JP2017206689A - Coloring composition, colored cured film, color filter, display element and light receiving-element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition suitable for forming a colored cured film that can achieve both heat resistance and solvent resistance at high levels.SOLUTION: A coloring composition contains (A) colorant, (B) resin and (C) polymerizable compound. The (B) resin contains (b1) a resin having a structure that produces a cyclic ether group by heating, and the (A) colorant has a content of 1 mass% or more in the solid content of the coloring composition.SELECTED DRAWING: None

Description

  The present invention relates to a colored composition, a colored cured film, a display element, and a light receiving element. More specifically, the present invention is used for a transmissive or reflective color liquid crystal display element, solid-state imaging element, organic EL display element, electronic paper, and the like. The present invention relates to a colored composition used for forming a colored cured film, a colored cured film formed using the colored composition, and a display element and a light receiving element including the colored cured film.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. A method of obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development is known (for example, see Patent Documents 1 and 2). In addition, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (for example, see Patent Document 4).

  In recent years, there has been a strong demand for higher contrast of liquid crystal display elements and higher definition of solid-state imaging elements, and in order to realize these, application of dyes as colorants is being studied. However, generally speaking, when a dye is applied, there are many problems in heat resistance, solvent resistance, and the like as compared with the case where a pigment is applied as a colorant.

  Under such a background, for example, Patent Document 5 proposes the use of a triarylmethane dye having an alkylsulfonylimide anion as a dye-containing coloring composition capable of forming a pixel having excellent heat resistance.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2012-83651 A

  However, the dye proposed in Patent Document 5 has been found to have a poor balance between pixel heat resistance and solvent resistance.

  Therefore, the subject of this invention is providing the coloring composition suitable for formation of the colored cured film which can make heat resistance and solvent resistance compatible in high level. Furthermore, the subject of this invention is providing the color filter, display element, and light receiving element which comprise the colored cured film formed using the said coloring composition, and this colored cured film.

  In view of such a situation, the present inventors have conducted intensive research. As a result, in any one or more of the colorant, the resin, and the polymerizable compound in the colored composition containing the colorant, the resin, and the polymerizable compound. By introducing a chemical structure that generates a cyclic ether group by heating, a colored composition capable of forming a colored cured film that not only achieves both high heat resistance and solvent resistance, but also has excellent migration resistance. It was found that it can be obtained. Here, “transferability” in the present specification means that the colorant in the pixels of the coloring pattern elutes and the color is transferred to the adjacent other color pixels or the cured film.

  That is, the present invention is a colored composition containing (A) a colorant, (B) a resin and (C) a polymerizable compound, wherein (A) the colorant, (B) the resin and (C) the polymerizable compound. Any one or more of them provide a colored composition having a chemical structure for generating a cyclic ether group by heating.

As a suitable aspect of the coloring composition of this invention, the coloring composition shown to following (1)-(3) can be mentioned.
(1) A coloring composition containing (A) a colorant, (B) a resin and (C) a polymerizable compound,
(B) the resin includes (b1) a resin having a structure that generates a cyclic ether group by heating;
(A) The coloring composition whose content rate of a coloring agent is 1 mass% or more in the solid content of the said coloring composition.
(2) A coloring composition containing (A) a colorant, (B) a resin and (C) a polymerizable compound,
(C) The coloring composition in which a polymeric compound contains the compound which has a structure which produces | generates a cyclic ether group by (c1) heating.
(3) A coloring composition containing (A) a colorant and (C) a polymerizable compound,
(A) A colored composition containing a compound in which the colorant has (a1) a structure that generates a cyclic ether group by heating and a dye structure.

  The present invention also provides a colored cured film formed using the colored composition, and a color filter, a display element and a light receiving element comprising the colored cured film. Here, in this specification, “colored cured film” refers to a bank (partition wall) that defines areas for forming each color pixel, interlayer insulating film, planarizing film, and light emitting layer used in display elements and solid-state imaging elements. , Black matrix, spacer, protective film and the like.

  ADVANTAGE OF THE INVENTION According to this invention, the coloring composition which can form the colored cured film which can not only satisfy heat resistance and solvent resistance at high level but is excellent also in dye transfer resistance can be provided. Therefore, the colored composition of the present invention can be used very suitably for the production of solid-state imaging devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.

Hereinafter, the present invention will be described in detail.
First, a preferred embodiment of the coloring composition of the present invention will be described in detail.
Coloring composition <first embodiment>
The coloring composition of the present embodiment includes (A) a colorant, (B) a resin, and (C) a polymerizable compound, and any of (A) the colorant, (B) resin, and (C) the polymerizable compound. 1 or more have a structure that generates a cyclic ether group by heating (hereinafter also referred to as “specific structure α”).
The specific structure α is not particularly limited as long as it generates a cyclic ether group by heating, but a cyclic carbonate structure having a 5-membered ring or a cyclic carbonate structure having a 6-membered ring is preferable, and a cyclic ether generated by heating The group is preferably an oxiranyl group or an oxetanyl group. Most preferred is a cyclic carbonate structure having a 5-membered ring that generates an oxiranyl group by heating. The cyclic carbonate structure having such a 5-membered ring is at least one selected from an ethylene carbonate structure represented by the following formula (1) and a cyclohexyl ethylene carbonate structure represented by the following formula (2). Is more preferable, and an ethylene carbonate structure represented by the following formula (1) is more preferable.

[In the formulas (1) and (2),
R ¹ independently of ^{one another} represents a halogen atom, a hydroxyl group, a nitro group, an amino group, a cyano group or a hydrocarbon group;
m represents 0 or 1,
n represents an integer of 0 to 3,
X represents, independently of each other, a single bond or a divalent hydrocarbon group,
* Indicates a bond. ]

  Such a cyclic carbonate structure can be decarboxylated by heating at 140 to 200 ° C. to form a cyclic ether structure, for example. By introducing such a structure into any one or more of (A) colorant, (B) resin and (C) polymerizable compound, for example, a colored cured film is formed using a colored composition. In the post-baking step, a cyclic ether is produced from any one or more of (A) the colorant, (B) resin and (C) the polymerizable compound, and (A) the colorant, (B) resin or ( C) A cross-linked structure can be formed between or within the molecules of the polymerizable compound. Thereby, the crosslinking density of the colored cured film is increased, and the heat resistance and solvent resistance can be significantly improved.

Examples of the halogen atom in R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Here, in the present specification, the “alicyclic hydrocarbon group” is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. In addition, in this specification, “alicyclic hydrocarbon group” and “aromatic hydrocarbon group” are not only a group consisting of only a ring structure, but also a divalent aliphatic hydrocarbon group substituted on the ring structure. In other words, the structure includes at least an alicyclic hydrocarbon or an aromatic hydrocarbon.
The aliphatic hydrocarbon group may be either a straight chain or branched chain, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. As an alkyl group, a C1-C20 alkyl group is preferable, a C1-C15 alkyl group is more preferable, and a C1-C10 alkyl group is still more preferable. Specific examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, Examples include octyl group, 2-ethylhexyl group, decyl group, dodecyl group and the like. Moreover, as an alkenyl group, a C2-C20 alkenyl group is preferable, a C2-C15 alkenyl group is preferable, and a C2-C10 alkenyl group is still more preferable. Specific examples of the alkenyl group include, for example, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, and 2-octynyl. Group, (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like. Moreover, as an alkynyl group, a C2-C20 alkynyl group is preferable, a C2-C15 alkynyl group is preferable, and a C2-C10 alkynyl group is still more preferable. Specific examples of the alkynyl group include, for example, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, and 2-octynyl. Group, (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like.

The alicyclic hydrocarbon group includes a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, a cyclic terpene hydrocarbon group, and the like. The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an alicyclic carbon group having 3 to 12 carbon atoms. A hydrogen group is more preferable. Specific examples of the alicyclic hydrocarbon group include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecanyl group, and decahydro-2. -Naphtyl group, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, pentacyclopentadecanyl group, isobornyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group, tricyclo A pentanyl group, a tricyclopentenyl group, etc. can be mentioned.

  As an aromatic hydrocarbon group, a C6-C20 aryl group is preferable and a C6-C10 aryl group is still more preferable. Here, in the present specification, the “aryl group” refers to a monocyclic to tricyclic aromatic hydrocarbon group such as a phenyl group, a benzyl group, an o-tolyl group, an m-tolyl group, and a p-tolyl group. Xylyl group, naphthyl group, anthryl group, phenanthryl group, azulenyl group, 9-fluorenyl group and the like.

Further, the hydrocarbon group may have one or more linking groups containing atoms other than carbon atoms and hydrogen atoms between carbon-carbon bonds or at the ends thereof. Examples of such a linking group include —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —CONR ^a — (R ^a is a hydrogen atom or a carbon number of 1 to 6). -NR ^<a> -(R ^<a> is as defined above). One or more linking groups can be present. In addition, a hydrocarbon group and a linking group may be bonded to form a ring structure. Examples of the hydrocarbon group having a linking group include an alkoxyl group, an aryloxy group, and an alkyloxyalkyl group. In addition, carbon number of the above-mentioned hydrocarbon group means the total carbon number of the part except the carbon atom which comprises a coupling group.

The alkoxyl group may be either a straight chain or branched chain form. As an alkoxyl group, a C1-C20 alkoxyl group is preferable, a C1-C15 alkoxyl group is more preferable, and a C1-C10 alkoxy group is still more preferable. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and an isopentyloxy group. .
The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group.
The alkyloxyalkyl group is preferably an alkyloxyalkyl group having 2 to 10 carbon atoms. For example, for example, a methoxymethyl group, a 2-methoxyethyl group, an ethoxymethyl group, a 2-ethoxyethyl group, 2- (n-propoxy) ) Ethyl group, 2- (n-isopropoxy) ethyl group and the like.

Among these, as R ¹ , a hydrocarbon group is preferable. The position of R ¹ is optional, and if having two or more, may be the same or different.

m is 0 or 1, but 0 is preferred.
n is an integer of 0 to 3, but 0 or 1 is preferable.

Examples of the divalent hydrocarbon group in X include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be either linear or branched, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be saturated hydrocarbons or unsaturated hydrocarbons. It may be a group.
Examples of the divalent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group, and the carbon number thereof is preferably 1 to 20, more preferably 2 to 12, and still more preferably 2 to 6. Specific examples include, for example, methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1, 3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, Pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, 2-methylpropane-1,2-diyl group, 2,2-dimethylpropane-1,3- Diyl group, ethene-1,1-diyl group, ethene-1,2-diyl group, propene-1,2-diyl group, propene-1,3-diyl group, propene-2,3-diyl group, 1- Butene-1,2-diyl group, 1-butene-1,3-diyl group 1-butene-1,4-diyl group, 2-pentene-1,5-diyl group, and a 3-hexene-1,6-diyl group.
As a bivalent alicyclic hydrocarbon group, a cycloalkylene group and a cycloalkenylene group are mentioned, for example, The carbon number becomes like this. Preferably it is 3-20, More preferably, it is 3-12. Specific examples include, for example, a monocyclic hydrocarbon ring group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclobutenylene group, a cyclopentenylene group, and a cyclohexenylene group; -Bridged ring hydrocarbon groups, such as norbornylene groups, such as norbornylene group and 2,5-norbornylene group, 1,5-adamantylene group, 2,6-adamantylene group, etc. can be mentioned.
Examples of the divalent aromatic hydrocarbon group include an arylene group, and a monocyclic to tricyclic arylene group having 6 to 14 carbon atoms is preferable. Specific examples include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, and an anthrylene group.

The divalent hydrocarbon group may have one or more linking groups containing atoms other than carbon atoms and hydrogen atoms between carbon-carbon bonds or at the ends thereof. As the linking group, as described above, —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —CONR ^a — (R ^a is a hydrogen atom or a carbon number) 1 to 6 alkyl groups) and -NR ^<a> -(R ^<a> is as defined above). One or more linking groups can be present. In addition, a divalent hydrocarbon group and the linking group may be bonded to form a ring structure.

  The compound having the specific structure α can be produced by a known method. For example, the compound having the cyclic carbonate structure represented by the formula (1) or (2) is, for example, the formula (1). Alternatively, in (2), the compound in which the 5-membered ring carbonate group is an oxiranyl group is reacted with carbon dioxide to be converted into a 5-membered ring carbonate.

The (A) colorant, (B) resin, or (C) polymerizable compound according to the present embodiment can take an appropriate structure as long as it has the specific structure α. This will be described in detail in the embodiment.
Moreover, the coloring composition of this embodiment can contain 1 type (s) or 2 or more types of a well-known coloring agent, a dispersing agent, a dispersing aid, binder resin, a photoinitiator, a solvent, an additive, etc. Specific embodiments thereof will be described in detail in second to fourth embodiments described later.

Second Embodiment
The colored composition of the present embodiment includes (A) a colorant, (B) a resin, and (C) a polymerizable compound, and (B) the resin has a structure in which (b1) a cyclic ether group is generated by heating. (A) The content rate of a coloring agent is 1 mass% or more in the solid content of the said coloring composition. By setting it as such an aspect, the colored cured film which can not only make heat resistance and solvent resistance compatible with high level but also is excellent also in dye transfer resistance can be formed.
Hereinafter, the components of the colored composition according to this embodiment will be described.

-(A) Colorant-
(A) The colorant is not particularly limited as long as it has colorability, and the color and material can be appropriately selected according to the use of the colored composition. As a coloring agent, it is possible to contain a well-known coloring agent, for example, a pigment and dye can be mentioned. Further, (a1) a compound having a specific structure α and a dye structure, which will be described in detail in a fourth embodiment described later, may be contained. For example, a known colorant can be contained together with (a1) a compound having a specific structure α and a dye structure, or (a1) instead of a compound having a specific structure α and a dye structure. (A) A coloring agent can contain 1 type (s) or 2 or more types. When a known colorant is contained, an organic pigment is preferable as the pigment and an organic dye is preferable as the dye from the viewpoint of obtaining a pixel having high luminance, contrast, and coloring power. Hereinafter, known colorants will be described.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists). Among them, the following color index (C.I. .) Those numbered can be preferably used.

C. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 264, C.I. I. Pigment red 269, C.I. I. Pigment red 279, C.I. I. Red pigments such as CI Pigment Red 280;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment green 59, C.I. I. Pigment green 62, C.I. I. Green pigments such as CI Pigment Green 63;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 79, C.I. I. Blue pigments such as CI Pigment Blue 80;
C. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 179, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 215, C.I. I. Yellow pigments such as CI Pigment Yellow 231;
C. I. Orange pigments such as CI Pigment Orange 38;
C. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Purple pigment such as CI Pigment Violet 29.
In addition, brominated diketopyrrolopyrrole pigments represented by the formula (Ic) of JP-T-2011-523433 can also be preferably used.

  Examples of inorganic pigments include carbon black and titanium black. In addition, JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-237384, JP-A-2010-237369, JP-A-2011-006602, JP-A-2011-145346, etc. Can be mentioned.

  In the present embodiment, the pigment can be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Further, these pigments may be used by modifying the particle surface with a resin, if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Laid-Open No. 8-179111 can be employed.

  The dye is not particularly limited. For example, a known dye may be used in addition to a compound classified as a dye in the color index (CI; issued by The Society of Dyer's and Colorists). Can do. Such dyes include, for example, triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitroline dyes, from the chromophore structure side. And dyes, quinoneimine dyes, phthalocyanine dyes, squarylium dyes, and the like. Among these, from the viewpoint of heat resistance, triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are preferable.

  In this embodiment, the dye may be composed of a cation moiety and an anion moiety. For example, a salt of a cationic chromophore and a counter anion (excluding the lake pigment), or anionic color development. It may be a salt of a group and a counter cation. As used herein, the term “anionic dye” means an ionic dye having a chromophore having an acidic group, and an ionic dye forming a salt with the acidic group is also an anionic dye. In the present specification, the “cationic dye” means an ionic dye having no acidic group among ionic dyes, and is usually a dye having a basic group. Furthermore, “nonionic dye” means a dye other than a cationic dye and an anionic dye.

Examples of cationic chromophores include triarylmethane chromophore, cyanine chromophore, xanthene chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, squarylium chromophore. And quinophthalone chromophore. Of these, triarylmethane chromophore, cyanine chromophore, xanthene chromophore, polymethine chromophore, and azo chromophore are preferable, and triarylmethane chromophore and cyanine chromophore are more preferable. Cationic chromophores include C.I. in the Color Index (issued by The Society of Dyers and Colorists). It is also possible to use a cationic part of a dye classified as I. basic.
Further, the counter anion is not particularly limited, and examples thereof include anions described in paragraph [0034] of JP-A-2015-129263, among which sulfonate anion, imide anion and carboxylate anion are preferable, and imide anion is more preferable. More preferred is a sulfonylimide anion.

Examples of anionic chromophore include triarylmethane chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, xanthene chromophore, squarylium chromophore, quinophthalone chromophore. A group can be mentioned. Among them, triarylmethane chromophore, azo chromophore, phthalocyanine chromophore, and xanthene chromophore are preferable, and triarylmethane chromophore having one or more substituents selected from —SO ₃ ^— and —CO ₂ ^— , and azo color development. More preferred are chromophores, phthalocyanine chromophores, or xanthene chromophores. As an anionic chromophore, C.I. It is also possible to use an anion portion of a dye classified as I. Acid.
Examples of the counter cation include an ammonium cation, a phosphonium cation, a sulfonium cation, an iodonium cation, and a diazonium cation. Among them, an ammonium cation and a phosphonium cation are preferable, and an ammonium cation is more preferable.

  When a known colorant is contained, it is preferable to include at least one selected from a dye and a pigment, and more preferable to include a dye and a pigment from the viewpoint of forming a colored cured film having excellent chromaticity characteristics. Among them, when the colored composition of the present invention is used for forming a blue colored cured film, it is preferable to include a dye and a blue pigment as a colorant. In this case, the dye has a high level of heat resistance and solvent resistance. From the viewpoint of achieving both, a salt of a cationic chromophore and a counter anion is preferred. In addition, when the colored composition of the present invention is used to form a red colored cured film, it is preferable to include a dye and a red pigment as known colorants. In this case, the dye has high heat resistance and solvent resistance. From the viewpoint of achieving both levels, an anionic chromophore and a counter cation salt are preferred. That is, when the colored composition of the present invention is used to form a colored cured film of blue or red, known colorants include salts of a cationic chromophore and a counter anion, a salt of an anionic chromophore and a counter cation, and It preferably contains at least one selected from the group consisting of pigments, and contains at least one selected from a salt of a cationic chromophore and a counter anion and a salt of an anionic chromophore and a counter cation and a pigment. It is preferable.

  In the present embodiment, a known dispersion aid may be contained. Examples of the dispersion aid include pigment derivatives.

  In the coloring composition according to the present embodiment, the content of the colorant (A) is 1% by mass or more in the solid content, but the pixel having excellent luminance, heat resistance and solvent resistance, or the black matrix having excellent light shielding properties. And from the point which forms a black spacer, Preferably it is 5-70 mass% in a solid content of a coloring composition, More preferably, it is 10-60 mass%, More preferably, it is 15-50 mass%. Here, “solid content” in the present specification means components other than the solvent described later.

-(B) Resin-
(B) The resin contains (b1) a resin having a specific structure α (hereinafter also referred to as “(b1) resin”). The specific structure α may be present at either the end or the side chain of the molecule, and may be present in the molecule at one or more. As described above, the (b1) resin can have an appropriate structure as long as it has the specific structure α, but from the viewpoint of production efficiency, the resin preferably has an ethylenically unsaturated monomer containing the specific structure α as a repeating unit. . The ethylenically unsaturated monomer is not particularly limited as long as it has a specific structure α, but the ethylenically unsaturated monomer having an ethylene carbonate structure represented by the formula (1) and the formula (2) Preferred is at least one selected from ethylenically unsaturated monomers having a cyclohexylethylene carbonate structure, and an ethylenically unsaturated monomer represented by the following formula (3) and the following formula (4): At least one selected from ethylenically unsaturated monomers represented by the formula (3) is more preferred, and an ethylenically unsaturated monomer represented by the following formula (3) is more preferred.

[In the formulas (3) and (4),
R ² independently of one another represents a hydrogen atom or a methyl group,
R ^1, m, n and X, ^R 1, m in the formula (1) and (2) in the same meaning as n, and X. ]

Here, as described above, X is a divalent hydrocarbon group which may have a linking group, but the group formed by bonding such a divalent hydrocarbon group to an ethylenically unsaturated group. As, ethynyl group, propynyl group, styryl group, α-methylstyryl group, vinyloxy group, styryloxyalkyl group, (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloyloxyalkyl group, (meth) An acryloyloxyalkyloxyalkyl group etc. can be mentioned. Specific embodiments of R ¹ , m and n are as described above.

  Specific examples of the ethylenically unsaturated monomer represented by the above formula (3) or (4) include compounds listed in the following compound group α.

  (B1) The resin may be composed only of an ethylenically unsaturated monomer having the specific structure α. From the viewpoint of improving heat resistance, solvent resistance, dye resistance and dispersibility, A copolymer containing another copolymerizable ethylenically unsaturated monomer other than the monomer is preferred. Such a copolymer may be a block copolymer containing an ethylenically unsaturated monomer having a specific structure α and another ethylenically unsaturated monomer, or a random copolymer. The copolymer containing an ethylenically unsaturated monomer having a specific structure α and another ethylenically unsaturated monomer includes an ethylenically unsaturated monomer having a specific structure α and other copolymers It means a copolymer having an ethylenically unsaturated monomer as a structural unit, and the same shall be interpreted in the following description.

  Other ethylenically unsaturated monomers include, for example, alkyl (meth) acrylate, alkenyl (meth) acrylate, aryl (meth) acrylate, hydroxylalkyl (meth) acrylate, aminoalkyl (meth) acrylate, and alicyclic (Meth) acrylic acid ester having a hydrocarbon group, aromatic vinyl compound, (meth) acrylic acid ester of polyhydric alcohol, N-substituted maleimide, aromatic vinyl compound, vinyl ether, ethylenic group having oxygen-containing saturated heterocyclic group Examples thereof include an unsaturated monomer, a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain (hereinafter also referred to as “unsaturated monomer (a)”). The amino group of the aminoalkyl (meth) acrylate may be substituted or unsubstituted, but is preferably substituted from the viewpoint of achieving heat resistance and solvent resistance at a high level. The unsaturated monomer (a) can be used alone or in combination of two or more.

(B1) Resin is a polymer of an ethylenically unsaturated monomer having a specific structure α, or a copolymer containing an ethylenically unsaturated monomer having a specific structure α and an unsaturated monomer (a) (A) It can have a function as a dispersing agent of a coloring agent. The resin (b1) functioning as such a dispersant can contain one or more kinds.
In addition, an ethylenically unsaturated monomer having a specific structure α and, if necessary, an unsaturated monomer (a) and an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). The function as a binder resin can be imparted by using a copolymer including a monomer (b) ". The resin (b1) that functions as the binder resin may be a block copolymer or a random copolymer. Moreover, (b1) resin which functions as this binder resin can contain 1 type (s) or 2 or more types, and even if it uses 1 type (s) or 2 or more types for an unsaturated monomer (b). Good.

Specific examples of the unsaturated monomer (a) are as follows.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
Examples of the alkenyl (meth) acrylate include vinyl (meth) acrylate and allyl (meth) acrylate.
Examples of the aryl (meth) acrylate include phenyl (meth) acrylate and benzyl (meth) acrylate.
Examples of the hydroxylalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate.
Examples of the substituted aminoalkyl (meth) acrylate include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, Examples include diethylaminobutyl (meth) acrylate, dimethylaminoethoxyethyl (meth) acrylate, dimethylaminoethoxypropyl (meth) acrylate, and diethylaminobutoxybutyl (meth) acrylate.
Examples of the (meth) acrylic acid ester having an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl ( And (meth) acrylate and dicyclopentenyl (meth) acrylate.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, acenaphthylene, and the like.
Examples of the (meth) acrylic acid ester of polyhydric alcohol include polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene Examples include glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, glycerol mono (meth) acrylate, and the like.
Examples of the N-substituted maleimide include N-phenylmaleimide and N-cyclohexylmaleimide.
Examples of the vinyl ether include cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and the like.

Examples of the ethylenically unsaturated monomer having an oxygen-containing saturated heterocyclic group include:
Glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, 2,3-bis Ethylene having an oxiranyl group such as (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl (meth) acrylate Unsaturated monomers;
(Vinyloxyalkyl) alkyloxetanes such as 3- (vinyloxymethyl) -2-methyloxetane, 2- (vinyloxyethyl) -2-methyloxetane;
(Meth) acryloyloxyalkyl oxetanes such as 3-[(meth) acryloyloxymethyl] oxetane, 2- [2- (meth) acryloyloxyethyl] oxetane;
3-[(meth) acryloyloxymethyl] -2-methyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-ethyloxetane, 2-[(meth) acryloyloxymethyl] -2-phenyloxetane [(Meth) acryloyloxyalkyl] phenyloxetane, 4- [3- (3-ethyloxetane-3-ylmethoxy) propoxy] styrene, 4- [7- (3-ethyloxetane-3-ylmethoxy) heptyloxy] styrene An ethylenically unsaturated monomer having an oxetanyl group such as
(Meth) acrylic acid ester having 3,4-epoxycyclohexyl group such as 3,4-epoxycyclohexylmethyl (meth) acrylate,
Examples thereof include (meth) acrylic acid esters having a tetrahydrofuranyl group such as tetrahydrofurfuryl methacrylate.

  Examples of the macromonomer include macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane. it can.

  Examples of the unsaturated monomer (b) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono ( And (meth) acrylate and p-vinylbenzoic acid.

  (B1) When the resin is used as a dispersant, the unsaturated monomer (a) is an alkyl (meth) acrylate, a substituted aminoalkyl (meth) acrylate, or a (meth) acrylate having an oxygen-containing saturated heterocyclic group. , Hydroxylalkyl (meth) acrylate, aryl (meth) acrylate, and an aromatic vinyl compound are preferred, and the alkyl (meth) acrylate and the ethylenically unsaturated monomer having an oxygen-containing saturated heterocyclic group are preferable. It is more preferable to contain at least one selected from a monomer and a substituted aminoalkyl (meth) acrylate, and it contains an alkyl (meth) acrylate and a substituted aminoalkyl (meth) acrylate, or an alkyl (meth) acrylate, oxygen-containing Ethylenically unsaturated monocyclic having a saturated heterocyclic group It is more preferable to contain the body and substituted aminoalkyl (meth) acrylate. (B1) When using resin as a dispersing agent, heat resistance and dye transfer property can further be improved by containing an ethylenically unsaturated monomer having an oxygen-containing saturated heterocyclic group.

  In the case of containing a substituted aminoalkyl (meth) acrylate as the unsaturated monomer (a), after polymerizing the monomer, the polymer is reacted with a halogenated hydrocarbon compound, and a partial amino group May be quaternized ammonium. As described above, the resin (b1) has at least one selected from the group consisting of a substituted amino group and a quaternary ammonium base, so that both heat resistance and solvent resistance can be achieved at a higher level. The dyeability can also be improved. In this case, it is preferable that 5 to 50% by mass, preferably 10 to 30% by mass in the substituted aminoalkyl (meth) acrylate is quaternized ammonium.

When (b1) resin is used as a dispersant, (b1) the copolymerization ratio of the monomer having the specific structure α in the resin is preferably 3 to 50% by mass, more preferably 10 to 45% by mass, 15 -40 mass% is still more preferable. Moreover, 5-80 mass% is preferable, as for the copolymerization ratio of the aminoalkyl (meth) acrylate in (b1) resin, 10-50 mass% is more preferable, and 15-40 mass% is still more preferable. Further, when (b1) the resin contains an ethylenically unsaturated monomer having an oxygen-containing saturated heterocyclic group, (b1) copolymerization of the ethylenically unsaturated monomer having an oxygen-containing saturated heterocyclic group in the resin The ratio is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, and still more preferably 5 to 25% by mass. In these cases, it is a block copolymer containing an A block containing a monomer having a specific structure α and a B block containing an aminoalkyl (meth) acrylate, from the viewpoint of heat resistance and solvent resistance. To preferred. When an ethylenically unsaturated monomer having an oxygen-containing saturated heterocyclic group is contained, it is preferably contained in the A block.
When (b1) resin is used as a dispersant, (b1) resin usually has a weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of 1,000 to 100,000. , Preferably 3,000 to 50,000. The ratio (Mw / Mn) of (b1) resin Mw to number average molecular weight (Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. In the present specification, “Mw” is a polystyrene equivalent weight average molecular weight measured by GPC (elution solvent: DMF), and “Mn” is a polystyrene equivalent number measured by GPC (elution solvent: DMF). Average molecular weight. By setting it as such an aspect, not only can heat resistance and solvent resistance be compatible with a high level, but the colored cured film which is excellent also in migration resistance can be formed.

In addition, when (b1) resin is used as a binder resin, together with unsaturated monomer (b), unsaturated monomer (a) includes alkyl (meth) acrylate, aryl (meth) acrylate, hydroxylalkyl. It is preferable to contain as a monomer at least one selected from (meth) acrylates, aromatic vinyl compounds and N-substituted maleimides.
When (b1) resin is used as the binder resin, the copolymerization ratio of the monomer having the specific structure α in (b1) resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, 15 -30 mass% is still more preferable. Moreover, 5-40 mass% is preferable and, as for the copolymerization ratio of the unsaturated monomer (b) in (b1) resin, 10-30 mass% is more preferable.
When (b1) resin is used as a binder resin, the (b1) resin has a polystyrene-equivalent Mw measured by GPC (elution solvent: DMF) of usually 1,000 to 100,000, preferably 3,000 to 50,000. Further, the ratio (Mw / Mn) of Mw and Mn of the (b1) resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. By adopting such an aspect, a colored cured film that can improve alkali developability and binding property to a substrate, and not only achieve both high heat resistance and solvent resistance at a high level, but also excellent in migration resistance. Can be formed.

  (B1) The resin can be produced by a known method, for example, by a method disclosed in JP 2003-222717 A, JP 2006-259680 A, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can also be controlled.

  In the present embodiment, the (B) resin can contain other resins in addition to the (b1) resin, and examples of such other resins include known binder resins and resin-type dispersants. be able to. In addition, the specific structure of a well-known binder resin is explained in full detail in 3rd Embodiment mentioned later. Examples of the resin-type dispersant include a resin containing a substituted aminoalkyl (meth) acrylate as a repeating unit. All or a part of the amino group of the resin is quaternized ammonium to form a quaternary ammonium base. It is good also as resin which has.

  Commercially available dispersants can be used as such resin-type dispersants. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 ( As described above, Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by Big Chemy (BYK)) as urethane-based dispersants such as Big Chemie (BYK)) Solsperse 76500 (manufactured by Lubrizol Co., Ltd.) and the like, polyethyleneimine-based dispersants, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc. PB821, Adisper PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like, can be mentioned, respectively. In addition, BYK-LPN21324 (manufactured by BYK Corporation (BYK)) can also be used.

  The content of (B) resin is usually 10 to 1,000 parts by mass with respect to 100 parts by mass of (A) colorant as the total amount of (b1) resin and other resins added as necessary. Preferably it is 20-500 mass parts. Moreover, it is preferable that content of (b1) resin is 20-500 mass parts with respect to 100 mass parts of (A) coloring agents, 70-400 mass parts is more preferable, 125-300 mass parts is still more preferable. . By adopting such an embodiment, the color development that can further enhance the alkali developability and the binding property to the substrate, and not only achieve a high level of both heat resistance and solvent resistance, but also excellent migration resistance. A film can be formed.

-(C) Polymerizable compound-
As the polymerizable compound (C) used in the present embodiment, a known polymerizable compound can be contained, and (c1) a polymerizable compound having a specific structure α, which will be described in detail in a third embodiment described later. Can also be contained. For example, a known polymerizable compound can be contained together with the polymerizable compound having the specific structure α (c1) or in place of the polymerizable compound having the specific structure α (c1). Hereinafter, known polymerizable compounds will be described.

  As the known polymerizable compound, a compound having two or more polymerizable groups is preferable. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. Among them, as the polymerizable compound (C), a compound having two or more (meth) acryloyl groups, a compound having two or more oxiranyl groups, and a compound having two or more oxetanyl groups are preferable. A compound having a (meth) acryloyl group and a compound having two or more oxetanyl groups are more preferable. (C) One or two or more polymerizable compounds can be contained.

  Specific examples of the compound having two or more (meth) acryloyl groups include polyfunctional (meth) acrylate, which is a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid, and a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate which is a reaction product of (meth) acrylate having hydroxyl group and polyfunctional isocyanate, (meth) acrylate having hydroxyl group and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group which is a reaction material with a thing can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dimethacrylate. Etc. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The polyfunctional (meth) acrylate modified with alkylene oxide is modified with at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Pentamethyl modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Penta modified with at least one selected from erythritol tri (meth) acrylate, ethylene oxide and propylene oxide Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from lithitol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

Examples of the compound having two or more oxiranyl groups include epoxy resins, (co) polymers of ethylenically unsaturated monomers having oxiranyl groups, and polyfunctional epoxy resins such as EHPE3150 (manufactured by Daicel Corporation). Can be used.
Moreover, as a compound which has 2 or more oxetanyl groups, in addition to the (co) polymer of the ethylenically unsaturated monomer which has an oxiranyl group, Aron oxetane OXT-121, OXT-221 (above, Toagosei Co., Ltd.) Manufactured).
Other aliphatic conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dimethyl-1,3-butadiene; divinylbenzene Non-conjugated divinyl compounds such as diisopropenylbenzene and trivinylbenzene can also be used.

  Among these polymerizable compounds, polyfunctional (meth) acrylate, which is a reaction product of trivalent or higher aliphatic polyhydroxy compound and (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylate, polyfunctional urethane (Meth) acrylates, polyfunctional (meth) acrylates having a carboxyl group, and (co) polymers of ethylenically unsaturated monomers having an oxiranyl group are preferred. Among them, from the viewpoint of further improving the heat resistance and solvent resistance, among the polyfunctional (meth) acrylate that is a reaction product of a trivalent or higher aliphatic polyhydroxy compound and (meth) acrylic acid, trimethylol Propane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate are preferred, and among polyfunctional (meth) acrylates having a carboxyl group, a reaction product of pentaerythritol triacrylate and succinic anhydride, A reaction product of dipentaerythritol pentaacrylate and succinic anhydride is preferred.

  (C) As for content of a polymeric compound, 10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agent, 20-800 mass parts is more preferable, 100-500 mass parts is still more preferable. . By setting it as such an aspect, the crosslinked density can be raised further and not only can heat resistance and solvent resistance be compatible at a higher level, but also a colored cured film having excellent migration resistance can be formed.

-Photopolymerization initiator-
The coloring composition of this embodiment can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present embodiment is a compound that generates an active species capable of initiating polymerization of the polymerizable compound (C) upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. is there. A photoinitiator can contain 1 type, or 2 or more types.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned. Among these, at least one selected from the group of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds is preferable.

  Among suitable photopolymerization initiators, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of the acetophenone compound include, for example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like can be given.

  Specific examples of biimidazole compounds include, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 '-Bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4 , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, the hydrogen donor can contain one kind or two or more kinds, but it is possible to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors. It is preferable in that the sensitivity can be further improved.

  Specific examples of the triazine compound include compounds described in paragraphs [0063] to [0065] of JP-B-57-6096 and JP-A-2003-238898.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9. -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuran) Nylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1) , 3-Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Corporation) and the like can also be used.

  In this embodiment, when using photoinitiators other than biimidazole compounds, such as an acetophenone compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this embodiment, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polymeric compound, and, as for content of a photoinitiator, 1-100 mass parts is still more preferable. By setting it as such an aspect, the crosslinked density can be raised further and the colored cured film which can not only make heat resistance and solvent resistance compatible with a high level but also is excellent also in dye transfer resistance can be formed.

-Solvent-
The colored composition of the present embodiment contains the components (A) to (C) as well as other components that are optionally added, but is usually prepared as a liquid composition by blending an organic solvent. The
As a solvent, as long as (A)-(C) component which comprises a coloring composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components and has moderate volatility, it is suitably. You can select and use. The solvent can contain 1 type (s) or 2 or more types.

Among such organic solvents, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, (poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Cyclic ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Fatty acid alkyl esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  Among these, (poly) alkylene glycol monoalkyl ether and (poly) alkylene glycol monoalkyl ether acetate are preferable from the viewpoints of solubility, dispersibility, coatability, and the like.

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the coloring composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. preferable. By setting it as such an aspect, it can be set as a coloring agent dispersion with favorable dispersibility and storage stability, and a coloring composition with favorable coating property and storage stability.

-Additives-
The coloring composition of this embodiment can also contain various additives as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicone surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropro Adhesion promoters such as rutrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butane Such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Examples include developability improvers and curing accelerators such as bis- (4-t-butylphenyl) iodonium nonafluorobutanesulfonate.

  The coloring composition of the present embodiment can be prepared by an appropriate method. For example, the components (A) to (C) are mixed together with a solvent and other components optionally added. Can be prepared. Among them, (A) a colorant in a solvent, in the presence of a dispersant, and optionally (B) a part of the resin, for example, using a bead mill, a roll mill, etc., mixed and dispersed to obtain a pigment dispersion. Then, a method of preparing the pigment dispersion by adding (C) a polymerizable compound, and (B) a resin, and if necessary, an additional solvent and other components and mixing them is preferable.

<Third Embodiment>
The colored composition of this embodiment includes (A) a colorant, (B) a resin, and (C) a polymerizable compound, and (C) the polymerizable compound has a structure in which (c1) a cyclic ether group is generated by heating. Contains compounds.
Hereinafter, the components of the colored composition according to this embodiment will be described.

-(A) Colorant-
(A) The colorant is selected from known colorants detailed in the second embodiment and (a1) a compound having a specific structure α and a dye structure described in detail in the fourth embodiment described later. It can contain seeds or two or more. The specific mode of the colorant in the third embodiment is the same as that in the second embodiment.

  The content ratio of the colorant (A) according to the present embodiment is such that a pixel having excellent luminance, heat resistance and solvent resistance, or a black matrix and black spacer having excellent light shielding properties are formed. Preferably, it is 5-70 mass%, More preferably, it is 10-60 mass%, More preferably, it is 15-50 mass%.

-(B) Resin-
As (B) resin, (b1) resin detailed in 2nd Embodiment can be contained. Moreover, it can replace with (b1) resin or replace with (b1) resin, and can contain another resin. Examples of other resins include known binder resins and resin-type dispersants. Although it does not specifically limit as a well-known binder resin, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group, and an unsaturated monomer (a) and an unsaturated monomer ( More preferred are copolymers with b). Specific configurations of the unsaturated monomer (a) and the unsaturated monomer (b) are as described in the second embodiment.

In the copolymer of the unsaturated monomer (a) and the unsaturated monomer (b), the copolymerization ratio of the unsaturated monomer (b) in the copolymer is preferably 5 to 50 mass. %, More preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b) in such a range, the alkali developability and the binding property to the substrate can be improved, and not only can the heat resistance and the solvent resistance be compatible at a high level, A colored cured film having excellent dye transfer resistance can be formed. The specific modes of the unsaturated monomer (a) and the unsaturated monomer (b) are as described in the second embodiment. The unsaturated monomer (a) and the unsaturated monomer (B) can contain 1 type (s) or 2 or more types, respectively.

In the present embodiment, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in JP-A-2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.
Specific examples of the carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain include, for example,
1) a copolymer obtained by reacting a polymerizable unsaturated compound having an oxiranyl group with a copolymer of a monomer containing an unsaturated carboxylic acid,
2) a polymer obtained by reacting an unsaturated carboxylic acid with a copolymer of monomers containing an unsaturated carboxylic acid and a polymerizable unsaturated compound having an oxiranyl group,
3) A polymer obtained by reacting an unsaturated isocyanate compound with a copolymer of a monomer containing an unsaturated carboxylic acid and a polymerizable unsaturated compound having a hydroxyl group can be exemplified.

  The known binder resin has an Mw measured by GPC of usually from 1,000 to 100,000, preferably from 3,000 to 50,000, and a ratio of Mw to Mn (Mw / Mn) is preferably It is 1.0-5.0, More preferably, it is 1.0-3.0. By adopting such an embodiment, the alkali developability and the binding property to the substrate can be further enhanced, and not only the heat resistance and the solvent resistance can be compatible at a higher level, but also coloring excellent in migration resistance. A cured film can be formed.

  A known binder resin can be produced by a known method, for example, a method disclosed in JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871 or the like. Thus, the structure, Mw, and Mw / Mn can be controlled.

(B) The resin can be used alone or in combination of two or more.
(B) Content of resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. By adopting such an embodiment, the color development which can further enhance the alkali developability and the binding property to the substrate, and not only achieve both high heat resistance and solvent resistance at a high level, but also excellent in migration resistance. A film can be formed.

-(C) Polymerizable compound-
The polymerizable compound (C) according to this embodiment is (c1) a polymerizable compound having a specific structure α (excluding the (b1) resin. Hereinafter, also referred to as “(c1) specific polymerizable compound”). Containing. In addition to (c1) the specific polymerizable compound, other polymerizable compounds can be contained. Specific modes of other polymerizable compounds are the same as those of the known polymerizable compounds described in detail in the second embodiment. Hereinafter, (c1) the specific polymerizable compound will be described.

  (C1) As a specific polymeric compound, the compound represented by following formula (5) can be mentioned, for example.

[In Formula (5),
Z represents an r-valent group,
Y represents an ethylene carbonate structure represented by the formula (1) or a cyclohexyl ethylene carbonate structure represented by the formula (2);
r represents an integer of 2 to 8. ]

The r-valent group in Z is preferably an r-valent group composed of 1 to 30 atoms excluding a hydrogen atom, composed of 2 to 30 atoms excluding a hydrogen atom, an alkanediyl group, a cycloalkylene group An r-valent group consisting of an arylene group, an ether group, a siloxy group (= Si-O-), a carbonyl group, an ester group, a cyanuric group (-C = N-), an amide group, and a combination of two or more thereof. Further preferred. Specific examples include groups obtained by removing r hydrogen atoms from polyhydric alcohols such as ethylene glycol, glycerin, pentaerythritol, dipentaerythritol, tripentaerythritol, etc .; cyclotrisiloxane, cyclotetrasiloxane, cyclopenta Examples thereof include a polysiloxane group obtained by removing an r-valent hydrogen atom from a cyclic siloxane such as siloxane; a group obtained by removing an r-valent hydrogen atom from a compound having a heterocyclic structure such as triazine or cyanuric acid.
For example, the cyclic siloxane having the specific structure α may be obtained by hydrolytic condensation of a group having the specific structure α and a silane compound having two hydrolyzable groups (for example, alkoxy groups). The triazine having the specific structure α may be obtained by, for example, reacting cyanuric chloride with an amine having the specific structure α. The cyanuric acid having the specific structure α is obtained by trimerizing an isocyanate having the specific structure α, for example. do it.
Although r shows the integer of 2-8, 2-6 are preferable and 2-4 are still more preferable.
The specific structure α is as described in the first embodiment.

  Specific examples of the polymerizable compound represented by the above formula (5) include compounds listed in the following compound group β.

(C) One or two or more polymerizable compounds can be contained, and (c1) one or more specific polymerizable compounds can also be contained.
The content of the (C) polymerizable compound is 10 to 10 parts by mass with respect to 100 parts by mass of the (A) colorant as the total amount of the (c1) specific polymerizable compound and other polymerizable compound added as necessary. 1,000 parts by mass are preferable, 20 to 800 parts by mass are more preferable, and 100 to 500 parts by mass are still more preferable. Further, the content ratio of (c1) the specific polymerizable compound is preferably 10 to 100% by mass with respect to the total amount of (c1) the specific polymerizable compound and other polymerizable compound added as necessary, and is preferably 30 to 100%. The mass% is more preferable. By setting it as such an aspect, the crosslinked density can be raised further and not only can heat resistance and solvent resistance be compatible at a higher level, but also a colored cured film having excellent migration resistance can be formed.

  The colored composition of the present embodiment can contain the photopolymerization initiator, solvent, and additives detailed in the second embodiment. Note that specific modes of the photopolymerization initiator, the solvent, and the additive are as described in the second embodiment.

<Fourth embodiment>
The colored composition of the present embodiment includes (A) a colorant and (C) a polymerizable compound, and (A) the colorant has (a1) a compound having a specific structure α and a dye structure (hereinafter referred to as “(a1) It is also referred to as “colorant”. By setting it as such an aspect, the colored cured film which can not only make heat resistance and solvent resistance compatible with high level but also is excellent also in dye transfer resistance can be formed.
Hereinafter, the components of the colored composition according to this embodiment will be described.

-(A) Colorant-
The (A) colorant according to this embodiment contains (a1) a colorant.
(A1) The colorant can take an appropriate structure, but the following (i) or (ii) is preferable.
(I) a salt of the cationic chromophore and the cationic chromophore and a counter anion having a specific structure α (ii) the chromophore is an anionic chromophore and the anionic chromophore And a counter cation having a specific structure α

  Specific configurations of the chromophore and the counter ion are as described in the second embodiment. The counter ion is not particularly limited as long as it has a specific structure α. For example, the counter ion may be in the following mode (iii) or (iv).

iii) a copolymer of an ethylenically unsaturated monomer having a counter anion having an anionic group and a monomer having a specific structure α
iv) Copolymer of an ethylenically unsaturated monomer having a cationic group as a counter cation and a monomer having a specific structure α

  Although the ethylenically unsaturated monomer having an anionic group or a cationic group is not particularly limited, examples of the ethylenically unsaturated monomer having an anionic group include those represented by the following formula. . In addition, the ethylenically unsaturated monomer which has an anionic group or a cationic group can contain 1 type (s) or 2 or more types, respectively.

  Examples of the monomer having the specific structure α include an ethylenically unsaturated monomer represented by the formula (3) and an ethylenically unsaturated monomer represented by the formula (4). it can. The ethylenically unsaturated monomer having the specific structure α can contain one or more.

  In addition, an embodiment in which the (a1) colorant according to this embodiment is a copolymer containing an ethylenically unsaturated monomer having a dye structure and an ethylenically unsaturated monomer having a specific structure α is also preferable. . In this case, other copolymerizable ethylenically unsaturated monomers other than these may be contained. Examples of such an ethylenically unsaturated monomer include the aforementioned unsaturated monomer (a). In addition, the unsaturated monomer (a) can contain 1 type (s) or 2 or more types. Further, when (a1) the colorant is a copolymer containing an ethylenically unsaturated monomer having a dye structure and an ethylenically unsaturated monomer having a specific structure α, the colorant is described in the third embodiment. Similar to the binder resin described above, the side chain may have a polymerizable unsaturated bond such as a (meth) acryloyl group.

  (A1) When the colorant is a copolymer containing an ethylenically unsaturated monomer having a dye structure and an ethylenically unsaturated monomer having a specific structure α, the dye structure in the copolymer 1-90 mass% is preferable, as for the copolymerization ratio of the ethylenically unsaturated monomer which has, 10-80 mass% is more preferable, and 20-70 mass% is still more preferable. The copolymerization ratio of the ethylenically unsaturated monomer having the specific structure α in the copolymer is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 30% by mass. . Such a copolymer may be a block copolymer or a random copolymer. By adopting such an embodiment, the storage stability of the colored composition can be further improved, and a colored cured film that not only has both heat resistance and solvent resistance at a high level, but also has excellent dye transfer resistance is formed. can do.

  (A1) When the colorant is a copolymer containing an ethylenically unsaturated monomer having a dye structure and an ethylenically unsaturated monomer having a specific structure α, the Mw measured by GPC is usually 1 1,000 to 100,000, preferably 2,000 to 30,000. Further, the ratio (Mw / Mn) between Mw and Mn of the copolymer is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. By setting it as such an aspect, not only can heat resistance and solvent resistance be compatible with a high level, but the colored cured film which is excellent also in migration resistance can be formed.

  The coloring composition of this embodiment may contain other coloring agents other than (a1) coloring agents. Examples of such other colorants include the dyes and pigments described in detail in the second embodiment. Another colorant can contain 1 type (s) or 2 or more types.

  (A) The content of the colorant is such that a pixel having excellent luminance, heat resistance and solvent resistance, or a black matrix and a black spacer having excellent light shielding properties are formed in the solid content of the coloring composition (a1). The total amount of the colorant and other colorant added as necessary is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 15 to 50% by mass. Further, the content ratio of the (a1) colorant is preferably 5 to 80% by mass, more preferably 10 to 60% by mass with respect to the total amount of the (a1) colorant and other colorant added as necessary. .

-(C) Polymerizable compound-
(C) The polymerizable compound described in detail in the second embodiment can be used as the polymerizable compound, and the specific configuration thereof is as described in the second embodiment. (C) One or two or more polymerizable compounds may be contained, and (c1) the specific polymerizable compound described in detail in the aforementioned third embodiment may also be contained. (C) By containing a polymerizable compound, the crosslink density can be further increased, and not only can heat resistance and solvent resistance be compatible at a higher level, but also a colored cured film having excellent migration resistance can be formed. Can do.

  (C) As for content of a polymeric compound, 10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agent, 20-800 mass parts is more preferable, 100-500 mass parts is still more preferable. . By setting it as such an aspect, the crosslinked density can be raised further and not only can heat resistance and solvent resistance be compatible at a higher level, but also a colored cured film having excellent migration resistance can be formed.

-(B) Resin-
The colored composition of this embodiment can further contain (B) a resin. (B) As the resin, for example, one type selected from the group consisting of the known binder resin and the known resin-type dispersant described in the third embodiment, and the (b1) resin described in the second embodiment It is possible to contain the above. These specific configurations are as described in the above embodiment.
(B) Content of resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts.

  The colored composition of the present embodiment can contain the photopolymerization initiator, solvent, and additives detailed in the second embodiment. Note that specific modes of the photopolymerization initiator, the solvent, and the additive are as described in the second embodiment.

Colored cured film and method for forming the same The colored cured film of the present invention is formed using the colored composition of the present invention. Specifically, each color pixel used in a display device or a solid-state imaging device, a black matrix , Black spacer, infrared cut filter and the like.

Hereinafter, the colored cured film used for the color filter which comprises a display element and a solid-state image sensor, and its formation method are demonstrated.
As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, a blue liquid composition of the radiation-sensitive colored composition of the present invention is applied on the substrate, and then pre-baked to evaporate the solvent to form a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or red, application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and red color. Are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of the three primary colors of blue, green and red is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. However, it is a radiation sensitive material in which a black colorant is dispersed. A colored composition can be used in the same manner as in the case of forming the pixel.

Examples of the substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the coloring composition to the substrate, an appropriate application method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), a bar coating method, or the like is employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

The pre-baking is usually about 70 to 110 ° C. for about 1 to 10 minutes.
The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.
Exposure of the radiation is generally preferred 10~10,000J / m ^2.

Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, and 1,8-diazabicyclo- [5.4.0] -7-undecene. An aqueous solution of 1,5-diazabicyclo- [4.3.0] -5-nonene is preferable.
For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a liquid composition of a blue thermosetting coloring composition is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a blue pixel pattern.

  Next, using the green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. As a result, a color filter in which the pixel patterns of the three primary colors of blue, green and red are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a radiation-sensitive colored composition in which a black colorant is dispersed is used, but the curable composition of the present invention can also be suitably used for forming such a black spacer.

The colored composition of the present invention can be suitably used in forming any colored cured film such as each color pixel, black matrix, and black spacer used in the color filter.
Since the color filter having the colored cured film of the present invention thus formed has extremely high luminance and color purity, it can be used in color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like. Very useful.

Color filter The color filter of the present invention comprises the colored cured film of the present invention. Specifically, what is necessary is just to comprise the colored cured film of this invention as members, such as each color pixel used for a color filter, a black matrix, a black spacer.

Display element The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Can be taken. Further, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (indium oxide doped with tin) electrode or an IZO (mixture of acid value indium and zinc oxide) electrode It is also possible to adopt a structure in which the substrate on which the substrate is formed faces the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed, or on the substrate side on which the ITO electrode or IZO electrode is formed.

  The color liquid crystal display element including the colored cured film of the present invention can include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display element having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical). An appropriate liquid crystal mode such as a Compensated Birefringence type is applicable.

Moreover, the organic EL display element provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
Moreover, the electronic paper provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-2007-41169.

Light-receiving element The light-receiving element of the present invention comprises the colored cured film of the present invention.
The light receiving element of the present invention can take an appropriate structure. For example, the colored cured film of the present invention is used as a color filter constituting a solid-state image sensor, and combined with a photodiode, an image sensor such as a solid-state image sensor can be obtained. Can be configured. Further, by using the colored cured film of the present invention as an infrared light transmission filter and combining it with a photodiode, an infrared light detection pixel can be configured.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

The abbreviations of the raw materials used in the following “(B) Synthesis of Resin” are as follows.
-THF: Tetrahydrofuran-PGMEA: Propylene glycol monomethyl ether acetate-AIBN: 2,2'-azobisisobutyronitrile-CCMA: (2-oxo-1,3-dioxolan-4-yl) methyl methacrylate-MA: Methacryl Acid / HOAMS: Succinic acid-2-acryloyloxyethyl (manufactured by Kyoeisha Chemical Co., Ltd., trade name HOA-MS)
ST: Styrene, PMI: N-Phenylmaleimide, MMA: Methyl methacrylate, HEMA: Hydroxyethyl methacrylate, EHMA: 2-ethylhexyl methacrylate, nBMA: Normal butyl methacrylate, DAMA: Dimethylaminoethyl methacrylate, OXMA: 3- ( Methacryloyloxymethyl) -3-ethyloxetane

<Measurement of Mw and Mw / Mn>
Mw and Mn of the resin (B) obtained in each of the following synthesis examples were measured by GPC having the following specifications.
・ Apparatus: GPC-104 (made by Showa Denko KK)
Column: KD-G, KF-603, KF-602, KF-601 were used in combination.
-Mobile phase: DMF
・ Standard: Polystyrene

-(B) Resin synthesis-
<Synthesis of dispersant>
Dispersant synthesis example 1
To a 300 mL flask, 100 mL of THF and 0.25 g of lithium chloride were added and cooled to −60 ° C. 3 mL of n-butyllithium hexane solution (concentration 2.0 mol / L) was added, and after stirring for 5 minutes, diphenylethylene (0.86 g) was added and stirred for 15 minutes. A mixed solution of MMA 6 g, nBMA 11.2 g, EHMA 6 g, and CCMA 8 g was dropped, and the reaction was continued for 15 minutes. Gas chromatography (hereinafter abbreviated as GC) was measured to confirm the disappearance of the monomer. Next, 8.8 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. After measuring GC and confirming the disappearance of the monomer, 0.5 g of ethanol was added to stop the reaction. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MMA, nBMA, EHMA, and CCMA was obtained. The obtained polymer had Mw of 11,000 and Mw / Mn of 1.3. The obtained copolymer is referred to as “copolymer (B-1)”. Copolymer (B-1) corresponds to (b1) resin.

Dispersant synthesis example 2
To the solution containing the copolymer (B-1) obtained in Synthesis Example 1, 1.4 g of benzyl chloride and 25.0 g of propylene glycol monomethyl ether were added, and then gently stirred, so that the temperature of the polymer solution was 80 ° C. The temperature was maintained for 8 hours to partially quaternize the dimethylamino group derived from DAMA. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. In this way, a block copolymer consisting of an A block having a DAMA-derived repeating unit, 20% by mass of which is quaternary ammoniumated, and a B block having a repeating unit derived from MMA, nBMA, EHMA, and CCMA. Coalescence was obtained. The obtained copolymer is referred to as “copolymer (B-2)”. Copolymer (B-2) corresponds to (b1) resin.

Dispersant synthesis examples 3 to 6
By operating in the same manner as in Dispersant Synthesis Example 1, copolymers B-3 to B-5 having the composition specified in Table 1 and comparative copolymer b-1 were obtained. In addition, the numerical value in Table 1 is a mass part. Copolymers (B-3) to (B-5) correspond to the (b1) resin, and the copolymer (b-1) does not correspond to the (b1) resin.

<Synthesis of binder resin>
Binder resin synthesis example 1
In a flask equipped with a condenser and a stirrer, St7g, PMI9g, HEMA9g, EHMA27.5g, CCMA20g, MA15g, and HOAMS12.5g were dissolved in propylene glycol monomethyl ether acetate 200g, and AIBN 3.0g and α-methylstyrene dimer 5 0.0 g was charged and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling and polymerized for 5 hours to obtain a solution containing 33% by mass of the binder resin (B-6). This binder resin (B-6) had Mw of 10,000 and Mw / Mn of 2.5. Binder resin (B-6) corresponds to (b1) resin.

Binder resin synthesis example 2
A solution containing 33% by mass of the binder resin (b-2) in the same manner as in the binder resin synthesis example 1 except that the type and amount of the monomer used were changed as shown in Table 2 in the binder resin synthesis example 1. Got. Binder resin (b-2) does not correspond to (b1) resin.

-(A) Synthesis of colorant-
<Synthesis of dye multimers>
Dye multimer synthesis example 1
In a reaction vessel equipped with a condenser, 5.5 g of p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt (hereinafter referred to as “super strong acid monomer A”), MMA 2.5 g, CCMA 2.0 g, α-thioglycerol 0 .13 g was added and dissolved in 20 g of cyclohexanone. The solution was heated to 80 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, a solution prepared by dissolving 0.098 g of α, α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. Continued. Thereafter, the reaction solution was cooled to room temperature, and then 60 g of acetone was added to make a uniform solution. This was added dropwise to 1.1 L of hexane, and the resulting precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 8.14 g of a polymer. The obtained polymer (1) had Mw of 7,800 and Mw / Mn of 2.2.
Next, 2.0 g of the obtained polymer (1) was dissolved in 40 mL of acetone. I. 1.56 g of Basic Blue 7 was added and stirred at room temperature for 1 hour. Thereafter, 200 mL of ion-exchanged water was added to the residue obtained by concentrating the reaction solution under reduced pressure, and the precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 2.54 g of a dye multimer represented by the following structural formula. By mixing 15 parts by mass of the obtained dye multimer and 85 parts by mass of cyclohexanone, a solution containing the dye multimer DB-1 was obtained. The dye multimer DB-1 corresponds to (a1) a colorant.

Dye multimer synthesis example 2
In Dye Multimer Synthesis Example 1, a polymer was synthesized in the same manner as Dye Multimer Synthesis Example 1 except that the amount of MMA was changed to 4.5 g and CCMA was not used. This is referred to as a polymer (2). Next, a dye multimer was obtained in the same manner as in dye multimer synthesis example 1 except that the polymer (2) was used instead of the polymer (1). By mixing 15 parts by mass of the obtained dye multimer and 85 parts by mass of cyclohexanone, a solution containing the dye multimer DB-2 was obtained. Dye multimer DB-2 does not correspond to (a1) colorant.

Dye multimer synthesis example 3
2.0 g of the polymer (1) was dissolved in 40 mL of acetone, 1.36 g of cyanine dye-1 represented by the following formula was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, 200 mL of ion-exchanged water was added to the residue obtained by concentrating the reaction solution under reduced pressure, and the precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 2.54 g of a dye multimer represented by the following structural formula. By mixing 15 parts by mass of the obtained dye multimer and 85 parts by mass of cyclohexanone, a solution containing the dye multimer DR-1 was obtained. The dye multimer DR-1 corresponds to (a1) a colorant.

Dye multimer synthesis example 4
In the dye multimer synthesis example 3, a dye multimer was obtained in the same manner as in the dye multimer synthesis example 3 except that the polymer (2) was used instead of the polymer (1). By mixing 15 parts by mass of the obtained dye multimer and 85 parts by mass of cyclohexanone, a solution containing the dye multimer DR-2 was obtained. The dye multimer DR-2 does not correspond to the (a1) colorant.

<Synthesis and Preparation of Dye for Blue Coloring Composition>
The following compound was obtained according to the method described in paragraph [0128] of JP-A-2015-143835. 15 parts by mass of the obtained compound and 85 parts by mass of cyclohexanone were mixed to obtain a dye solution (BLUEDYE-1).

<Preparation of pigment dispersion for blue coloring composition>
Preparation Example 1
As a coloring agent, C.I. I. 15 parts by weight of CI Pigment Blue 15: 6, 12.5 parts by weight of copolymer (B-1) as a dispersant (solid content concentration 40% by weight), and 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (A-1) was prepared by processing with a bead mill.

Preparation Examples 2-6
In Preparation Example 1, pigment dispersions (A-2) to (A-) were prepared in the same manner as in Preparation Example 1, except that the copolymers shown in Table 3 below were used instead of the copolymer (B-1). 6) was prepared.

<Preparation of blue coloring composition>
Example 1
13.5 parts by mass of pigment dispersion (A-1) and 7.2 parts by mass of a dye solution (BLUEDYE-1) as a colorant, 9.9 parts by mass of a binder resin (B-6) solution as a binder resin, (C) 15.4 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a polymerizable compound, and 2-benzyl-2 as a photopolymerization initiator -1.8 parts by mass of N-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) and NCI-930 (produced by ADEKA) 0.1 part by mass, 0.2 part by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, And propylene glycol monomethyl ether acetate as a solvent was mixed to prepare a colored composition (BLUE-1) having a solid content concentration of 20% by mass.

Evaluation of Solvent Resistance After applying the blue coloring composition (BLUE-1) on a soda glass substrate having a SiO ₂ film formed on its surface to prevent elution of sodium ions, using a spin coater, 90 ° C. Pre-baking was performed for 2 minutes on a hot plate to form a coating film having a film thickness of 2.5 μm.
Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed with the exposure amount of 400 J / m < ² > to the coating film through the photomask using the high pressure mercury lamp. Then, shower development was performed for 50 seconds by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a dot pattern on the substrate. Thereafter, the substrate was immersed in propylene glycol monomethyl ether acetate at 80 ° C. for 40 minutes.
Chromaticity coordinate values (x, y) and stimulation values (Y) were measured before and after immersion, and the color change before and after immersion, that is, ΔE ^* ab was evaluated. As a result, when the value of ΔE ^* ab is less than 2.0, it is “1”, when it is 2.0 or more and less than 3.0, “2”, when it is 3.0 or more and less than 4.0, “3”, The case of 4.0 or more and less than 5.0 was evaluated as “4”, and the case of 5.0 or more was evaluated as “5”. The evaluation results are shown in Table 4. It can be said that the smaller the ΔE ^* ab value, the better the solvent resistance.

Evaluation of heat resistance After applying a blue coloring composition (BLUE-1) on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed using a spin coater, hot at 90 ° C. The plate was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 μm.
Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed with the exposure amount of 400 J / m < ² > to the coating film through the photomask using the high pressure mercury lamp. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 200 ° C. for 30 minutes to form a dot pattern on the substrate.
About the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a chromaticity coordinate value (x, y) and a stimulus value (Y) in the CIE color system with a 2-degree field of view. Was measured.
Next, after the substrate was additionally baked at 230 ° C. for 90 minutes, the chromaticity coordinate values (x, y) and the stimulus value (Y) were measured, and the color change before and after the additional baking, that is, ΔE ^* ab was evaluated. . As a result, when the value of ΔE ^* ab is less than 2.0, it is “1”, when it is 2.0 or more and less than 3.0, “2”, when it is 3.0 or more and less than 4.0, “3”, The case of 4.0 or more and less than 5.0 was evaluated as “4”, and the case of 5.0 or more was evaluated as “5”. The evaluation results are shown in Table 4. In addition, it can be said that heat resistance is so favorable that (DELTA ⁾ E ^* ab value is small.

Evaluation of transferability After applying a blue coloring composition (BLUE-1) on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, Pre-baking was performed for 2 minutes on a hot plate to form a coating film having a thickness of 2.4 μm.
Next, after cooling this substrate to room temperature, the entire surface was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 400 J / m ² without using a photomask using a high-pressure mercury lamp. . Thereafter, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged onto the substrate at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Thereafter, the substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a blue cured film on the substrate.
After coating the transparent protective film composition (OC-1) prepared by the method described later on the blue cured film using a spin coater, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 2 A 5 μm coating film was formed. The process from application of the transparent protective film composition (OC-1) on the blue cured film to pre-baking for 2 minutes on a hot plate at 90 ° C. is referred to as (Process-1).
(Step-1) The stimulus value (Y) of the blue cured film was measured before and after, and the stimulus value change before and after (Step-1), that is, ΔY was evaluated. As a result, the case where the value of ΔY was less than 0.2 was evaluated as “1”, the case of 0.2 or more and less than 0.4 was evaluated as “2”, and the case of 0.4 or more was evaluated as “3”. The evaluation results are shown in Table 4. It can be said that the smaller the ΔY value, the more the dye transfer property is suppressed.

The method for preparing the transparent protective film composition (OC-1) used for the evaluation of the transferability is as follows.
In a flask equipped with a condenser and a stirrer, 1 part by mass of 2,2′-azobis-isobutyronitrile, 4 parts by mass of bis (n-octylmercapto-thiocarbonyl) disulfide immediately after synthesis, and 200 parts by mass of propylene glycol monomethyl ether acetate Prepared the department. Subsequently, after 70 parts by mass of glycidyl methacrylate and 30 parts by mass of styrene were charged and purged with nitrogen, stirring was started gently. The solution temperature was raised to 95 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer. The solid content concentration of the obtained polymer solution was 32.8% by mass. This copolymer had Mw = 11,000 and Mw / Mn = 1.4.
20 parts by mass of bisphenol A novolak type epoxy resin (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.) is added to the solution containing the copolymer (amount corresponding to 100 parts by mass (solid content) of the copolymer). 30 parts by mass of hexahydrophthalic anhydride (C-1) as a curing agent and 1 part by mass of benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate (D-1) as a heat-sensitive acid generator After adding propylene glycol monomethyl ether acetate so that the solid content concentration becomes 20% by mass, the composition for transparent protective film (OC-1) was prepared by filtering through a Millipore filter having a pore size of 0.5 μm.

Examples 2-9 and Comparative Examples 1-2
In Example 1, coloring compositions (BLUE-2) to (BLUE-) were obtained in the same manner as in Example 1 except that the types of the pigment dispersion, binder resin, dye solution and polymerizable compound were changed as shown in Table 4. 11) was prepared.
Next, evaluation was performed in the same manner as in Example 1 except that (BLUE-2) to (BLUE-11) were used instead of (BLUE-1). The results are shown in Table 4. The polymerizable compounds A and B used in Examples 8 to 9 are represented by the following structural formula.

<Preparation of pigment dispersion for red coloring composition>
Preparation Example 7
As a coloring agent, C.I. I. 10.0 parts by mass of Pigment Red 254, 40.0 parts by mass of copolymer (B-1) as a dispersant (solid content concentration: 40% by mass), and 48.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent. The pigment dispersion (R-1) was prepared by treatment with a bead mill.

Preparation Examples 8-12
In Preparation Example 7, pigment dispersions (R-2) to (R-) were prepared in the same manner as Preparation Example 7, except that the copolymers shown in Table 5 below were used instead of the copolymer (B-1). 8) was prepared.

<Synthesis and Preparation of Dye for Red Coloring Composition>
Preparation Example 13
15 parts by mass of the compound represented by the formula (Ia-7) in International Publication No. 2014/192773 pamphlet and 85 parts by mass of cyclohexanone were mixed to obtain a dye solution (REDDYE-1).

Preparation Example 14
According to the method described in paragraph [0143] of Japanese Patent No. 5737078, C.I. I. A salt-forming compound of Acid Red 289 and dialkyl (alkyl is C14 to C18) dimethylammonium chloride was obtained. 15 parts by mass of the obtained salt-forming compound and 85 parts by mass of cyclohexanone were mixed to obtain a dye solution (REDDYE-2).

Example 10
<Preparation of red coloring composition>
42.3 parts by mass of pigment dispersion (R-1) as a colorant and 10.0 parts by mass of a dye solution (REDDYE-1), 11.0 parts by mass of a binder resin (B-6) solution as a binder resin (B) (C) 15.4 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as the polymerizable compound, and 2-benzyl- as the photopolymerization initiator 1.8 parts by mass of 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) and NCI-930 (produced by ADEKA Corporation) ) 0.1 part by mass, 0.2% by mass of MegaFac F-554 (manufactured by DIC Corporation) as a fluorosurfactant Part and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (RED-1) having a solid concentration of 20% by mass.

Evaluation of solvent resistance The solvent resistance was evaluated in the same manner as in Example 1 except that the red colored composition (RED-1) was used instead of the blue colored composition (BLUE-1) in Example 1. The results are shown in Table 6.

Evaluation of heat resistance The solvent resistance was evaluated in the same manner as in Example 1 except that the red coloring composition (RED-1) was used instead of the blue coloring composition (BLUE-1) in Example 1. The results are shown in Table 6.

Evaluation of transferability A red cured film (on the substrate) was prepared in the same manner as in Example 1 except that the red colored composition (RED-1) was used instead of the blue colored composition (BLUE-1) in Example 1. RED-1) was formed.
After applying the green coloring composition (GREEN-1) prepared by the method described later on the red cured film (RED-1) using a spin coater, pre-baking on a hot plate at 90 ° C. for 2 minutes, A coating film having a thickness of 2.5 μm was formed. Next, after cooling the substrate to room temperature, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged to the substrate at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm). The coating film consisting of the green coloring composition was removed. Thereafter, the substrate was washed with ultrapure water and air-dried. The process from applying the green coloring composition (GREEN-1) on the red cured film (RED-1) to air drying is referred to as (Process-2).
(Step-2) The stimulus value (Y) of the red cured film (RED-1) was measured before and after, and the stimulus value change before and after (Step-2), that is, ΔY was evaluated. As a result, the case where the value of ΔY was less than 0.2 was evaluated as “1”, the case of 0.2 or more and less than 0.4 was evaluated as “2”, and the case of 0.4 or more was evaluated as “3”. The evaluation results are shown in Table 6. It can be said that the smaller the ΔY value, the more the dye transfer property is suppressed.

The preparation method of the green coloring composition (GREEN-1) used for transferability evaluation is as follows. C. I. 45.0 parts of pigment dispersion containing 11 parts of Pigment Green 36, C.I. I. 15.0 parts of a pigment dispersion containing 11 parts of Pigment Yellow 150, 11.0 parts by weight of a binder resin (b-3) solution (solid concentration 33% by weight) as a binder resin, and trimethylolpropane triacrylate (as a polymerizable compound) "NK ester ATMPT" made by Shin-Nakamura Chemical Co., Ltd.), 1.2 parts "Irgacure 907" made by Ciba Japan as a photopolymerization initiator, and "EAB-F" made by Hodogaya Chemical Co., Ltd. as a sensitizer. Is mixed with 0.4 parts of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, and 23.2 parts of ethylene glycol monomethyl ether acetate as a solvent, to give a green coloring composition A product (GREEN-1) was prepared.

Examples 11-19 and Comparative Examples 3-4
In Example 10, colored compositions (RED-2) to (RED-) were obtained in the same manner as in Example 10 except that the types of the pigment dispersion, the binder resin, the dye solution, and the polymerizable compound were changed as shown in Table 6. 12) was prepared.
Next, evaluation was performed in the same manner as in Example 1 except that (RED-2) to (RED-12) were used instead of (RED-1). The results are shown in Table 6.

Example 20
13.5 parts by mass of pigment dispersion (A-1) and 7.2 parts by mass of a dye solution (BLUEDYE-1) as a colorant, 9.9 parts by mass of a binder resin (b-2) solution as a binder resin, (C) As a polymerizable compound, 7.2 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) and 7.2 parts by mass of polyfunctional oxetane, light As a polymerization initiator, 1.8 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) and NCI -930 (manufactured by ADEKA Corporation) 0.1 parts by mass, bis- (4-tert-butylphenyl) yo as a curing accelerator Mixing 0.3 parts by mass of donium nonafluorobutanesulfonate, 0.2 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, and propylene glycol monomethyl ether acetate as a solvent A colored composition (BLUE-12) having a solid content concentration of 20% by mass was prepared. In addition, the polyfunctional oxetane used in this example is ETERNACOLL. This is a resin obtained by homopolymerizing OXMA (manufactured by Ube Industries, Ltd.) by a known method.
In Example 1, it evaluated similarly to Example 1 except having used (BLUE-12) instead of the coloring composition (BLUE-1), solvent resistance was "1", and heat resistance. Was "1" and the transferability was "1".

Reference example 1
As a coloring agent, C.I. I. 5 parts by weight of Pigment Blue 15: 6 pigment dispersion (pigment concentration 12% by weight, binder resin B-7 concentration 0.8% by weight, dispersant concentration 3.8% by weight, solvent is propylene glycol monomethyl ether acetate) As a dye, 30 parts by mass of 10 mass% diacetone alcohol solution of pigment multimer TAM1 and 4 parts by mass of 10 mass% diacetone alcohol solution of pigment multimer Xa1 were mixed to obtain a colored liquid. Here, the dispersing agent is a methacrylic AB block copolymer described in paragraph 0296 of JP-A-2006-038584. Next, 16.7 parts by mass of the binder resin B-8 solution (solid content concentration 33% by mass), 8.3 parts by mass of the polymerizable compound C2, and 1.4 parts by mass of the photopolymerization initiator E2 are added to the colored liquid. Then, 1.5 parts by mass of the additive F1 solution, 0.5 part by mass of the additive LiFABA and 32.6 parts by mass of the solvent G1 were added, and the mixture was stirred well to be uniform. B-7, B-8, C2, E2, F1, G1, LiFABA, dye multimer TAM1 and dye multimer Xa1 are as described below. Then, 100 mass parts of blue coloring compositions (BLUE-101) were prepared by filtering with a membrane filter (made by Advantech Co., Ltd.) with a hole diameter of 1 micrometer. The content ratio of the colorant contained in the blue coloring composition (BLUE-101) is C.I. I. Pigment Blue 15: 6 / Dye Multimer TAM1 / Dye Multimer Xa1 = 15/75/10 (mass ratio).
Here, the coloring composition (BLUE-101) satisfies the following conditions A to C.
Condition A: The total concentration of each component excluding the solvent of the coloring composition is 20% by mass.
-Condition B: The content rate of a coloring agent is 20 mass% with respect to the sum total of components other than the solvent of a coloring composition.
Condition C: The total content of the binder resin and the content ratio of the polymerizable compound is 40/60 (mass ratio).

Reference Examples 2 to 57
In Reference Example 1, blue colored compositions (BLUE-102) to (BLUE-157) were prepared in the same manner as Reference Example 1, except that the types and amounts of the components used were changed as shown in Tables 7 to 8. did. In Tables 7 to 8, each component is as described below. In addition, the colored compositions (BLUE-102) to (BLUE-157) all satisfy the above conditions A to C.
When preparing the colored liquid, each pigment dispersion (pigment concentration 12% by mass, binder resin B-7 concentration 0.8% by mass, dispersant concentration 3.8% by mass, solvent is propylene glycol monomethyl ether acetate) And a 10% by mass diacetone alcohol solution of each dye multimer and a 10% by mass ethyl lactate solution of each low molecular dye in a mass part described in the “Mixing amount during preparation” column. . In Reference Examples 2 to 17 in which the coloring composition contains only one kind of colorant, 40 parts by mass of a 10% by mass diacetone alcohol solution of each dye multimer was used as it was as a coloring liquid.
The content ratio (mass ratio) of the colorant contained in the obtained colored composition is as shown in the “kind and content ratio” column.

In Tables 7-8, each component is as follows.
<Pigment>
-B15: 6: C.I. I. Pigment Blue 15: 6
B15: 3: C.I. I. Pigment Blue 15: 3
B15: 4: C.I. I. Pigment Blue 15: 4

<Dye (pigment multimer)>
Dye multimer TAM1-6: synthesized according to the following dye multimer synthesis examples 5-10, triarylmethane dye multimer Xa1-6: synthesized according to the following dye multimer synthesis examples 11-16, Xanthene Dye Multimer / Dye Multimer Cy: Cyanine Dye Multimer / Dye Multimer DPM: Dipyromethene Dye Multimer Synthesized according to Dye Multimer Synthesis Example 17 below

<Dye (low molecular dye)>
Xa7: Xanthene dye which is a salt-forming compound of a cation moiety of a monomer represented by the following formula (17) and a bis (trifluoromethanesulfonyl) imide anion. Xa8: Synthesis example of JP2013-19077A 1 and C.I. I. Xanthene dye, SB45: C.I. I. Solvent Blue 45 (anthraquinone dye)
SB70: C.I. I. Solvent Blue 70 (phthalocyanine dye)
TAP: tetraazaporphyrin dye represented by the following formula (12)

<Ingredients other than colorants>
B-7: methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / methyl methacrylate / styrene / glycidyl methacrylate = 16/16/38/10/20 (mass ratio) Binder resin obtained by reacting methacrylic acid with 100 mol% of the epoxy group of the copolymer of B: B: methacrylic acid / styrene / benzyl methacrylate / 2-hydroxyethyl methacrylate / 2-ethylhexyl methacrylate / N-phenyl 33% by weight propylene glycol monomethyl ether acetate solution of binder resin of maleimide / monosuccinic acid mono (2-acryloyloxyethyl) = 20/10/5/15/23/12/15 (parts by mass). LiFABA: lithium tetrakis (Pentafluorophenyl) bo Over door (Tosoh Finechem Co., Ltd.)
LiTFSI: Lithium bis (trifluoromethanesulfonyl) imide (manufactured by Kishida Chemical Co., Ltd.)
LFBS: lithium nonafluorobutanesulfonate (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.)
LiPF6: lithium hexafluorophosphate (manufactured by Wako Pure Chemical Industries, Ltd.)
LiSbF6: lithium hexafluoroantimonate (Wako Pure Chemical Industries, Ltd.)
LiBF4: lithium tetrafluoroborate (manufactured by Kishida Chemical Co., Ltd.)
C3: KAYARAD DPHA (Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) and pentaerythritol tetraacrylate (Toagosei Co., Ltd., trade name Aronix M-450) 1 (mass ratio) mixture E1: NCI-930 (manufactured by ADEKA Corporation)
E2 / NCI-831 (manufactured by ADEKA Corporation) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by BASF, trade name IRGACURE 369) 1 (mass ratio) mixture E3: Compound No. described in Chemical Formula 4 of JP-T-2006-527329 42
E4: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by BASF, trade name IRGACURE OXE-02 )
-F1 solution: 5 mass% propylene glycol monomethyl ether acetate solution of MegaFac F-554 (manufactured by DIC Corporation)

Dye multimer synthesis example 5
(Synthesis of dye multimer TAM1)
In a reaction vessel equipped with a cooling tube, 5.48 g of a monomer represented by the following formula (13), 1.20 g of methacrylic acid, 1.30 g of methyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Corporation) (Trade name Cyclomer M100) 1.99 g, 0.13 g of α-thioglycerol and 20 g of cyclohexanone were added, mixed and dissolved. The solution was heated to 100 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, a solution prepared by dissolving 98.0 mg of α, α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours. Continued. After the reaction solution was cooled to room temperature, 60 g of acetone was added to make a uniform solution, which was added dropwise to 1.1 L of hexane. The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain a polymer. This is designated as “polymer (5)”.
2.0 g of the polymer (5) was dissolved in 40 mL of acetone. Next, an equimolar amount of lithium tetrakis (pentafluorophenyl) borate (manufactured by Tosoh Finechem Co., Ltd.) is added to the number of moles of the structural unit derived from the monomer represented by formula (13), and 1 at room temperature. Stir for hours. Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer TAM1).

Dye multimer synthesis example 6
(Synthesis of dye multimer TAM2)
In a reaction vessel equipped with a cooling tube, 5.48 g of the monomer represented by the above formula (13), 1.20 g of methacrylic acid, 2-acryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd., trade name HOA-) MS) 0.50 g, 1.00 g of styrene, 1.00 g of N-phenylmaleimide, 0.80 g of 2-ethylhexyl methacrylate, 0.13 g of α-thioglycerol and 20 g of cyclohexanone were mixed and dissolved. The solution was heated to 100 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, a solution prepared by dissolving 98.0 mg of α, α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours. Continued. After the reaction solution was cooled to room temperature, 60 g of acetone was added to make a uniform solution, which was added dropwise to 1.1 L of hexane. The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain a polymer. This is designated as “polymer (6)”.
2.0 g of the polymer (6) was dissolved in 40 mL of acetone. Next, an equimolar amount of lithium tetrakis (pentafluorophenyl) borate (manufactured by Tosoh Finechem Co., Ltd.) is added to the number of moles of the structural unit derived from the monomer represented by formula (13), and 1 at room temperature. Stir for hours. Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer TAM2).

Dye multimer synthesis example 7
(Synthesis of dye multimer TAM3)
In a reaction vessel equipped with a condenser tube, 5.48 g of the monomer represented by the above formula (13), 2.70 g of methacrylic acid, 0.50 g of 2-ethylhexyl methacrylate, 0.80 g of phenyl methacrylate, 2-hydroxyethyl methacrylate 0.50 g and 20 g of cyclohexanone were added, mixed and dissolved. The solution was heated to 100 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, a solution prepared by dissolving 98.0 mg of α, α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours. Continued. After the reaction solution was cooled to room temperature, 60 g of acetone was added to make a uniform solution, which was added dropwise to 1.1 L of hexane. The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain a polymer. This is designated as “polymer (7-1)”.
In a reaction vessel equipped with a cooling tube, 5.0 g of the polymer (7-1), 0.07 g of tetrabutylammonium bromide, 0.02 g of 4-methoxyphenol, and 20 g of cyclohexanone were added, mixed and dissolved. This solution was heated to 110 ° C., glycidyl methacrylate was added dropwise at the same temperature over 15 minutes, and the reaction was carried out for 9 hours while maintaining this temperature. The amount of glycidyl methacrylate used here is 60 mol% with respect to the number of moles of methacrylic acid. After the reaction solution was cooled to room temperature, 60 g of acetone was added to make a uniform solution, which was added dropwise to 1.1 L of hexane. The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain a polymer. This is designated as “polymer (7-2)”.
2.0 g of the polymer (7-2) was dissolved in 40 mL of acetone. Next, an equimolar amount of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Kishida Chemical Co., Ltd.) is added with respect to the number of moles of the structural unit derived from the monomer represented by formula (13), and the room temperature is 1 hour. Stir. Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer TAM3).

Dye multimer synthesis example 8
(Synthesis of dye multimer TAM4)
In Dye Multimer Synthesis Example 5, dye multimer synthesis except that 5.48 g of p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt was used instead of 5.48 g of the monomer represented by formula (13). Reaction was carried out in the same manner as in Example 5 to obtain a polymer. This is designated as “polymer (8)”.
2.0 g of the polymer (8) was dissolved in 40 mL of acetone. Next, an equimolar amount of the monomer represented by the formula (13) was added to the number of moles of the structural unit derived from p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, and the mixture was stirred at room temperature for 1 hour. . Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer TAM4).

Dye multimer synthesis example 9
(Synthesis of dye multimer TAM5)
In Dye Multimer Synthesis Example 6, dye multimer synthesis except that 5.48 g of p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt was used instead of 5.48 g of the monomer represented by formula (13). Reaction was carried out in the same manner as in Example 6 to obtain a polymer. This is designated as “polymer (9)”.
2.0 g of the polymer (9) was dissolved in 40 mL of acetone. Next, an equimolar amount of the monomer represented by the formula (13) was added to the number of moles of the structural unit derived from p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, and the mixture was stirred at room temperature for 1 hour. . Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer TAM5).

Dye multimer synthesis example 10
(Synthesis of dye multimer TAM6)
In Dye Multimer Synthesis Example 7, dye multimer synthesis except that 5.48 g of p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt was used instead of 5.48 g of the monomer represented by formula (13). Reaction was carried out in the same manner as in Example 7 to obtain a polymer. This is designated as “polymer (10-1)”. Subsequently, the polymer was obtained in the same manner as in Dye Multimer Synthesis Example 7 except that the polymer (10-1) was used instead of the polymer (7-1). This is designated as “polymer (10-2)”.
2.0 g of the polymer (10-2) was dissolved in 40 mL of acetone. Next, an equimolar amount of the monomer represented by the formula (13) was added to the number of moles of the structural unit derived from p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, and the mixture was stirred at room temperature for 1 hour. . Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer TAM6).

Dye Multimer Synthesis Example 11
(Synthesis of Dye Multimer Xa1)
In Dye Multimer Synthesis Example 5, a dye multimer synthesis example except that 5.48 g of the monomer represented by the following formula (14) was used instead of 5.48 g of the monomer represented by the formula (13). Reaction was carried out in the same manner as in Example 5 to obtain a polymer. This is designated as “polymer (11)”.
2.0 g of the polymer (11) was dissolved in 40 mL of acetone. Next, an equimolar amount of lithium tetrakis (pentafluorophenyl) borate (manufactured by Tosoh Finechem Co., Ltd.) is added to the number of moles of the structural unit derived from the monomer represented by formula (14), and 1 at room temperature. Stir for hours. Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried at 50 ° C. under reduced pressure to obtain the target compound (pigment multimer Xa1).

Dye Multimer Synthesis Example 12
(Synthesis of Dye Multimer Xa2)
In Dye Multimer Synthesis Example 6, a dye multimer synthesis example except that 5.48 g of the monomer represented by the formula (14) was used instead of 5.48 g of the monomer represented by the formula (13). Reaction was carried out in the same manner as in Example 6 to obtain a polymer. This is designated as “polymer (12)”.
2.0 g of the polymer (12) was dissolved in 40 mL of acetone. Next, an equimolar amount of lithium tetrakis (pentafluorophenyl) borate (manufactured by Tosoh Finechem Co., Ltd.) is added to the number of moles of the structural unit derived from the monomer represented by formula (14), and 1 at room temperature. Stir for hours. Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer Xa2).

Dye Multimer Synthesis Example 13
(Synthesis of Dye Multimer Xa3)
In Dye Multimer Synthesis Example 7, a dye multimer synthesis example except that 5.48 g of the monomer represented by the formula (14) was used instead of 5.48 g of the monomer represented by the formula (13). Reaction was carried out in the same manner as in Example 7 to obtain a polymer. This is designated as “polymer (13-1)”. Subsequently, a polymer was obtained in the same manner as in Dye Multimer Synthesis Example 7 except that the polymer (13-1) was used instead of the polymer (7-1). This is designated as “polymer (13-2)”.
2.0 g of the polymer (13-2) was dissolved in 40 mL of acetone. Next, an equimolar amount of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Kishida Chemical Co., Ltd.) is added with respect to the number of moles of the structural unit derived from the monomer represented by the formula (14), and 1 hour at room temperature Stir. Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer Xa3).

Dye multimer synthesis example 14
(Synthesis of Dye Multimer Xa4)
2.0 g of the polymer (8) obtained in Dye Multimer Synthesis Example 8 was dissolved in 40 mL of acetone. Next, an equimolar amount of the monomer represented by the formula (14) was added to the number of moles of the structural unit derived from p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, and the mixture was stirred at room temperature for 1 hour. . Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer Xa4).

Dye multimer synthesis example 15
(Synthesis of Dye Multimer Xa5)
2.0 g of the polymer (9) obtained in Dye Multimer Synthesis Example 9 was dissolved in 40 mL of acetone. Next, an equimolar amount of the monomer represented by the formula (14) was added to the number of moles of the structural unit derived from p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, and the mixture was stirred at room temperature for 1 hour. . Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer Xa5).

Dye Multimer Synthesis Example 16
(Synthesis of Dye Multimer Xa6)
2.0 g of the polymer (10-2) obtained in Dye Multimer Synthesis Example 10 was dissolved in 40 mL of acetone. Next, an equimolar amount of the monomer represented by the following formula (15) is added to the number of moles of the structural unit derived from p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, and the mixture is stirred at room temperature for 1 hour. did. Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer Xa6).

Dye Multimer Synthesis Example 17
(Synthesis of dye multimer Cy)
In Dye Multimer Synthesis Example 5, a dye multimer synthesis example except that 5.48 g of the monomer represented by the following formula (11) was used instead of 5.48 g of the monomer represented by the formula (13). Reaction was carried out in the same manner as in Example 5 to obtain a polymer. This is designated as “polymer (17)”.
2.0 g of the polymer (17) was dissolved in 40 mL of acetone. Next, an equimolar amount of lithium tetrakis (pentafluorophenyl) borate (manufactured by Tosoh Finechem Co., Ltd.) is added to the number of moles of the structural unit derived from the monomer represented by formula (11), and 1 at room temperature. Stir for hours. Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (dye multimer Cy).

Dye Multimer Synthesis Example 18
(Synthesis of Dye Multimer DPM)
In Dye Multimer Synthesis Example 5, Dye Multimer Synthesis Example except that 5.48 g of the monomer represented by the following formula (16) was used instead of 5.48 g of the monomer represented by the formula (13). Reaction was carried out in the same manner as in Example 5 to obtain a polymer. This is designated as “polymer (18)”.
2.0 g of the polymer (18) was dissolved in 40 mL of acetone. Next, an equimolar amount of lithium tetrakis (pentafluorophenyl) borate (manufactured by Tosoh Finechem Co., Ltd.) is added to the number of moles of the structural unit derived from the monomer represented by formula (16), and 1 at room temperature. Stir for hours. Thereafter, the reaction solution was concentrated under reduced pressure, 200 mL of ion-exchanged water was added to the resulting residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target compound (pigment multimer DPM).

  Here, the monomer represented by the formula (11) is described as “Compound No. 14” in Chemical Formula 4 of Japanese Patent No. 5955584, and the monomer represented by the formula (13) It is described as “Compound I-2” in Chemical Formula 54 of Japanese Patent No. 2015-092217, and the monomer represented by the formula (16) is described as “Exemplary Compound A-1” in Chemical Formula 41 of Patent 5722267. Have been described. Moreover, the monomer represented by Formula (14) is compoundable according to the synthesis example 1 of patent 5482878.

Example 101
The red coloring composition (RED-2) was applied on a glass substrate using a spin coater and then pre-baked for 10 minutes on a hot plate at 80 ° C. to form a coating film having a thickness of 2.5 μm. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp is used to expose each coating film with radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 1,000 J / m ² through a photomask. did. Thereafter, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged for 90 seconds at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 220 ° C. for 30 minutes to form a red cured film. This red cured film is the colored cured film of the present invention.
Next, the green coloring composition (GREEN-1) was applied on the glass substrate on which the red cured film was formed using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a film. A coating film having a thickness of 2.5 μm was formed. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp is used to expose each coating film with radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 1,000 J / m ² through a photomask. did. Thereafter, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged for 90 seconds at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 220 ° C. for 30 minutes to form a green cured film.
Subsequently, the blue coloring composition (BLUE-101) was applied on the glass substrate on which the red cured film and the green cured film were formed using a spin coater, and then pre-baked for 10 minutes on an 80 ° C. hot plate. And a coating film having a thickness of 2.5 μm was formed. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp is used to expose each coating film with radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 1,000 J / m ² through a photomask. did. Thereafter, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged for 90 seconds at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Thereafter, the substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 220 ° C. for 30 minutes to form a blue cured film. In this way, a color filter (CF-101) in which colored cured films of red, green and blue were formed was produced.
It was confirmed that the color filter (CF-101) was excellent in contrast and chromaticity characteristics.

Examples 102-157
In Example 101, a color filter (CF−) was prepared in the same manner as in Example 101 except that the blue colored compositions (BLUE-102) to (BLUE-157) were used instead of the blue colored composition (BLUE-101). 102) to (CF-157) were produced. It was confirmed that all of the color filters (CF-102) to (CF-157) were excellent in contrast and chromaticity characteristics.

Claims (13)

A coloring composition containing (A) a colorant, (B) a resin and (C) a polymerizable compound,
(B) the resin includes (b1) a resin having a structure that generates a cyclic ether group by heating;
(A) The coloring composition whose content rate of a coloring agent is 1 mass% or more in the solid content of the said coloring composition. A coloring composition containing (A) a colorant, (B) a resin and (C) a polymerizable compound,
(C) The coloring composition in which a polymeric compound contains the compound which has a structure which produces | generates a cyclic ether group by (c1) heating. A coloring composition containing (A) a colorant and (C) a polymerizable compound,
(A) A colored composition containing a compound in which the colorant has (a1) a structure that generates a cyclic ether group by heating and a dye structure.   The coloring composition of Claim 1 or 3 which has a structure which produces | generates a cyclic ether group by heating as a repeating unit. The structure that generates a cyclic ether group by heating is at least one selected from an ethylene carbonate structure represented by the following formula (1) and a cyclohexyl ethylene carbonate structure represented by the following formula (2). The coloring composition of any one of Claims 1-4.

[In the formulas (1) and (2),
R ¹ independently of ^{one another} represents a halogen atom, a hydroxyl group, a nitro group, an amino group, a cyano group or a hydrocarbon group;
m represents 0 or 1,
n represents an integer of 0 to 3,
X represents, independently of each other, a single bond or a divalent hydrocarbon group,
* Indicates a bond. ]   The colorant (A) contains at least one selected from the group consisting of (a2) a salt of a cationic chromophore and a counter anion, a salt of an anionic chromophore and a counter cation, and a pigment. 6. The coloring composition according to any one of 5 above.   The coloring composition according to claim 3, wherein the dye structure is a cationic chromophore, and the cationic chromophore is a salt with a counter anion.   (B1) The colored composition according to claim 1, wherein the resin having a structure that generates a cyclic ether group by heating further has at least one selected from the group consisting of a substituted amino group and a quaternary ammonium base.   The colored cured film formed using the coloring composition of any one of Claims 1-8.   The manufacturing method of a colored cured film which forms the coating film of the coloring composition of any one of Claims 1-8 on a board | substrate, exposes and develops this coating film, and carries out post-baking.   A color filter comprising the colored cured film according to claim 9.   A display device comprising the colored cured film according to claim 9.   A light receiving element comprising the colored cured film according to claim 9.