the like. Coumarin dyes having a complex belly, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, and others, JP-A-47-2528, JP-A-54 -155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, Japanese Laid-Open Patent Publication No. 59-56403, Japanese Laid-Open Patent Publication No. 2-69, Japanese Laid-Open Patent Publication No. 57-168088, Japanese Laid-Open Patent Publication No. 5-107761, -210240, JP-like dyes having a dialkyl aminobenzene skeleton are described in, JP-A-4-288818 discloses the like.

  It is preferable to make content as the whole sensitizer into the range of 0.01-20 mass% in the total solid amount in the colored curable composition of this invention. More preferably, it is 0.1-15 mass%, More preferably, it is 0.5-10 mass%.

<(E) Other ingredients>
The colored curable composition of the present invention can contain other components. Examples of other components include (E-1) chain transfer agent, (E-2) solvent, (E-3) binder resin, (E-4) thermal polymerization inhibitor, (E-5) plasticizer, (E-6) Dispersant, (E-7) Dispersion aid, (E-8) Surfactant, storage stabilizer, surface protective agent, smoothing agent, coating aid, adhesion improver, coatability improver , Development improvers, silane coupling agents, and the like.

(E-1) Chain transfer agent Examples of the chain transfer agent that can be added to the colored curable composition of the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester. , 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, mercapto compounds having a heterocyclic ring such as 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

(E-2) Solvent Examples of the solvent that can be applied to the colored curable composition of the present invention include glycol ethers and / or alkoxy esters.

  Specific examples of glycol ethers include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-n-butyl ether, Ethylene glycol acetate, ethylene glycol diacetate, ethylene glycol diethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol diethyl coether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n- Butylue Ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, tripropylene glycol methyl ether.

  Specific examples of alkoxyesters include ethyl acetate, methyl isobutyrate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid. Examples include propyl, butyl 3-methoxypropionate, butyl acetate, butyl acetate (n, sec, t-), butyl stearate, ethyl propionate, ethyl benzoate, ethyl orthoformate, ethyl caprylate, propyl acetate and the like. .

  In addition, for example, diisopropyl ether, mineral spirit, n-pentane, amyl ether, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, n-octane, Barsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, Apco Thinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl noninoreketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, amyl chloride, butylene glycol diacetate, methoxymethyl pentanone, methyl butyl ketone, methyl hexyl Ketone, benzonitrile, methyl cellosolve acetate, methylenoisoamyl ketone, methyl isobutyl ketone, amyl acetate, amyl formate, bicyclohexyl, dipentene, methoxymethyl pentanol, methyl amyl ketone, methyl isopropyl ketone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve , Ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl lactate, propylene glycol, 3-methyl Kishipuropion acid, 3-ethoxy propionate, diglyme, ethyl carbitol, butyl carbitol, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate and the like.

A solvent may be used individually by 1 type and may use 2 or more types together.
The content of the solvent in the entire colored curable composition of the present invention is appropriately set in the range of usually 50 to 95% by mass, depending on the ratio (concentration) of the total solid content. More preferred is 70 to 90% by mass, and particularly preferred is 75 to 90% by mass.
If the content of the solvent is too small, the viscosity becomes too high to be applied, and if it is too large, it becomes difficult to form a coating film.

(E-3) Binder resin The binder resin is appropriately selected in consideration of the formability and performance of the target pixel image, the manufacturing method to be employed, and the like.
Specific examples of the binder resin include, for example, homopolymers such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, and maleimide. Or a copolymer containing these monomers, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetylcellulose, novolac resin, resole resin, polyvinylphenol, polyvinyl butyral, and the like. JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, It can be used known polymer compounds described in Open 2003-233179 Patent Publication.

  Among the binder resins, preferred are polymer compounds containing no nitrogen atom, and more preferred is the embodiment (I) or (II) below.

  (I) An alkali-soluble resin having at least one group that promotes alkali solubility (hereinafter abbreviated as “alkali-soluble resin”).

  (II) (A): 5 to 90 mol% of an epoxy group-containing (meth) acrylate, (B): copolymerized with 10 to 95 mol% of another radical polymerizable compound that can be copolymerized with the component (A). (C) Unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group contained in the resulting copolymer, and 10 to 100 mol% of the hydroxyl group produced when the component (C) is added. (D) A resin obtained by adding a polybasic acid anhydride {hereinafter abbreviated as resin (II)}.

In the colored curable composition of the present invention, an alkali-soluble resin can be used as a binder polymer for the purpose of improving film properties.
The alkali-soluble resin used in the present invention is a linear organic polymer, and at least one molecule in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).

More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-25957, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, maleic acid as described in JP-A-59-53836 and JP-A-59-71048 Copolymers, partially esterified maleic acid copolymers, etc., as well as those of acrylic copolymers such as acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group with an acid anhydride added. It is done.
The acid value is preferably in the range of 20 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, more preferably 50 to 150 mgKOH / g.

  As a specific configuration of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include CH ₂ ═C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ Represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ].
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) ) Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms) ), Hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferable. As the polyalkylene oxide chain, a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof can be used, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable.
Examples of the acrylic copolymer having a polyalkylene oxide chain in the side chain include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. , And compounds in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate, etc. An acrylic copolymer as a component.

As the vinyl compound, CH ₂ = CR ¹ R ² [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. , R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
Other monomers that can be copolymerized can be used singly or in combination of two or more. Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.

As described above, the acrylic resin preferably has an acid value in the range of 20 to 200 mgKOH / g. When the acid value exceeds 200, the acrylic resin becomes too soluble in alkali and the appropriate development range (development latitude) becomes narrow. On the other hand, if it is too small, such as less than 20, the solubility in alkali is small and it takes too much time for development, which is not preferable.
In addition, the weight average molecular weight Mw of the acrylic resin (polystyrene conversion value measured by the GPC method) is used to realize a viscosity range that is easy to use in a process such as applying a color resist, and to secure film strength. , Preferably from 2,000 to 100,000, more preferably from 3,000 to 50,000.

In order to improve the crosslinking efficiency of the colored curable composition in the present invention, an alkali-soluble resin having a polymerizable group may be used alone or in combination with an alkali-soluble resin having no polymerizable group.
As the alkali-soluble resin having a polymerizable group, a polymer having an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and further has photocurability and thermosetting properties. Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as each molecule contains an alkali-soluble group such as a COOH group and an OH group and a carbon-carbon unsaturated bond. .

(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin,
(2) an unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule;
(3) Acid pendant type epoxy acrylate resin,
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Among the above, the resins (1) and (2) are particularly preferable.

As a specific example, a copolymer of an OH group, for example, 2-hydroxyethyl acrylate, a COOH group, for example, methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable therewith Further, a compound obtained by reacting an epoxy ring having reactivity with an OH group and a compound having an unsaturated bond group between carbon (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, in addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group, or an acryloyl group can also be used.
Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyurethane acrylic oligomer, Diamond Shamrock Co. Ltd .; Biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).

  Suitable alkali-soluble resins include, as monomer components, one or more selected from (meth) acrylic acid, maleic acid, maleic anhydride, and crotonic acid, methyl (meth) acrylate, butyl (meth) acrylate, and phenyl (meth) And a copolymer having at least one selected from acrylate, benzyl (meth) acrylate, and styrene.

  As addition amount of alkali-soluble resin, it is preferable that it is the range of 3-70 mass% in the total solid amount of the colored curable composition of this invention, and 5-60 mass% is more preferable.

In preparing the resist, it is preferable to add the following epoxy resin in addition to the alkali-soluble resin. The epoxy resin is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( As described above, manufactured by Tohto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103 etc. In addition, bisphenol F type and bisphenol S type epoxy resins similar to these can also be used.
Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used. Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Tohto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei), and biphenyl type Examples of alicyclic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT. -401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. (manufactured by Toto Kasei), Epilon 430, 673, 695, 850S, 4032 (Dainippon Ink) It can be mentioned. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine-type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resins can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient and the reliability is poor or the flatness is poor.
Specific compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl- 4,4 'diglycidyl biphenyl, ceroxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, etc. are mentioned.

  Resin (II) component (A): 5 to 90 mol% of epoxy group-containing (meth) acrylate, (B): copolymerized with 10 to 95 mol% of other radical polymerizable compound that can be copolymerized with component (A) (C) an unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group contained in the resulting copolymer, and 10 to 100 of the hydroxyl group produced when the component (C) is added. The resin obtained by adding (D) polybasic acid anhydride to mol% will be described below.

  (A): Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxy Examples thereof include butyl (meth) acrylate glycidyl ether, and glycidyl (meth) acrylate is particularly preferable. These (A) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  (A): Copolymerization ratio of epoxy group-containing (meth) acrylate (copolymerization ratio when copolymerizing (A) component and (B) component to produce a copolymer). ") Is 5 to 90 mol% as described above, preferably 20 to 80 mol%, more preferably 30 to 70 mol%. Within this range, heat resistance and strength are excellent, and the addition amount of the polymerizable component and the alkali-soluble component is sufficient, which is preferable.

  On the other hand, the copolymerization ratio of the other radical polymerizable compound that can be copolymerized with the component (B) :( A) is 10 to 95 mol% as described above, preferably 20 to 80 mol%, and more Preferably it is 30-70 mol%. At this ratio, the addition amount of the polymerizable component and the alkadi-soluble component is sufficient, and the heat resistance and strength are excellent.

  As the other radical polymerizable compound that can be copolymerized with the component (B) :( A), one or more of mono (meth) acrylates having a structure represented by the following general formula (4) are used. It is preferable.

In General Formula (4), R ^{4 to} R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and R ¹⁰ and R ¹¹ are each independently Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or may be linked to form a ring. The ring formed by connecting R ¹⁰ and R ¹¹ is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms. )

  In the said General formula (4), the mono (meth) acrylate which has a structure represented by following formula (5), (6) or (7) is preferable. By introducing these structures into the binder resin, it is possible to increase heat resistance and strength. Of course, these mono (meth) acrylates may be used alone or in combination of two or more.

  As the mono (meth) acrylate having the structure represented by the formula (4), various known ones can be used, and those represented by the following general formula (8) are particularly preferable.

In the general formula (8), R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents the chemical formula (4).
The content of the mono (meth) acrylate having the structure of the chemical formula (4) in the copolymerization monomer is usually 5 to 90 mol%, preferably 10 to 70 mol%, and more preferably 15 to 50 mol%. It is.

  Moreover, although it does not specifically limit as (B) radically polymerizable compound other than the above, The following can be mentioned as the specific example.

Styrene, α-, o-, m-, p-alkyl, nitro, cyano, amido ester derivatives of styrene.
Gens such as butadiene, 2,3-dimethyl-butadiene, isoprene and 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, (tert) -butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid-2- Ethylhexyl, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, (meth) Isobornyl acrylate, adamantyl (meth) acrylate, (meth) a Allyl acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, (meth ) Salicyl acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, (meta ) Cresyl acrylate, (meth) acrylic acid-1,1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro (meth) acrylate -Iso-propyl, triphenylmethyl (meth) acrylate, (meth ) (Meth) acrylic such as cumyl acrylate, (meth) acrylic acid-3- (N, N-dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl Acid esters.

(Meth) acrylic acid amide, (meth) acrylic acid: ES1N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N -(Meth) acrylic acid amides such as di-iso-propylamide, (meth) acrylic acid anthracenylamide.
Vinyl compounds such as (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate.
Unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate and diethyl itaconate.
Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide.
N- (meth) acryloylphthalimide and the like can be mentioned.

In order to impart more excellent heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the component (B).
In this case, the copolymerization ratio selected from styrene, benzyl (meth) acrylate and monomaleimide is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.

A known solution polymerization method is applied to the copolymerization reaction between the component (A) and the component (B). The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Specific examples thereof include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isoallopyl acetate, cellosolve acetate, and butyl cellosolve acetate;
Diethylenedadicol monoalkylate / oleate acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate;
Propylene glycol monoalkyl ether acetates;
Acetates such as dipropylene glycol monoalkyl ether acetates;
Ethylene glycol dialkyl ethers;
Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol;
Triethylene glycol dialkyl ethers;
Propylene glycol dialkyl ethers;
Dipropylene glycol dialkyl ethers;
Ethers such as 1,4-dioxane and tetrahydrofuran;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone;
Hydrocarbons such as bengan, toluene, xylene, octane, decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha;
Lactate esters such as methyl lactate, ethyl lactate and butyl lactate;
Examples include dimethylformamide and N-methylpyrrolidone.

  These solvents may be used alone or in combination of two or more. The amount of these solvents used is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, with respect to 100 parts by mass of the resulting copolymer. When the amount of the solvent used is within this range, it is easy to control the molecular weight of the copolymer.

The radical photopolymerization initiator used in the copolymerization reaction between the component (A) and the component (B) is not particularly limited as long as it can initiate radical polymerization, and is generally used organic peroxidation. An object or an azo compound can be used.
Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.
Specific examples of the radical photopolymerization initiator include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxide. Oxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2 , 5-Bis (t-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t- Butylcyclohexyl) peroxydicarbonate Diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, laudyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1 , 1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarbonamide and the like, radical light having an appropriate half-life depending on the polymerization temperature One or more polymerization initiators are selectively used.
The amount of the radical photopolymerization initiator used is 0.5 to 20 parts by mass, preferably 1 to 10 parts per 100 parts by mass of the monomer used in the copolymerization reaction, that is, the total of the component (A) and the component (B). Part by mass.

  The copolymerization reaction between the component (A) and the component (B) may be carried out by dissolving the monomer and radical photopolymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring. You may carry out by dripping the monomer which added the polymerization initiator in the solvent which heated and stirred. Further, the monomer may be added dropwise while the radical photopolymerization initiator is added to the solvent and the temperature is raised. The reaction conditions can be freely changed according to the target molecular weight.

(C) component added to the epoxy group contained in the copolymer of (A) component and (B) component is an unsaturated monobasic acid.
(C) As a component, a well-known thing can be used, The unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned, As an example, acrylic acid, methacrylic acid, crotonic acid, o-, Examples thereof include monocarboxylic acids such as m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano substitution. Of these, acrylic acid and / or methacrylic acid are preferred.
These (C) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

Component (C) is added to 10 to 100 mol% of the epoxy group contained in the copolymer obtained by the copolymerization reaction of component (A) and component (B), preferably 30 to 100 mol%. More preferably, it is added to 50 to 100 mol%. When the addition ratio of the component (C) is within this range, the stability over time is excellent.
As a method for adding the component (C) to the copolymer of the component (A) and the component (B), a known method can be employed.
As the (D) polybasic acid anhydride to be added to the hydroxyl group produced when the (C) component is added to the copolymer of the (A) component and the (B) component, known ones can be used, Dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimedite anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid Examples thereof include polybasic acid anhydrides such as anhydrides and biphenyltetracarboxylic acid anhydrides. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable.
(D) A component may be used individually by 1 type and may be used in mixture of 2 or more types. By adding such components, the Novainder resin used in the present invention can be made alkali-soluble.

  Component (D) is added to 10 to 100 mol% of the hydroxyl group produced when component (C) is added, preferably 20 to 90 mol%, more preferably 30 to 80 mol%. . When the ratio is within this range, the remaining film ratio during development is good and the solubility is sufficient.

  As a method of adding the component (D) to the hydroxyl group produced when the component (C) is added to the copolymer of the component (A) and the component (B), a known method may be adopted. it can.

In the present invention, in order to further improve the photosensitivity, (D) after addition of polybasic acid anhydride, a glycidyl ether compound having a glycidyl (meth) acrylate or a polymerizable unsaturated group in a part of the generated carboxyl group is added. In order to add or improve developability, after adding (D) polybasic acid anhydride, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl group, Both of these may be added.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (manufactured by Nagase Chemical Industries, Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol) EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like.
These resin structures are described in, for example, JP-A-8-297366 and JP-A-2001-89533, and are already known.

As a polystyrene conversion weight average molecular weight (Mw) measured by GPC of such resin (II), 3000-100000 are preferable and 5000-50000 are especially preferable. When the molecular weight is in this range, heat resistance, film strength and solubility are excellent.
The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2.0 to 5.0.

  Binder resin may be used individually by 1 type, and may use 2 or more types together. The proportion of the binder resin is preferably selected in the range of 10 to 80% by mass in the total solid content in the colored curable composition of the present invention, and particularly preferably 20 to 70% by mass.

  A silane coupling agent can be blended for the purpose of improving the affinity of the interface between the colorant and the binder resin. The ratio of the silane coupling agent is preferably selected in the range of 1 to 10% by mass in the total solid content.

(E-4) Thermal polymerization inhibitor Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol, and the like. .
The blending amount of these thermal polymerization inhibitors is preferably selected in the range of 0 to 3% by mass with respect to the total solid content in the colored curable composition.

(E-5) Plasticizer Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, todiethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. .
The blending amount of these plasticizers is preferably selected in the range of 0 to 10% by mass with respect to the total solid content in the curable colored resin composition.

(E-6) Dispersant As the dispersant, for example, acrylic acid and styrene, acrylic acid ester and methacrylic acid, acrylic acid and methacrylic acid ester, styrene and maleic acid copolymer, amide type, etc. Compounds, urethane compounds, lactam compounds, barbituric acid compounds, etc., and resin-type dispersants such as polyamide compounds and polyurethane compounds (in the commercial product, Dispavic 130, Dispavic 161, Dispa Bic 182, Dispavik 170, Efka 46, Efka 47, etc. manufactured by Efka Corporation) can be used.
Among these, a dispersant having a nitrogen-containing functional group is preferable, and an acrylic dispersant, a urethane dispersant, and a graft copolymer dispersant are more preferable.

As an acrylic dispersing agent, an AB block copolymer and / or a BAB block comprising an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base. A copolymer is preferred.
The A block constituting the block copolymer of the acrylic dispersant is a quaternary ammonium base, preferably -N ⁺ R _1a R _2a R _3a · Y ⁻ (where R _1a , R _2a , and R _3a are each Independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R _1a , R _2a , and R _3a are bonded to each other to form a cyclic structure; Y ⁻ represents a counter anion.) And has a quaternary ammonium base. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R _1a R _2a R _3a , as a cyclic structure formed by combining two or more of R _1a , R _2a , and R _3a with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

In said formula, R represents either group among R < _1a > -R < _3a >.
These cyclic structures may further have a substituent. As _R 1a _{to R 3a} in the ^{_{-N + R 1a R 2a R 3a}} , and more preferably may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a phenyl group or a benzyl group which may have a substituent.

  As the A block, those containing a partial structure represented by the following general formula (9) are particularly preferable.

In the general formula (9), R _1a , R _2a and R _3a each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R _1a , R _2a , and R _3a may be bonded to each other to form a cyclic structure. R _4a represents a hydrogen atom or a methyl group. X represents a divalent linking group, and Y ⁻ represents a counter anion.

In the general formula (9), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R _5a —, —COO—R _6a — (provided that R _5a and R _6a is a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R _7a —O—R _8a —: R _7a and R _8a are each independently an alkylene group). And the like, and preferably —COO—R _6a —.

Examples of Y ⁻ of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.

Two or more kinds of partial structures containing a specific quaternary ammonium base such as the general formula (9) may be contained in one A block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done.
The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. Most preferably, it is not included in the A block.

  On the other hand, as the B block constituting the block copolymer of the dispersant, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) methacrylate , Isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate (Meth) acrylate monomers such as glycidyl ethyl acrylate and N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, N-methylolacrylamide, , N-dimethyl-acrylamide, (meth) acrylamide monomers such as N, N-dimethylaminoethyl acrylamide; vinyl acetate; acrylonitrile; azyl glycidyl ether, crotonic acid glycidyl ether; N-methacryloylmorpholine Polymer structures.

  The B block is preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (10).

In the general formula (10), R _9a represents a hydrogen atom or a methyl group. R _10a 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. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be.
When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 50% by mass, more preferably 0 to 20% by mass, but it is most preferable that a partial structure other than the (meth) acrylic acid ester monomer is not included in the B block.

The acrylic dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block, and such a block copolymer. Is prepared, for example, by the living polymerization method shown below.
The diving polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical diving polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

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

  In synthesizing such an acrylic dispersant, JP-A-9-62002 and P.I. Lutz. P. Massoneta]. , Polym. Bull. 12, 79 (1984), B.I. C. Ande: rson, G.M. D. Andrewseta 1, Macromolecules, 14, 1601 (1981), K.M. Hatada, K .; Ute, etal, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawaki, Polymer Journal, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W .; R. Known methods described in, for example, Hertierta 1, Macromolecules, 20, 1473 (1987) can be employed.

  Whether the dispersant used in the present invention is an AB block copolymer or a B-A-B block copolymer, the A block / B block ratio (mass ratio) constituting the copolymer. Is usually in the range of 1/99 or more, especially 5/95 or more, and usually 80/20 or less, especially 60/40 or less. Outside this range, it may not be possible to combine good heat resistance and dispersibility.

Further, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the B-A-B block copolymer according to the present invention is usually preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.
Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mg-KOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and expressing it in mg of KOH corresponding to the acid value.

  Moreover, although the acid value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, it is generally preferable that the acid value is low, and is usually 100 mg-KOH / g or less, and its molecular weight is The weight average molecular weight (Mw) in terms of polystyrene measured by GPC is usually in the range of 1000 or more and 100,000 or less. When the molecular weight of the block copolymer is too small, the dispersion stability is lowered, and when it is too large, the developability and the resolution tend to be lowered.

In the present invention, as the dispersant, a commercially available urethane-based and / or acrylic-based dispersant having a structure similar to that described above can also be applied.
Examples of urethane dispersants include (1) polyisocyanate compounds, (2) compounds having one or two hydroxyl groups in the same molecule, and (3) compounds having active hydrogen and tertiary amino groups in the same molecule. A dispersion resin obtained by reacting is preferable.

(1) Polyisocyanate compound Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-didiphenylmethane diisocyanate, naphthalene-1,5-diisocyanate. , Aromatic diisocyanates such as tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) ), Alicyclic diisocyanates such as ω, ω′-diisocyne trimethylcyclohexane, xylylene diisocyanate, α, aliphatic diisocyanates having an aromatic ring such as α, α ′, α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), todiisocyanate such as tris (isocyanatephenyl) thiophosphate, and their trimers, water adducts, and their polyols Examples include adducts.

  Preferred as the polydiisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used individually by 1 type, and may mix and use 2 or more types.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. For example, a method of obtaining a desired isocyanurate group-containing polyisocyanate by performing trimerization and stopping the trimerization by addition of a catalyst poison, and then removing the polyisocyanate at the end reaction by solvent extraction and thin-film distillation.

(2) Compounds having one or two hydroxyl groups in the same molecule Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and these compounds. And a mixture of two or more of these having one end hydroxyl group alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these.
Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.
Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxydetramethylene) adipate.

  Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (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, neopentyl glycol 2-methyl-1,3-propane-diol, 2-methyl-2-propyl-1,3-propane-diol, 2-butyl-2-ethyl-1,3-propane-diol, 1,5-pentane Diol, 1,6-hexanediol, 2-methyl-2 4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene Glycol, aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromas such as xylylene glycol and bishydroxyethoxybenzene Group glycol, N-alkyl dialkanolamine such as N-methyl-diethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc. Diols or carbon number 1-2 Monohydric alcohol polylactone diol obtained by using as an initiator or polylactone monool, for example polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof.

  Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. .

Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.
Of the 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 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

(3) Compound having active hydrogen and tertiary amino group in the same molecule The compound having active hydrogen and tertiary amino group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  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 can be mentioned.

  In addition, as the tertiary amino group is a nitrogen-containing heterocycle, 4-pyrazole ring, imidazole ring, todiazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazonole ring N-containing hetero 5-membered rings such as benzothiazole ring and benzothiadiazole ring, and nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinidine ring, acridine ring and isoquinoline ring. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. .
Further, specific examples of the compound having a todiazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 2,4-todiazole, 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. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.

  A preferable blending ratio of the urethane-based dispersant raw material is 10 to 200 parts by mass of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. Is 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass. .

  The polystyrene-converted weight average molecular weight (Mw) measured by GPC of such a urethane-based dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. Range. Within this molecular weight range, the dispersibility and dispersion stability are excellent, the solubility and dispersibility are excellent, and at the same time, the reaction is easily controlled.

The production of such a urethane-based dispersant is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl One or more of aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.
In the production, a usual urethanization reaction catalyst is used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned.

The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mg-KOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of the basic group with an acid. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.
In addition, when an isocyanate group remains in the dispersion resin obtained by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability with time of the product becomes high.

  As the graft copolymer dispersant, those having a repeating unit containing a nitrogen atom in the main chain are preferable. Especially, it is preferable to have a repeating unit represented by the following general formula (11) or / and a repeating unit represented by Formula (12).

In General Formula (11), R ₁ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any of the following General Formulas (13) to (15).

In the general formula (11), R ¹ represents a chain-like or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably. Ethylene group. A represents a hydrogen atom or any one of the following general formulas (13) to (15), and is preferably general formula (13).

In the general formula ^{(12), R} 1, A has the same meaning as ^R 1, A of formula (11).

In the above formula (13), W ₁ represents Kawatoji or branched alkylene group having 2 to 10 carbon atoms, among others butylene, pentylene, an alkylene group having 4-7 carbon atoms such as hexylene preferred. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the above formula (14), Y ₁ represents a divalent linking group. Also preferred are alkylene groups having 1 to 4 carbon atoms such as ethylene and propylene, and alkyleneoxy groups having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy.
W ₂ represents a bottomed or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, butylene, etc. Among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable.
Y ₂ represents a hydrogen atom or —CO—R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms such as ethyl-, propyl, butyl, pentyl, hexyl, etc., among which carbon number such as ethyl, propyl, butyl, pentyl, etc. 2-5 alkyl groups are preferred).
q represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the above formula (15), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, and among them, 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 (11) or (12) in the graft copolymer of the present invention is preferably as high as possible, usually 50 mol% or more, and preferably 70 mol% or more. The repeating unit represented by the formula (11) and the repeating unit represented by the formula (12) may both be present, and the content ratio is not particularly limited, but preferably the formula (11) It is preferable to contain a larger number of repeating units.
The total number of repeating units represented by formula (11) or formula (12) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50.

Moreover, repeating units other than Formula (11) and Formula (12) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. The graft copolymer of the present invention preferably has a terminal having —NH ₂ and —R ₁ —NH ₂ (R ₁ is as defined above for R ₁ ).
In the graft copolymer of the present invention, the main chain may be linear or branched.

  The amine value of the graft copolymer of the present invention is usually from 5 to 100 mgKOH / g, preferably from 10 to 70 mgKOH / g, and more preferably from 15 to 40 mgKOH / g. When the amine value is within this range, the dispersion stability is good, the viscosity is stable, the residual liquid is reduced, and the electrical characteristics after the liquid crystal panel is formed are also improved.

  As a weight average molecular weight measured by GPC of the said dispersing agent, 3,000-100,000 are preferable and 5,000-50,000 are especially preferable. When the weight average molecular weight is within this range, aggregation of the colorant can be prevented, the viscosity itself is not too high, and the solubility in an organic solvent is good.

  As a method for synthesizing the dispersing agent, a known method can be employed. For example, a method described in JP-B-63-30057 can be used.

The said dispersing agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
The blending amount of the dispersant is preferably selected in the range of 0 to 30% by mass with respect to the total solid content in the colored curable composition.
Moreover, in the colored curable composition for color filters of the present invention, the content of the dispersant is usually 10 to 300% by mass, preferably 20 to 100% by mass, and particularly preferably based on the colorant. 30 to 80% by mass. When the content of the dispersing agent is within this range, aggregation can be prevented, the film thickness becomes an appropriate thickness, and when used in a color filter, cell gap control failure in the liquid crystal cell forming process is suppressed. It is possible.

  The colored curable composition in the present invention may be used in combination with a conventionally known dispersant (pigment dispersant) shown below in addition to the polymer dispersant.

Known dispersants (pigment dispersants) include polymer dispersants [for example, polyamidoamines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic types. Copolymers], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of known dispersants (pigment dispersants) that can be used in the present invention include "Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 161, 162, 163, 164, 165, 166" manufactured by BYK Chemie. , 170 (polymer copolymer) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide) manufactured by EFKA ), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Ajisper PB821, PB822 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd., Poly Low No. 50E, No. 300 (acrylic copolymer) ”,“ Dispalon # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ”manufactured by Enomoto Kasei Co., Ltd.,“ "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "acetamine 86 (stearylamine acetate)", "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester) manufactured by Lubrizol Amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate) "manufactured by Nikko Chemical Co., Ltd. , M YS-IEX (polyoxyethylene monostearate) ”and the like.

  In the present invention, when a known dispersant as described above is used, with respect to the compound having the acid value of 20 to 300 mg / g and the weight average molecular weight in the range of 3,000 to 100,000, It can be used in the range of 10 to 100% by mass, that is, 1/10 to 1/1 (equal amount).

(E-7) Dispersion aid Examples of the dispersion aid include pigment derivatives.
As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine And derivatives such as pigments.

  As the substituent of the pigment derivative, a sulfonic acid group, a sulponamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. are directly in the pigment skeleton or an alkyl group, an aryl group, Examples thereof include those bonded via a group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, more preferably a sulfonic acid group. In addition, these substituents may be substituted by a plurality of pigment skeletons, or may be a mixture of compounds having different substitutions.

  Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of anthraquinone pigments, sulphonic acid derivatives of quinacridone pigments, and sulfonic acids of diketopyrrolopyrrole pigments. And sulfonic acid derivatives of dioxazine pigments.

  Examples of commercially available pigment derivatives include azo-based Solvase 22000 manufactured by Avicia, phthalocyanine-based Solsperse 5000, and Fuka 475 manufactured by Fuka. These pigment derivatives may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The blending amount of the dispersion aid is preferably selected in the range of 0 to 20% by mass with respect to the total solid content in the colored curable composition.

(E-8) Surfactant As the surfactant, various substances such as anion, cation, non-ion (nonion), amphoteric surfactant and the like can be used. It is preferable to use a nonionic surfactant.

Examples of the anionic surfactant include alkyl sulfate ester surfactants such as EMAL 10 manufactured by Kao Corporation, alkyl naphthalene sulfonate salts such as Perex NB-L, and homogenol L-18. And special polymer surfactants such as L-100.
Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

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

  As the nonionic surfactant, it is preferable to use at least one selected from the group of compounds represented by the following general formulas (A) to (D).

In the above general formulas (A) to (D), PO represents propylene oxide, and EO represents ethylene oxide. In the propylene oxide, propylene includes both — (CH ₂ ) ₃ — and —CH ₂ CH (CH ₃ ) —.

In general formula (A) and general formula (B), (Style) represents ph-CH = CH-, and (benzyl) represents ph-CH _2- . Here, ph is a phenyl group.
N is an integer of 1 to 3, preferably 1. m is an integer of 7 to 30, preferably an integer of 8 to 20. l is an integer of 0 to 10, preferably an integer of 0 to 5. a is 0-20, b is 0-20, c is an integer of 6-30, Preferably, a is 0-10, b is 0-10, c is 10-20, respectively.

In general formula (C) and general formula (D), x is an integer of 5-100, Preferably it is an integer of 5-50. Moreover, y is an integer of 20-100. Note that x and y satisfy 0.1 ≦ x / y ≦ 2.0, preferably 0.2 ≦ x / y ≦ 1.0.
Here, four x and y which exist in general formula (C) and general formula (D) are respectively the same or different integers. That is, in the general formula (C) and the general formula (D), four ethylene oxide blocks exist, but the number of ethylene oxide units constituting each of the four blocks may be the same or different. . Moreover, although four propylene oxide blocks exist in General Formula (C) and General Formula (D), the number of propylene oxide units constituting each of the four blocks may be the same or different. .

In the present invention, among the compound groups represented by the general formulas (A) to (D), the compound represented by the general formula (A) and the compound represented by the general formula (B) are preferable. .
More specifically, in the general formula (A), n is 1, l is an integer of 0 to 5 and m is an integer of 8 to 20, and specific examples include addition of ethylene oxide 8 of styrylphenol. , 10 adducts, 12 adducts, 16 adducts, 20 adducts and the like.
In the general formula (B), a compound in which n is 1 to 3, a is 0 to 10, b is 0 to 10, and c is an integer of 10 to 20 is preferable. As a specific example, monostyrylbenzylphenyl Is an addition compound in which a is 4, b is 2, and c is 10, tristyrylbenzylphenyl is an adduct in which a is 0, b is 0, c is 16, tristyrylbenzylphenyl is a is 6, b is 2, c Is an adduct of 10 and an adduct of tristyrylbenzylphenyl wherein a is 8, b is 6, and c is 18.

Moreover, in this invention, well-known surfactant other than the compound group represented by the said general formula (A)-general formula (D) may be used, and these may be used together.
As the surfactant to be used, surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600 are preferable.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers, Polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters and the like are preferable.

  Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acids Ester, there is nonionic surfactants such as polyoxyalkylene sorbitan fatty acid esters.

Specific examples of nonionic surfactants include, for example, Adeka Pluronic series, Adecanol series i, Tetronic series (above ADEKA), Emulgen series, Rheodor series (above Kao), Eleminol series, Noni Pole series, Octapole series, Dodecapol series, New Pole series (Sanyo Kasei Co., Ltd.), Pionein series (Takemoto Yushi Co., Ltd.), Nissan Nonion series (Nippon Yushi Co., Ltd.), etc. It is. These commercially available products can be used as appropriate.
A preferable HLB value is 8 to 20, more preferably 10 to 17.

  Examples of the silicone surfactant include SH8400 manufactured by Toray Silicone Co., Ltd., KP341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

Examples of the fluorosurfactant include Megafac F172, F173, F176, F177, F177, F183, 470, F475, F780, F780 (Dai Nippon Ink Co., Ltd.), Novec FC-4430, FC-4432 (manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Seimi Chemical) Ftop EF351, 352, 801, 802 (manufactured by JEMCO) and the like.
When a fluorosurfactant is used as the surfactant, the compounding amount of the surfactant is 0.01% by mass or more and 1.00% by mass or less with respect to the total solid content of the colored curable composition. It is preferably 0.1% by mass or more and 3.0% by mass or less. When the blending amount of the surfactant is within the above range, wettability and leveling properties are improved.

  When a surfactant other than the fluorosurfactant is used, the blending amount is preferably 0.001% by mass or more and 1.0% by mass or less based on the total solid content of the colored curable composition. More preferably, the content is 0.01% by mass or more and 0.5% by mass or less.

[Method for producing colored curable composition]
Next, a method for preparing the colored curable composition for a color filter of the present invention will be described.
First, a predetermined amount of each of the colorant and the solvent is weighed, and in the dispersion treatment step (the colorant is dispersed in the solvent to obtain a liquid hatchable resin composition (ink-like material). Conditioners, sand grinders, ball mills, roll mills, stone mills, jet mills, homogenizers, etc. Since the colorant is formed into fine particles by this dispersion treatment, the coating characteristics of the colored curable composition are improved and transmission is improved. A color filter with improved light transmittance can be obtained.

When the colorant is dispersed in the solvent, it is preferable that the binder resin and / or the polymerizable compound, the dispersant, the dispersion aid, and the like be used in combination as appropriate. In particular, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time. For example, when the dispersion treatment is performed using sandgrawing, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several millimeters.
The temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably room temperature to 80 ° C. The dispersion time varies depending on the composition of the ink-like material {colorant, solvent, dispersant, dispersion aid}, the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted as appropriate.

  A binder resin and / or a polymerizable compound, a photopolymerization initiator, and other components are mixed with the ink-like material obtained by the dispersion treatment step to obtain a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and mixing, since a fine dust may mix, it is preferable to filter the obtained ink-like thing with a filter etc.

In the colored curable composition of the present invention, the ratio (concentration) of the total solid content in the entire colored curable composition is preferably 2 to 50% by mass. More preferred is 8 to 30% by mass, and particularly preferred is 12 to 25% by mass.
If the ratio of the total solid amount is too large, application stripes are likely to occur, which is not preferable. If the ratio of the total solid amount is too small, the viscosity decreases, the colored curable composition flows during drying, and drying unevenness and dent defects occur, which is not preferable.

  In particular, when producing a color filter having a thin coating film thickness after drying, the ratio of the total solid amount is usually 30% by mass or less, preferably 20% by mass or less, more preferably 18% by mass or less, and particularly preferably. Is less than 16% by mass, usually 2% by mass or more, preferably 4% by mass or more, and more preferably 8% by mass or more.

  On the other hand, particularly when a color filter having a thick coating film thickness after drying is produced, the ratio of the total solid amount is usually 8% by mass or more, preferably 10% by mass or more, and more preferably 12% by mass or more. Particularly preferably, it is 14% by mass or more, usually 30% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.

[Color filter]
Next, the color filter of the present invention will be described.
The color filter of the present invention has a pixel or black matrix formed of the colored curable composition of the present invention on a substrate.
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

To improve surface properties such as adhesion, transparent substrate and black matrix forming substrate are subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins as necessary. You may go.
The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

  The color filter of the present invention can be manufactured by providing a black matrix on a transparent substrate and forming pixel images of red, green and blue colors. The colored curable composition is used as at least one resist forming coating solution of black, red, green, and blue. The black resist is formed on the transparent glass surface on the transparent substrate, and the red, green, and blue colors are formed on the resin black matrix forming surface formed on the transparent substrate or using a chromium compound or other light shielding metal material. A pixel image of each color is formed on the metal black matrix forming surface by applying, heating and drying, image exposure, development and thermosetting.

The black matrix is formed on a transparent substrate using a light shielding metal thin film or a black matrix pigment dispersion. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloys, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, etching is performed by mixing nitric ammonium nitrate and perchloric acid for chromium. Other materials are etched using an etchant according to the material, and finally a positive photoresist is stripped with a dedicated stripper to form a black matrix.

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

  When using a pigment dispersion for a black matrix, a black matrix is formed using a colored curable composition containing a black colorant. For example, black colorant such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or red, green, blue or the like appropriately selected from inorganic or organic pigments and dyes Using a colored curable composition containing a black colorant by mixing, black matrices can be formed in the same manner as in the following method for forming red, green, and blue pixel images.

  On a transparent substrate provided with a black matrix, a colored curable composition for a color filter containing a colorant of one color of red, green, and blue is applied, and after drying, a photomask is overlaid on the coating film, Through this photomask, a pixel image is formed by image exposure, development, and thermal curing or photocuring as necessary to create a colored layer. A color filter image can be formed by performing this operation for each of the colored curable compositions for three color filters of red, green, and blue.

  The colored curable composition for the color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred.

  The application conditions by the die coating method may be appropriately selected depending on the composition of the color filter curable composition, the type of color filter to be produced, and the like. For example, the lip width at the nozzle tip is preferably 50 to 500 μm, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 μm. In order to adjust the thickness of the coating film, the running speed of the lip and the discharge amount of the liquid colored curable composition from the lip may be adjusted.

Furthermore, in the colored curable composition, the upper limit of the steady viscosity at a shear rate of 10 ³ s ⁻¹ or less is preferably 5 mPa · s or less, more preferably 4 mPa · s or less, and even more preferably 3.8 mPa · s. s or less, particularly preferably 3.5 mPa · s or less.

Further, the lower limit of the steady viscosity of the colored curable composition at a shear rate of 10 ³ s ⁻¹ or less is usually 1 mPa · s or more. However, in the die coating method, the coating film thickness after drying (that is, after the final step) Is a thin film (usually less than 1.5 μm; hereinafter referred to as “thin film” unless otherwise specified), the color filter is preferably 1.5 mPa · s or more. Preferably it is 2 mPa * s or more, Most preferably, it is 2.5 mPa * s or more.
When manufacturing a color filter having a coating film thickness after drying (usually 1.5 μm or more; hereinafter, unless otherwise specified, it is defined as “thick film” in the present application), preferably 3 mPa · s. It is above, More preferably, it is 3.2 mPa * s or more.

By making the steady viscosity within this range, when producing a color filter with a thin coating film thickness after drying in the die coating method, there is no liquid breakage even when the coating limit speed is increased, and the tip of the die lip It is possible to form a color filter having no coating streaks due to the non-uniformity.
The application limit speed means an upper limit application speed at which uniform application can be performed without forming a stripe-shaped application film due to running out of liquid in the steady application part, and is usually 0.1 m / second, preferably 0. .2 m / sec, more preferably 0.3 m / sec.

On the other hand, when manufacturing a color filter with a thick coating film thickness after drying, excessive flow during drying is suppressed by keeping the steady viscosity within the range, and drying is performed even when thick film coating is performed by die coating. Unevenness, dent defects, and the like can be suppressed, and a color filter having no coating streaks caused by unevenness of the die lip tip can be formed.
In addition, even when manufacturing a color filter of either a thin film or a thick film, if the steady viscosity is too low, the liquid stability is deteriorated.

  Moreover, when the surface tension of a colored curable composition is 25 dyne / cm or more, since leveling property is good, it is preferable. The higher the surface tension, the better, but it is usually 40 dyne / cm or less.

  In the colored curable composition having a surface tension within the above range, the surfactant moderately moderates the surface tension gradient, so that in addition to preventing the occurrence of coating consultation, the unevenness can be flattened and the unevenness of the stripes can be suppressed.

  The color filter produced using the colored curable composition having the above rheological properties should be a high-quality color filter in which good pixels with less foreign matter, coating unevenness and coating streaks are formed by a uniform resist layer. Can do.

  The coating film after the colored curable composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. If necessary, preliminary drying may be performed before reheating drying described later. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 80 ° C., preferably 30 to 50 to 70 ° C., depending on the type of solvent and the performance of the dryer used. It is selected in the range of seconds to 3 minutes.

  The reheat drying temperature condition is 50 to 200 ° C higher than the predrying temperature, preferably 70 to 160 ° C, particularly preferably 70 to 130 ° C. The drying time is preferably 10 seconds to 10 minutes, and more preferably 15 seconds to 5 minutes, depending on the heating temperature. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the photopolymerization initiator may be decomposed to induce thermal polymerization and cause poor development.

The thickness of the coating film of the colored curable composition for a color filter after drying is usually 0.4 μm or more, preferably 0.6 μm or more, and usually 1.5 μm or less, when producing a thin color filter. Preferably it is 1.0 micrometer or less. When a thick color filter is manufactured, it is usually 1.5 μm or more, preferably 3 μm or more, and usually 10 μm or less, preferably 5 μm or less.
In this coating film drying process, a reduced pressure drying method may be used in which drying is performed in a reduced pressure chamber without increasing the temperature.

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

The light source used for said image exposure is not specifically limited. As the light source, it is desirable that the radiation irradiated at the time of exposure at this time has a wavelength of 280 to 465 nm, and may have other wavelengths. In particular, ultraviolet rays such as g-line, h-line, i-line, and j-line are preferable, and ultraviolet rays including j-line and i-line, h-line, and g-line are preferable.
The exposure machine can use any of a proximity system, a mirror projection system, and a stepper system. When irradiating and using light of a specific wavelength, an optical filter can be used.

  The color filter of the present invention is obtained by performing image exposure of the coating film of the colored curable composition of the present invention with the above-mentioned light source and then developing with an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. It can be prepared by forming an image on a substrate. This aqueous solution may further contain an organic solvent, a buffering agent, a rosinizing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono- or triethanolamine, mono- or triethanolamine, mono-ge Or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), co The organic alkaline compound such emissions and the like. These alkaline compounds may be used individually by 1 type, and may use 2 or more types together.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglycedide alkyl esters, and alkylbenzenes. Examples thereof include anionic surfactants such as sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate salts, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

  There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

In addition to the manufacturing method described above, the color filter of the present invention is obtained by applying (1) a colored curable composition containing a solvent, a phthalocyanine pigment as a colorant, and a polyimide resin as a binder resin to a substrate. It can also be manufactured by a method of forming a pixel image by an etching method.
Also, (2) a method of forming a pixel image directly on a transparent substrate using a colored curable composition containing a phthalocyanine pigment as a colored ink, and (3) a colored curable composition containing a phthalocyanine pigment. A method of depositing a colored film on an ITO electrode having a predetermined pattern by immersing the substrate as an electrodeposition solution and immersing the substrate in the electrodeposition solution may be used.
Further, (4) a method in which a film coated with a colored curable composition containing a phthalocyanine pigment is attached to a transparent substrate and peeled off, image exposure and development to form a pixel image, and (5) a phthalocyanine pigment is contained. Examples thereof include a method of forming a pixel image with an ink jet printer using a curable composition with colored ink.
The manufacturing method of a color filter employ | adopts the method suitable for this according to the composition of the colored curable composition for color filters.

  The color filter after the development is subjected to a heat curing process. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

[Colored curable composition and color filter]
The colored curable composition is excellent in developability even when exposed at a low exposure amount. Therefore, when manufacturing the colored curable composition of this invention, since the burden in an exposure process can be reduced, a throughput can be enlarged.

  Moreover, the color filter produced using the colored curable composition of the present invention has high color purity and excellent patternability. Furthermore, as described above, since the colored curable composition of the present invention is suitable for slit coating, a color filter free from foreign matter, coating unevenness, and coating streaks can be obtained.

[Liquid Crystal Display]
The color filter of the present invention is used as a part of a component such as a color display or a liquid crystal display device by forming a transparent electrode such as ITO on the pixel as it is. When the color filter of the present invention is applied to a liquid crystal display device, the color filter of the present invention is provided on at least a part of a substrate, a liquid crystal layer is sandwiched between two substrates, and a polarizing plate and a backlight are further provided.

  Furthermore, in order to improve surface smoothness and durability, an overcoat layer of a transparent resin can be provided on the pixels as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

[Example 1]
The following pigment dispersion composition was blended to prepare a pigment dispersion.

-Pigment dispersion-
(Pigment)
Pigment Green 36 (average particle diameter 19 nm in SEM observation) 7 parts Pigment Yellow 150 (average particle diameter 22 nm in SEM observation) 3 parts (dispersant)
Product name: BYK-161 (manufactured by BYK, active ingredient 30% by mass) 13.3 parts (solvent)
32.7 parts of propylene glycol monomethyl ether acetate

-Transparent resist solution-
Binder: Acrylic resin represented by the following formula (16) 4 parts Ethylene compound: Dipentaerythritol hexaacrylate 4 parts Photopolymerization initiator: 0.6 part of photopolymerization initiator listed in Table 1 Sensitizer: Following Sensitizer (i) 0.1 part Chain transfer agent: Chain transfer agent shown in Table 0.3 0.3 part Fluorosurfactant: Sumitomo 3M FC4430 0.023 part Nonionic surfactant: Kao Emulgen A-60 0.5 part Solvent: Propylene glycol monomethyl ether acetate 70 parts Ethyl 3-ethoxypropionate 20 parts

  In the general formula (16), a: b: c: d = 15: 20: 10 (mol%), and Mw is 12000.

  The pigment dispersion and the transparent resist solution were mixed and stirred. Thereafter, 300 g of zirconia beads having a particle diameter of 0.5 mm was added to this mixed solution, and after being dispersed by shaking for 5 hours with a paint conditioner, a uniform color resist (colored curable composition) was obtained. .

  The obtained color resist 16 is discharged from a discharge port of a slit die 12 having a width of 550 mm in which a shim 10 having a protrusion as shown in FIG. 1 is incorporated as shown in FIG. It apply | coated to the glass substrate 14 (Corning company make 1737, 0.7 mm thickness) so that a film thickness might be set to 2.0 micrometers after a post-baking process. In addition, the dimensional unit in FIG. 1 is mm.

At this time, the fluctuation of the streaky film thickness unevenness 18 caused by the protrusions of the shim 10 was measured with a stylus type film thickness meter DECTAC-3 manufactured by ULVAC after post-baking. The results are shown in Table 2.
Further, the occurrence of fine streaky irregularities at the coating start portion of the coated substrate was evaluated by visual observation with a sodium lamp. The results are shown in Table 2.

Next, the coated substrate was treated with a vacuum drying apparatus at 0.5 torr for 60 seconds, and then pre-baked with a hot plate at 90 ° C. for 60 seconds.
Next, using a HITACHI exposure machine LE5565 (all wavelengths) equipped with a high-pressure mercury lamp, exposure was performed at 100 mJ / cm ² with a proximity gap of 300 μm with a mask having a line width of 15 μm (exposure area of 15 μm) (illuminance: 20 mW). / Cm ² ). Thereafter, development was performed with a 1.0% developer (25 ° C.) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) to form a pattern.

The development latitude was obtained by dividing the number of development seconds at which the pattern began to appear by the number of seconds until the pattern began to be missing. The smaller this value, the higher the development latitude, and the higher the process suitability for development. The results are shown in Table 2.
After development, it was rinsed with pure water and post-baked in a convection oven at 230 ° C. for 60 minutes. The line width of the obtained pattern was measured with a microscope. A wider line width indicates higher sensitivity.

  The obtained line width was divided by the mask dimension to obtain sensitivity. In this evaluation, the larger the numerical value, the higher the sensitivity. The results are shown in Table 2.

  Except for exposing without pattern mask at the time of exposure, the chromaticity and transmittance of the green solid substrate (colored layer thickness is 2.0 μm) after post-bake treatment are made by Otsuka Electronics Co., Ltd. Measured by MCPD2000. The results are shown in Table 2.

[Examples 2-3]
A pattern was formed and evaluated in the same manner except that the sensitizer used in Example 1 was changed to the following sensitizer shown in Table 1. The results are shown in Table 2.

[Example 4]
A pattern was formed and evaluated in the same manner except that the photopolymerization initiator used in Example 1 was changed to the photopolymerization initiator shown in Table 1. The results are shown in Table 2.

[Comparative Examples 1-3]
A pattern was formed and evaluated in the same manner except that the sensitizer used in Example 1 was changed to the following sensitizer shown in Table 1. The results are shown in Table 2.

It is a top view which shows the shim used for application | coating of a color resist in an Example. It is a perspective view which shows the application state by the slit die which attached the shim of FIG.

Explanation of symbols

10 Shim 12 Slit die 14 Glass substrate 16 Color resist 18 Streaks

Claims (9)

Containing a colorant, a polymerizable compound, a photopolymerization initiator, and a sensitizer;
The color curable composition for a color filter, wherein the sensitizer is at least one selected from the following general formula (1).

[In General Formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, a hydrocarbon ring group, a heterocyclic group, or —SO ₃ —R ^0. (R ⁰ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a quaternary ammonium group), R ⁷ represents an alkyl group having 6 to 15 carbon atoms, and X ¹ and X ² are each independently, Represents a halogen atom, an alkyl group, an aryl group, an aralkyl group, or an aromatic heterocyclic group. These groups may be further substituted.   The colored curable composition for a color filter according to claim 1, wherein the polymerizable compound is a compound containing three or more (meth) acryloyl groups in one molecule.   The color curable composition for a color filter according to claim 1 or 2, wherein the content of the colorant with respect to the total solid content of the curable colored resin composition is 30% by mass or more and 70% by mass or less. object. The color curable composition for a color filter according to any one of claims 1 to 3, wherein one or more kinds from the following group A and one or more kinds from the following group B are used in combination as the colorant. Composition.
Group A: Color Index Pigment Green 7,36
Group B: Color Index Pigment Yellow 138, 139, 150, 185   The polymerizable compound is at least one selected from dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Item 5. The colored curable composition for a color filter according to any one of Items 4. Furthermore, it contains an alkali-soluble resin,
The alkali-soluble resin has at least one monomer component selected from (meth) acrylic acid, maleic acid, maleic anhydride, and crotonic acid, methyl (meth) acrylate, butyl (meth) acrylate, and phenyl (meth). Including at least one copolymer having at least one selected from acrylate, benzyl (meth) acrylate, and styrene,
The content rate of the said alkali-soluble resin with respect to the total solid amount of curable coloring resin composition is 5 mass% or more and 30 mass% or less, The any one of Claims 1-5 characterized by the above-mentioned. Colored curable composition for color filters. Furthermore, a surfactant having a fluorine atom content of 5% by mass or more and 20% by mass or less,
The content rate of the said surfactant with respect to the total solid of a curable coloring resin composition is 0.01 mass% or more and 1.00 mass% or less, The any one of Claims 1-6 characterized by the above-mentioned. The coloring curable composition for color filters in the item.   The color filter produced using the colored curable composition for color filters in any one of Claims 1-7. With backlight,
A polarizing plate;
At least two substrates;
A liquid crystal layer sandwiched between the substrates;
The color filter layer according to claim 8 provided on at least a part of the substrate;
A liquid crystal display device.

Images