JP6299329B2 - Colored composition, colored cured film, and display element - Google Patents

Description

  The present invention relates to a colored composition, a colored cured film, and a display element, and more specifically, a colored cured film 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 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. For example, Patent Document 5 proposes the use of a specific xanthene dye.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2010-254964 A

However, when the dye proposed in Patent Document 5 is used, there is a problem that the contrast of the pixel is lowered. On the other hand, when a dye is used, there are many problems that the voltage holding ratio and heat resistance of the color filter deteriorate. Therefore, there is a strong demand for the development of a coloring composition suitable for producing a color filter that can achieve both good voltage holding ratio, high contrast, and high heat resistance.
Accordingly, an object of the present invention is to provide a colored composition capable of forming a colored cured film capable of achieving both good voltage holding ratio, high contrast and high heat resistance when a dye is used as a colorant. And providing a compound applicable as a coloring agent of the coloring composition. Moreover, the subject of this invention is providing the display element which comprises the color filter provided with the colored cured film formed from the said coloring composition, and the said color filter.

  In view of such circumstances, the present inventors have conducted extensive research and found that the above-described problems can be solved by using a dye having a specific structure as a colorant, and the present invention has been completed. .

  That is, the present invention provides (A) a colorant comprising a compound having a structure represented by the following formula (1) (hereinafter also referred to as “the present colorant”), (B) a binder resin, and (C) a polymerizability. The present invention provides a coloring composition containing a compound.

[In Formula (1),
m represents an integer of 0 to 5, and when m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
R ^{1 to} R ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted heterocyclic group. However, the hydrocarbon group may have a linking group selected from —CO—, —COO—, and —CONH— between C—C bonds.
R ⁵ independently represents a monovalent group.
However, one or more of R ^{1 to} R ⁴ are groups selected from the following requirements (i) to (v).
(I) A substituted or unsubstituted unsaturated aliphatic hydrocarbon group, or a substituted or unsubstituted unsaturated alicyclic hydrocarbon group. However, the unsaturated aliphatic hydrocarbon group may have a linking group selected from —CO—, —COO— and —CONH— between C—C bonds.
(Ii) An alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group It is a group.
(Iii) A substituted or unsubstituted heterocyclic group, or a hydrocarbon group substituted with a heterocyclic group.
(Iv) a hydrocarbon group substituted with at least one selected from the group consisting of —CN, —NO ₂ , —NH ₂ , —SH and —CONH ₂ (hereinafter also referred to as “substituent group α”); is there.
(V) A substituted or unsubstituted aliphatic hydrocarbon group having 11 or more carbon atoms. ]

  Moreover, this invention provides the display element which comprises the colored cured film formed using the said coloring composition, and this colored cured film. Here, the “colored cured film” means each color pixel, black matrix, black spacer, and the like used for a display element and a solid-state imaging element.

  Furthermore, this invention provides the compound which has a structure represented by the said Formula (1).

If the colored composition of the present invention is used, a colored cured film having excellent voltage holding ratio, contrast, and heat resistance can be formed.
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.
Coloring composition will be described in detail components of the colored composition of the present invention.

-(A) Colorant-
The coloring composition of this invention contains this coloring agent as (A) coloring agent.

Examples of the hydrocarbon group in R ^{1 to} R ⁴ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. These hydrocarbon groups may have a linking group selected from —CO—, —COO— and —CONH— between the C—C bonds.

  The aliphatic hydrocarbon group may be saturated or unsaturated, and specific examples include an alkyl group, an alkenyl group, and an alkynyl group. 1-30 are preferable, as for carbon number of these aliphatic hydrocarbon groups, 1-24 are more preferable, and 1-20 are especially preferable. These aliphatic hydrocarbon groups may be linear or branched. Specifically, as the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl Group, decyl group, undecyl group, 1-methyldecyl group, dodecyl group, 1-methylundecyl group, 1-ethyldecyl group, tridecyl group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyloctyl group, hexadecyl group , Octadecyl group, heneicosan-1-yl group, docosan-1-yl group, tricosan-1-yl group, tetracosan-1-yl group and the like. Examples of the alkenyl group include ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1,3-butadienyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl. Group, 2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group and the like. Examples of the alkynyl group include 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. Examples of the group having a linking group selected from —CO—, —COO— and —CONH— between the C—C bonds of the aliphatic hydrocarbon group include, for example, a (meth) acrylethyl group, a (meth) acrylpropyl group. Group, (meth) acrylamidoethyl group, (meth) acrylamidopropyl group and the like.

As an alicyclic hydrocarbon group, a C3-C30 alicyclic hydrocarbon group is preferable. The alicyclic hydrocarbon group may be saturated or unsaturated, and specifically includes a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, a cyclic terpene carbonization. A hydrogen group etc. can be mentioned. More specifically, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a cycloalkenyl group such as a 1-cyclohexenyl group; Condensed polycyclic hydrocarbon groups such as cyclodecanyl group, decahydro-2-naphthyl group, adamantyl group; tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, pentacyclopentadecanyl group, Bridged ring hydrocarbon groups such as isobonyl group, dicyclopentenyl group, tricyclopentenyl group; monovalent group obtained by removing one hydrogen atom from spiro [3,4] heptane, spiro [3,4] octane, etc. Spiro hydrocarbon groups; cyclic terpene hydrocarbon groups such as monovalent groups obtained by removing one hydrogen atom from p-menthane, tujang, caran, etc. Can. The cycloalkyl group and cycloalkenyl group preferably have 3 to 12 carbon atoms.

  As an aromatic hydrocarbon group, a C6-C20 thing is preferable and a C6-C10 thing is more preferable. Specific examples of the aromatic hydrocarbon group include an aryl group. Here, the “aryl group” in this specification refers to a monocyclic to tricyclic aromatic hydrocarbon group, and specifically includes a phenyl group, a benzyl group, an o-tolyl group, an m-tolyl group, p. -Tolyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group, azulenyl group, 9-fluorenyl group and the like can be mentioned.

The heterocyclic group in R ^{1 to} R ⁴ is not particularly limited as long as it is a monovalent heterocyclic ring, but is preferably a 3-membered to 10-membered monocyclic or condensed bicyclic heterocyclic group, specifically Is an alicyclic group such as oxiranyl group, oxetanyl group, pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, morpholinyl group, theomorpholinyl group, piperidyl group, piperidino group, piperazinyl group, homopyrerazinyl group, 1,3-dioxolan-2-yl group Heterocyclic group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, quinolyl group, isoquinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, imidazolyl group, pyrazolyl group, triazoyl group, tetrazolyl group, thiazolyl group, benzothiazolyl group, oxazolyl group Group, indolyl group, indazolyl group, Nzoimidazoriru group, phthalimide group, a thienyl group, a furyl group, pyranyl group, and aromatic heterocyclic groups such as a purinyl group.

Of these, hydrocarbon groups are preferred as R ^{1 to} R ⁴ . The hydrocarbon group is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ^{1 to} R ⁴ are all aromatic hydrocarbon groups, and R ¹ and R ⁴ are aromatic hydrocarbon groups. Further, an embodiment in which R ² and R ³ are aliphatic hydrocarbon groups is more preferable.

R ⁵ is not particularly limited as long as it is a monovalent group, but is preferably a monovalent group containing a hetero atom, such as —CO ₂ ⁻ , —CO ₂ H, —CO ₂ M, —CO ₂ R ⁶ , — SO ₃ ⁻ , —SO ₃ H, —SO ₃ M, —SO ₃ R ⁷ , —SO ₂ NHR ⁸ , —SO ₂ NR ⁹ R ¹⁰ , —SO ₂ —O—N═CR ¹¹ R ¹² , —SO ₂ NHNHR ^13, -SO ₂ SR ^14, can be mentioned -SO ₂ NHSO ₂ R ^15. Here, R ^{6 to} R ¹¹ and R ^{13 to} R ¹⁵ each independently represent a substituted or unsubstituted hydrocarbon group, and R ¹² represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. , M represents a sodium atom or a potassium atom.

As the hydrocarbon group in R ^{6 to} R ¹¹ and R ^{13 to} R ¹⁴ , an aliphatic hydrocarbon group and an aromatic hydrocarbon group are preferable, and an alkyl group having 1 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms are preferable. More preferred. 1-24 are preferable and, as for carbon number of this alkyl group, 1-18 are more preferable. 6-20 are preferable and, as for carbon number of this aryl group, 6-10 are more preferable.
R ¹² is preferably an aliphatic hydrocarbon group, more preferably an alkyl group having 1 to 24 carbon atoms, and still more preferably an alkyl group having 1 to 12 carbon atoms.
R ¹⁵ is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms.
Specific examples of these hydrocarbon groups are the same as those described above.

The hydrocarbon group in R ^{1 to} R ⁴ and R ^{6 to} R ¹⁵ and the heterocyclic group in R ^{1 to} R ⁴ may further have a substituent without departing from the gist of the present invention. The position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different. Examples of such substituents include halogen atoms, hydroxyl groups, cyano groups, formyl groups, carboxy groups, nitro groups, amino groups, mercapto groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-substituted amino groups, Amide group, alkylcarbonyl group, alkyloxycarbonyl group, alkylsulfonyl group, alkylsulfamoyl group, trialkylsilyl group, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, etc. Can be mentioned. These substituents may further have a substituent.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group include C _1-12 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, a dodecyloxy group, and a t-dodecyloxy group. be able to. Examples of the aryloxy group include a phenoxy group and a benzyloxy group.

Examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, pentylthio group, isopentylthio group, neopentylthio group, cyclopentylthio group, hexylthio group, cyclohexylthio group, heptylthio group. Group, cycloheptylthio group, octylthio group, 2-ethylhexylthio group, cyclooctylthio group, nonylthio group, decanylthio group, tricyclodecanylthio group, methoxypropylthio group, ethoxypropylthio group, hexyloxypropylthio group, 2-ethylhexyloxy propyl thio group, a methoxy hexyl thio group, undecylthio group, a dodecylthio group, tetradecyl thio group, t-dodecylthio group, a hexadecylthio group, C _1-20 alkylthio and octadecyl thio group It can be mentioned. Examples of the arylthio group include a phenylthio group.

Examples of the substituent in the N-substituted amino group include a C _1-6 alkyl group, a C _6-10 aryl group, and the like, and specific examples thereof are the same as those described above.

Examples of the alkylcarbonyl group include C _1-6 alkylcarbonyl groups such as a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group.

Examples of the alkyloxycarbonyl group include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, a butyloxycarbonyl group, a hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a dodecylcarbonyl group, Examples thereof include C _1-20 alkyloxycarbonyl groups such as octadecylcarbonyl group.

As the alkylsulfonyl group, for example, methylsulfonyl group, ethylsulfonyl group, hexylsulfonyl group, decanylsulfonyl group, undecylsulfonyl group, dodecylsulfonyl group, tetradecylsulfonyl group, t-dodecylsulfonyl group, hexadecylsulfonyl group, Examples thereof include C _1-20 alkylsulfonyl groups such as octadecylsulfonyl group.

Examples of the alkylsulfamoyl group include methylsulfamoyl group, ethylsulfamoyl group, dimethylsulfamoyl group, propylsulfamoyl group, isopropylsulfamoyl group, butylsulfamoyl group, hexylsulfamoyl group, Examples thereof include C _1-20 alkylsulfamoyl groups such as octylsulfamoyl group, 2-ethylhexylsulfamoyl group, undecylsulfamoyl group, dodecylsulfamoyl group, and 1-heptyloctylsulfamoyl group.

Examples of the trialkylsilyl group include a tri-C _1-6 alkylsilyl group such as a trimethylsilyl group.
Specific examples of the aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the heterocyclic group include those described above.

  Although m is an integer of 0-5, 0-3 are preferable and 1 or 2 is more preferable.

One or more of R ^{1 to} R ⁴ in the formula (1) are required to be groups selected from the following requirements (i) to (v).
(I) A substituted or unsubstituted unsaturated aliphatic hydrocarbon group, or a substituted or unsubstituted unsaturated alicyclic hydrocarbon group. However, the unsaturated aliphatic hydrocarbon group may have a linking group selected from —CO—, —COO— and —CONH— between C—C bonds.
(Ii) An alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group It is a group.
(Iii) A substituted or unsubstituted heterocyclic group, or a hydrocarbon group substituted with a heterocyclic group.
(Iv) A hydrocarbon group substituted with at least one selected from the substituent group α.
(V) A substituted or unsubstituted aliphatic hydrocarbon group having 11 or more carbon atoms.

Examples of the unsaturated aliphatic hydrocarbon group in the requirements (i) and (ii) include the same as those described above, and among them, an alkenyl group is preferable. The carbon number is preferably 2-20, more preferably 2-10, and particularly preferably 2-6.
Examples of the unsaturated alicyclic hydrocarbon group in the requirements (i) and (ii) include the same as those described above, and among them, a cycloalkenyl group is preferable. The carbon number is preferably 4 to 8, and more preferably 5 or 6.
Examples of the heterocyclic group in the requirement (iii) include the same ones as described above, but an alicyclic heterocyclic group is preferable. Further, the hydrocarbon group in the requirement (iv) is preferably a saturated hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group. 1-20 are preferable, as for carbon number of a saturated aliphatic hydrocarbon group, 1-10 are more preferable, and 2-6 are especially preferable.
As the substituent group α in the requirement (iv), —CN and —NO ₂ are more preferable. In addition, the hydrocarbon group in the requirement (iv) is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. 1-20 are preferable, as for carbon number of the said aliphatic hydrocarbon group, 1-10 are more preferable, and 2-6 are especially preferable.
The aliphatic hydrocarbon group having 11 or more carbon atoms in the requirement (v) may be saturated or unsaturated. Specific examples thereof include saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups having 11 or more carbon atoms among those described above. 11-20 are preferable and, as for carbon number of the said aliphatic hydrocarbon group, 11-16 are more preferable. As the substituent in the requirement (v), a halogen atom, hydroxyl group, cyano group, formyl group, carboxy group, nitro group, amino group, mercapto group, alkoxy group, aryloxy group, alkylthio group, arylthio group, N-substituted amino group An alkylcarbonyl group, an alkyloxycarbonyl group, an alkylsulfonyl group, an alkylsulfamoyl group, a trialkylsilyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, and the like. Specific examples of these substituents are the same as those described above.

Among the above requirements (i) to (v), at least one of R ^{1 to} R ⁴ is an aromatic carbon atom substituted with a substituted or unsubstituted unsaturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. A hydrogen group, a hydrocarbon group substituted with a heterocyclic group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group substituted with at least one selected from the substituent group α, a substituted or unsubstituted group having 11 or more carbon atoms It is preferably an aliphatic hydrocarbon group, and is at least one selected from a substituted or unsubstituted unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, and a substituent group α. An aliphatic hydrocarbon group or an aromatic hydrocarbon group substituted with a seed is preferred.

Examples of the structure represented by the formula (1) include the following structures. Among these, structural formulas (a1), (a10), (a16), (a17), (a19), (a20), (a22), and (a39) to (a45) are preferable. R ^a represents a 2-ethylhexyl group.

  When the structure represented by Formula (1) is cationic, it has an anion so that the compound which has a structure represented by Formula (1) may become electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, and a methide anion. More specifically, for example, the anions described in JP-T-2007-503477 can be mentioned.

  When the structure represented by the formula (1) is anionic, it has a cation so that the compound having the structure represented by the formula (1) is electrically neutral. Examples of the cation include a metal cation and an onium cation. Examples of the metal cation include a monovalent metal cation such as lithium ion, sodium ion and potassium ion, and a divalent metal cation such as magnesium ion and calcium ion. Examples of the onium cation include an ammonium cation and a phosphonium cation. Examples of the ammonium cation include tetramethylammonium, tetraethylammonium, monostearyltrimethylammonium, distearyldimethylammonium, tristearylmonomethylammonium, cetyltrimethylammonium, trioctylmethylammonium, dioctyldimethylammonium, monolauryltrimethylammonium, and dilauryl. Dimethylammonium, trilaurylmethylammonium, triamylbenzylammonium, trihexylbenzylammonium, trioctylbenzylammonium, trilaurylbenzylammonium, benzyldimethylstearylammonium, benzyldimethyloctylammonium, dialkyl (alkyl is C14 to C18) dimethylammonium And the like can be given. Examples of the phosphonium cation include tetraalkylphosphonium such as methyltrioctylphosphonium, octyltributylphosphonium, dodecyltributylphosphonium, hexadecyltributylphosphonium, dihexyldioctylphosphonium, aryltrialkylphosphonium such as benzyltributylphosphonium, and dibutyldiphenylphosphonium. Examples thereof include alkyltriphenylphosphonium such as dialkyldiarylphosphonium and butyltriphenylphosphonium, and tetraarylphosphonium such as benzyltriphenylphosphonium.

The colorant can be produced by an appropriate method, and examples thereof include the same method as in Example 3 of JP2010-254964A and Example 3 of JP2013-011869A. it can. The colorant thus obtained is soluble in various organic solvents including ketones such as cyclohexanone and has excellent heat resistance.
In this invention, this coloring agent can be used individually or in mixture of 2 or more types.

  The coloring composition of this invention can contain another coloring agent further as a coloring agent with this coloring agent. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application.

  As the other colorant, any of pigments, dyes other than the present colorant, and natural pigments can be used, but organic pigments and organic dyes are preferred in terms of obtaining pixels with high luminance and color purity. In particular, organic pigments are preferred.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) numbers. Can be mentioned.

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. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. 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. Pigment orange 38;
C. I. Pigment Violet 23.
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.

  Moreover, as said dye, a triarylmethane dye, an anthraquinone dye, an azo dye, etc. are preferable. More specifically, it is described in International Publication No. 10/123071, pamphlet, JP-A 2011-116803, JP-A 2011-117995, JP-A 2011-133844, JP-A 2011-174987, and the like. Mention may be made of organic dyes.

  The colored composition of the present invention is preferably used for forming a blue pixel. In this case, the (A) colorant preferably contains at least one selected from the group consisting of a blue pigment, a blue dye, a violet pigment and a violet dye as another colorant together with the present colorant. In this case, the content ratio of the present colorant is preferably 0.1 to 80% by mass, more preferably 1 to 80% by mass, still more preferably 5 to 60% by mass, particularly 10 to 40% in all colorants. Mass% is preferred.

  In the present invention, other pigments to be arbitrarily mixed can be used after being purified 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 Application Laid-Open No. 08-179111 can be employed.

  Moreover, in this invention, a well-known dispersing agent and a dispersing aid can also be contained with the other coloring agent mixed arbitrarily. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Dispersants, polyester dispersants, acrylic dispersants and the like can be mentioned, and examples of the dispersion aid include pigment derivatives.

  Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK)) Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemie (BYK)), Solsperse 76500 (Lubrisol) As a polyethylenimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc. As a polyester-based dispersant, Azisper PB8 1, AJISPER PB822, Ajisper PB880, Ajisper PB881 (or, Ajinomoto Fine-Techno Co., Ltd.) and the like, can be exemplified respectively.

  Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, sulfonic acid derivatives of quinophthalone, and the like.

  In the present invention, other colorants can be used alone or in admixture of two or more.

  When other colorants are contained, the content ratio of the other colorants is preferably 99.9% by mass or less, more preferably 99% by mass or less, and further 95% by mass or less, based on the total content of the colorants. Especially 90 mass% or less is preferable. The lower limit is not particularly limited and may be 0.01% by mass or more.

  (A) The content ratio of the colorant is usually 5 in the solid content of the colored composition from the viewpoint of forming a pixel having high heat resistance and high brightness and excellent color purity, or a black matrix and black spacer excellent in light shielding properties. -70 mass%, Preferably it is 5-60 mass%, More preferably, it is 10-40 mass%. Here, solid content is components other than the solvent mentioned later.

-(B) Binder resin-
Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (b2)”). .

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (polymerization degree 2 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, 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 Kaikai 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.

  The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably Is 3,000 to 50,000. By setting it as such an aspect, the remaining-film rate of a film, a pattern shape, heat resistance, an electrical property, and the resolution can be improved further, and generation | occurrence | production of the dry foreign material at the time of application | coating can be suppressed at a high level.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here says the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, binder resin can be used individually or in mixture of 2 or more types.

  In this invention, content of binder 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, More preferably, it is 50-150 mass parts. . By setting it as such an aspect, alkali developability, the storage stability of a coloring composition, and chromaticity characteristic can be improved further.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product react 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 diester. A methacrylate etc. can be mentioned. 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 alkylene oxide-modified polyfunctional (meth) acrylate is 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. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol 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 taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, among polyfunctional (meth) acrylates having a carboxyl group, obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

  In the present invention, the content of the polymerizable compound (C) is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, and 30 to 500 parts by mass with respect to 100 parts by mass of the colorant (A). Is more preferable, and 50 to 150 parts by mass is particularly preferable. By setting it as such an aspect, sclerosis | hardenability and alkali developability can be improved further and generation | occurrence | production of a ground stain, a film | membrane residue, etc. on the board | substrate of a non-exposed part or a light shielding layer can be suppressed at a high level.

-Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

  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.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, 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 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.

  Specific examples of the biimidazole compound include 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, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  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, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -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 commercial products of O-acyloxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, manufactured by Daito Chemix Corporation), etc. may be used. it can.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type 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 invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polymeric compounds, and, as for content of a photoinitiator, 1-100 mass parts is still more preferable, 10-60 mass parts preferable. By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be improved further.

-Solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components that are optionally added, but is usually prepared as a liquid composition by blending a solvent.
As said solvent, (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, but suitably has volatility. You can choose to use.

Among such 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, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as 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;
Other 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;
Alkoxycarboxylic esters 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 Other 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.

  Of these solvents, (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, and other ethers from the viewpoints of solubility, pigment dispersibility, coatability, etc. , Ketones, diacetates, alkoxycarboxylic acid esters, and other esters are preferred, especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-hept Non, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3- Methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethyl pyruvate and the like are preferable.

  In this invention, a solvent can be used individually or in mixture of 2 or more types. When used in combination, mix at least (poly) alkylene glycol monoalkyl ethers and (poly) alkylene glycol monoalkyl ether acetates, (poly) alkylene glycol monoalkyl ether acetates and alkoxycarboxylic acid esters. Are preferably used.

  Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the coloring composition becomes 5-50 mass% is preferable, and the quantity used as 10-40 mass% More preferred. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive 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 fluorine-based surfactants and silicon-based surfactants; Methoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxy Silane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy) -5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5.5] undecane, thiodiethylenebis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate] and the like; anti-aggregation agents such as sodium polyacrylate; 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- Residue improvers such as amino-1,3-propanediol and 4-amino-1,2-butanediol; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acrylic Examples include developability improvers such as leuoxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate. In the present invention, it is not always necessary to contain an ultraviolet absorber such as benzotriazole, benzophenone, benzoate, or cyanoacrylate.

  The coloring composition of the present invention can be prepared by an appropriate method, and examples of the preparation method include methods disclosed in JP 2008-58642 A, JP 2010-132874 A, and the like. be able to. When both a dye and a pigment are used as the colorant, as disclosed in JP 2010-132874 A, after passing the dye solution through the first filter, the dye solution that has passed through the first filter is used. Alternatively, it is possible to employ a method of preparing by mixing with a separately prepared pigment dispersion and passing the obtained colored composition through a second filter. In addition, the dye, the above components (B) to (C), and other components to be used as necessary are dissolved in a solvent, and the obtained solution is passed through the first filter, and then the first filter is used. You may employ | adopt the method prepared by mixing the solution which passed through with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 2nd filter. Also, after passing the dye solution through the first filter, the dye solution that has passed through the first filter, the above components (B) to (C), and other components used as necessary are mixed and dissolved. The obtained solution is passed through a second filter, and the solution that has passed through the second filter is further mixed with a separately prepared pigment dispersion, and the resulting colored composition is passed through a third filter. The method of doing can also be employ | adopted.

Colored cured film and production method thereof The colored cured film of the present invention is formed using the colored composition of the present invention, specifically, each color pixel, black matrix, black spacer, etc. used in the color filter. Means.

Hereinafter, a colored cured film used for a color filter and a method for forming the same will be described.
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, after applying a red liquid composition of the radiation-sensitive colored composition of the present invention on the substrate, pre-baking is performed to evaporate the solvent, thereby forming 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 red pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or blue, 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 blue 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. It can also be formed in the same manner as in the case of forming the above-mentioned pixel using a sexually colored composition.

Examples of the substrate used when forming the color filter 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 radiation-sensitive coloring composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally 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, 1,8-diazabicyclo- [5.4.0] -7-. An aqueous solution of undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene or the like 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 blue liquid composition of the thermosetting coloring composition of the present invention is ejected 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 colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored 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 including the colored cured film of the present invention thus formed has extremely high luminance and coloring power, it can be used in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic papers, and the like. Very useful. In addition, the display element mentioned later should just have at least 1 or more of the colored cured film formed using the coloring composition of this invention.

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. In addition, 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 IZO (acid value indium and zinc oxide) It is also possible to adopt a structure in which the substrate on which the electrode is formed is opposed to 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.

  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.

<Synthesis of this coloring agent>
Synthesis example 1
20 parts by mass of a compound represented by the following formula (1) and 200 parts by mass of N-dodecylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under shading conditions, and the resulting solution was stirred at 110 ° C. for 6 hours. The obtained reaction solution was cooled to room temperature, added to a mixed solution of 800 parts by mass of water and 50 parts by mass of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were subjected to suction filtration, and the obtained residue was dried to obtain 24 parts by mass of the compound represented by the formula (A-1). From the MS spectrum, it was confirmed that the obtained red solid was a compound represented by the following formula (A-1). Let the obtained compound be a coloring agent (A-1).

Comparative Synthesis Example 1
According to the description of Synthesis Example 1 of JP 2010-254964 A, a mixture of compounds represented by the following formulas (a-1-1) to (a-1-5) was synthesized. Let the mixture of the obtained compounds be a coloring agent (a-1).

Comparative Synthesis Example 2
A compound represented by the following formula (a-2) was synthesized according to the description in Synthesis Example 2 of JP2012-181505A. Let the obtained compound be a coloring agent (a-2).

<Preparation and evaluation of dye solution>
Preparation Example 1
5 parts by mass of the colorant (A-1) and 95 parts by mass of cyclohexanone as a solvent were mixed to prepare a dye solution (A-1).

Preparation Examples 2-7
In Preparation Example 1, a dye solution (A) was prepared in the same manner as Preparation Example 1 except that the colorants represented by the following formulas (A-2) to (A-14) were used instead of the colorant (A-1). A-2) to (A-14) were prepared.

Preparation Examples 15-16
A dye solution (a-1) was prepared in the same manner as in Preparation Example 1 except that Colorant (a-1) to Colorant (a-2) were used instead of Colorant (A-1) in Preparation Example 1. -A dye solution (a-2) was prepared.

<Preparation of pigment dispersion>
Preparation Example 17
As a coloring agent, C.I. I. 15 parts by weight of CI Pigment Blue 15: 6, 12.5 parts by weight of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration 40% by weight), and 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent Was used to prepare a pigment dispersion (a-3).

<(B) Synthesis of binder resin>
Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had Mw of 12,200 and Mn of 6,500. This binder resin is referred to as “binder resin (B1)”.

<Preparation and evaluation of coloring composition>
Example 1
46.0 parts by mass of the pigment dispersion (a-3), 24.3 parts by mass of the dye solution (A-1), 24.6 parts by mass of the binder resin (B1) solution as the binder resin, and manufactured by Toagosei Co., Ltd. as the crosslinking agent M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 7.1 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 as a photopolymerization initiator -On (Ciba Specialty Chemicals Co., Ltd., trade name IRGACURE 369) 2.1 parts by mass, megafac F-554 (manufactured by DIC Corporation) as a surfactant, 0.05 parts by mass, and ethyl lactate as a solvent By mixing, a colored composition having a solid content concentration of 20% by mass was prepared.

The obtained colored composition 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 three coating films having different film thicknesses.
Next, after cooling the substrate to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 2,000 J / m ² without using a high pressure mercury lamp. did. In this way, a blue evaluation cured film was formed on the substrate.

The substrate on which the contrast evaluation cured film is formed is sandwiched between two deflection plates, and the front side deflection plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the rear side, and a luminance meter LS-100 (Minolta) The maximum value and the minimum value of the transmitted light intensity were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value y = 0.080 was obtained. The evaluation results are shown in Table 1. Note that the larger the numerical value, the better the contrast ratio.

The substrate heat resistance evaluation cured film is formed, using a color analyzer (Otsuka Electronics Co., Ltd. MCPD2000), at the C light source, 2 ° visual field, the chromaticity coordinate values in the CIE colorimetric system (x, y) And the stimulation value (Y) was measured.
Next, after post-baking in a clean oven at 230 ° C. for 1 hour, chromaticity coordinate values (x, y) and stimulus values (Y) were measured, and color change before and after the additional baking, that is, ΔE ^* _ab was evaluated. . As a result, the case where ΔE ^* _ab was less than 3.0 was evaluated as “◎”, the case where 3.0 or more and less than 5.0 was evaluated as “◯”, and the case where 5.0 or more was evaluated as “×”. The evaluation results are shown in Table 1.

Evaluation of voltage holding ratio An SiO ₂ film that prevents elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape on a soda glass substrate, After spin coating, prebaking was performed for 1 minute on a hot plate at 100 ° C. to form a coating film having a thickness of 2.0 μm. Subsequently, the coating film was exposed at an exposure amount of 700 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-treated at 230 ° C. for 30 minutes. Baking was performed and the coating film was cured to form a permanent cured film. Next, the substrate on which the permanent cured film is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 1.8 mm glass beads, and then Merck liquid crystal (MLC6608) is injected. Thus, a liquid crystal cell was produced. Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (VHR-1A type, Toyo Technica Co., Ltd.). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is a value obtained by (liquid crystal cell potential difference after 16.7 milliseconds / voltage immediately after application). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a risk of causing "burn-in".

Examples 2-14 and Comparative Examples 1-2
In Example 1, a colored composition was prepared in the same manner as in Example 1, except that the types and amounts of the pigment dispersion and the dye solution were changed as shown in Table 1. Then, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Claims (6)

(A) A coloring composition containing a colorant comprising a compound having a structure represented by the following formula (1), (B) a binder resin, and (C) a polymerizable compound.

[In Formula (1),
m represents an integer of 0 to 5, and when m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
R ^{1 to} R ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted heterocyclic group. However, the hydrocarbon group may have a linking group selected from —CO—, —COO—, and —CONH— between C—C bonds.
R ⁵ independently represents a monovalent group.
However, one or more of R ^{1 to} R ⁴ are groups selected from the following requirements (i) and (ii) .
(I) A substituted or unsubstituted unsaturated aliphatic hydrocarbon group, or a substituted or unsubstituted unsaturated alicyclic hydrocarbon group. However, the unsaturated aliphatic hydrocarbon group may have a linking group selected from —CO—, —COO— and —CONH— between C—C bonds.
(Ii) An alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group It is a group . ] R ⁵ is —CO ₂ ⁻ , —CO ₂ H, —CO ₂ M, —CO ₂ R ⁶ , —SO ₃ ⁻ , —SO ₃ H, —SO ₃ M, —SO ₃ R ⁷ , —SO ₂ NHR ^{8 _{, -SO 2 NR 9 R 10,}} -SO 2 -O-N = CR 11 R 12, -SO 2 NHNHR 13, a -SO ₂ SR ¹⁴ or -SO ₂ NHSO ₂ R ^15,
R ^{6 to} R ¹¹ and R ^{13 to} R ¹⁵ are each independently a substituted or unsubstituted hydrocarbon group,
R ¹² is a hydrogen atom or a substituted or unsubstituted hydrocarbon group,
The coloring composition according to claim 1, wherein M is a sodium atom or a potassium atom. The coloring composition according to claim 1 or 2 , further comprising at least one selected from the group consisting of a blue pigment, a blue dye, a purple pigment, and a purple dye as a colorant. The colored cured film formed using the coloring composition of any one of Claims 1-3 . A display element comprising the colored cured film according to claim 4 . The compound which has a structure represented by following formula (1).

[In Formula (1),
m represents an integer of 0 to 5, and when m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
R ^{1 to} R ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted heterocyclic group. However, the hydrocarbon group may have a linking group selected from —CO—, —COO—, and —CONH— between C—C bonds.
R ⁵ independently represents a monovalent group.
However, one or more of R ^{1 to} R ⁴ are groups selected from the following requirements (i) and (ii) .
(I) a substitution or unsubstituted unsaturated alicyclic hydrocarbon group.
(Ii) An alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group It is a group . ]