JP6350335B2 - 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. Generally speaking, however, heat resistance often occurs when a dye is applied, compared to when a pigment is applied as a colorant. Under such a background, as a coloring composition capable of forming a coloring pattern excellent in heat resistance and the like, for example, Patent Document 5 proposes a coloring composition containing a dye multimer as a colorant.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2013-28764 A

However, the present inventors have found that a coloring pattern formed using a coloring composition as described in Patent Document 5 has extremely low contrast and is not suitable for each color pixel used in a color filter or the like. It became clear by examination.
Accordingly, an object of the present invention is to provide a coloring composition that is excellent in heat resistance and suitable for forming a colored cured film with high contrast. Moreover, the subject of this invention is providing the colored cured film formed using the said coloring composition, and the display element which comprises the same.

  As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a specific compound having a fluorescent site as a colorant and a specific compound having a fluorescent site. .

That is, the present invention is a colored composition comprising (A) a colorant and (B) a polymerizable compound,
(A) the colorant is
Selected from a monomer (α1) having a fluorescent site and a polymerizable group, and a polymer (α2) including the monomer (α1) as a structural unit (hereinafter also referred to as “compound group α ¹ ”) At least one selected from
The monomer (β1) having the fluorescence-absorbing moiety and a polymerizable group, and a polymer (β2) containing the monomer (β1) as a structural unit (hereinafter also referred to as “compound group β ¹ ”) A colored composition comprising a combination with at least one selected from (provided that (A) the colorant is a combination of the monomer (α1) and the monomer (β1)). Is.

The present invention also provides a colored composition comprising (A) a colorant and (B) a polymerizable compound,
(A) the colorant is
A monomer (α3) having at least one chromophore selected from a xanthene chromophore and a cyanine chromophore and a polymerizable group, and a polymer (α4) (hereinafter referred to as a structural unit) , Also referred to as “compound group α ² ”),
Monomer (β3) having at least one chromophore selected from a triarylmethane chromophore and an anthraquinone chromophore and a polymerizable group, and a polymer (β4) containing the monomer (β3) as a structural unit (Hereinafter, also referred to as “compound group β ² ”), a colored composition comprising a combination with at least one selected from the group consisting of the monomer (α3) and the monomer (β3 ) Except for the case of a combination of).

Here, the polymer containing a monomer as a structural unit may be a homopolymer or a copolymer as long as it has the monomer as an essential structural unit. Hereinafter, “compound group α ¹ and compound group α ² ” are referred to as “compound group α”, “compound group β ¹ and compound group β ² ” are referred to as “compound group β”, “monomer (α1) and single amount “Monomer (α3)” is “Monomer α”, “Monomer (β1) and Monomer (β3)” is “Monomer β”, “Polymer (α2) and Polymer (α4)” Is sometimes referred to as “polymer α”, and “polymer (β2) and polymer (β4)” are sometimes referred to as “polymer β”.

  Furthermore, this invention provides the colored cured film formed using the said coloring composition, and the display element which comprises 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.

If the colored composition of the present invention is used, a colored cured film having excellent heat resistance and high contrast 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 colored composition of the present invention contains a combination of at least one selected from the compound group α and at least one selected from the compound group β as a colorant.

Among the compound groups α, the compound group α ¹ is a monomer (α1) having a fluorescent site and a polymerizable group, and a polymer (α2) containing the monomer (α1) as a structural unit. Examples of the fluorescent site include xanthene chromophore and cyanine chromophore. As a preferred embodiment of the compound group α ¹ , a monomer (α3) having at least one chromophore selected from a xanthene chromophore and a cyanine chromophore and a polymerizable group, and a structure of the monomer (α3) Examples thereof include a polymer (α4) (compound group α ² ) contained as a unit. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. Among these, an ethylenically unsaturated group is preferable. As a preferred embodiment of the monomer (α1), an ethylenically unsaturated monomer having a fluorescent site, more preferably an ethylenically unsaturated monomer having at least one chromophore selected from a xanthene chromophore and a cyanine chromophore. A saturated monomer is mentioned, For example, it can represent with a following formula (1-1).

[In Formula (1-1),
R ¹ independently represents a hydrogen atom or a methyl group.
X ¹ is independently of each other a direct bond, a substituted or unsubstituted divalent hydrocarbon group, or the divalent hydrocarbon group, and one or more linking groups containing atoms other than carbon atoms and hydrogen atoms. A divalent group formed by combining
P represents a site that emits fluorescence.
g represents an integer of 1 or more. ]

In addition, the compound group β ¹ of the compound group β has a structure of the monomer (β1) having a site that absorbs fluorescence emitted from the monomer (α1) and a polymerizable group, and the monomer (β1). It is a polymer (β2) contained as a unit. Examples of the site that absorbs fluorescence emitted from the monomer (α1) include a triarylmethane chromophore and an anthraquinone chromophore. As a preferred embodiment of the compound group β ¹ , a monomer (β3) having at least one chromophore selected from a triarylmethane chromophore and an anthraquinone chromophore and a polymerizable group, and the monomer (β3) As a structural unit, a polymer (β4) (compound group β ² ) can be given. Moreover, as a polymeric group, the thing similar to what was illustrated in the above-mentioned compound group (alpha) is mentioned, Among these, an ethylenically unsaturated group is preferable. As a preferred embodiment of the monomer (β1), an ethylenically unsaturated monomer having a site that absorbs fluorescence emitted from the monomer (α1), more preferably selected from a triarylmethane chromophore and an anthraquinone chromophore. Examples thereof include an ethylenically unsaturated monomer having at least one chromophore, and can be represented by, for example, the following formula (1-2).

[In Formula (1-2),
R ² represents a hydrogen atom or a methyl group.
X ² is a direct bond, a substituted or unsubstituted divalent hydrocarbon group, or a combination of the divalent hydrocarbon group and one or more linking groups containing atoms other than carbon atoms and hydrogen atoms. Indicates a valent group.
Q represents a site that absorbs fluorescence.
h represents an integer of 1 or more. ]

Hereinafter, the symbols in the formulas (1-1) and (1-2) will be described.
R ¹ and R ² can be appropriately selected from a hydrogen atom or a methyl group.
Examples of the divalent hydrocarbon group related to X ¹ and X ² include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. . In the present specification, the “alicyclic hydrocarbon group” is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. 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. 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.

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.

In the divalent group formed by combining a divalent hydrocarbon group and one or more linking groups containing atoms other than carbon atoms and hydrogen atoms, examples of the linking group include -O- and -S-. , —SO ₂ —, —CO—, —COO—, —OCO—, —CONR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —NR ³ — (R ³ represents , Which are the same as those described above). The bonding position of the linking group is arbitrary, and for example, it can have a terminal of a divalent hydrocarbon group or between C-C bonds, but among them, it is preferable to have one terminal or between C-C bonds. In addition, a divalent hydrocarbon group and the linking group may be bonded to form a ring structure. In addition, the carbon number in paragraph [0020] means the total carbon number of the part except the carbon atom which comprises this coupling group.

Specific examples of the divalent hydrocarbon group having the linking group between C—C bonds include, for example, —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH ₂ —, —CH ₂ —CH ( _{-CH 3) -CH 2 -COO-CH} 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -OCO-CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -COO _{-CH 2 -CH (CH 2 -CH 3} ) -CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH 3) - _{CH 2 -CH 2 -CH 2 -CH 2} -, - (CH 2) 5 -COO- (CH 2) 11 -CH 2 -, - CH 2 -CH 2 -CH 2 -C- (COO-CH 2 - _{CH 3) 2 -, - CH} 2 -CH 2 -O-CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -O-CH 2 -CH 2 -, - (CH 2 -CH 2 -O ) _n - H ₂ - (n is an integer from 1 to _{8), - (CH 2 -CH 2} -CH 2 -O) m -CH 2 - (m is an integer of 1 to 5), - CH ₂ -CH _{(CH 3) -O-CH 2} -CH 2 -, - CH 2 -CH- (OCH 3) -, - CH 2 -CH 2 -COO-CH 2 -CH 2 -O-CH 2 -CH (CH 2 _{-CH 3) -CH 2 -CH 2 -CH} 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -O-CO-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 - _{CH 2 -CH 2 -, - CH} 2 -CH 2 -COO-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 - _{CH 2 -CH 2 -, - CH} 2 -CH 2 -NH-COO-CH 2 -CH 2 -, - CH 2 -CH 2 -OCO-CH 2 - is and the like, are limited to With things There is no.

  Specific examples of the group having a ring structure formed by bonding a divalent hydrocarbon group and the linking group include the following, but are not limited thereto.

  Examples of the substituent that the divalent hydrocarbon group has include a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkoxyl group, and a substituted or unsubstituted aryloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxyl group may be either a straight chain or branched chain, and preferably has 1 to 6 carbon atoms. Specific examples include methoxy group, ethoxy group, propoxy group, butoxy group and the like. 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. Examples of the substituent for the alkoxyl group and aryloxy group include a halogen atom, a nitro group, a hydroxyl group, an amino group, a carboxyl group, and a sulfanyl group. Furthermore, when the divalent hydrocarbon group is a divalent aromatic hydrocarbon group, it may be substituted with a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. The alkyl group and alkenyl group preferably have 1 to 6 carbon atoms, and 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- Examples of the alkenyl group include, for example, ethenyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 2-ethyl-2-yl group and the like. A butenyl group etc. are mentioned. In addition, as a substituent of an alkyl group and an alkenyl group, the same thing as the substituent of the above-mentioned bivalent hydrocarbon group can be mentioned.

P is not particularly limited as long as it is a group derived from a fluorescent compound, but is preferably a xanthene chromophore or a cyanine chromophore. The xanthene chromophore or cyanine chromophore is a residue obtained by removing g hydrogen atoms from a xanthene compound or cyanine compound, and is a residue that can be linked to g X ^{1 in} the formula (1-1). is there.

Q is not particularly limited as long as it is a group derived from a compound that absorbs fluorescence, but a triarylmethane chromophore or an anthraquinone chromophore is preferred. The triarylmethane chromophore or anthraquinone chromophore is a residue obtained by removing h hydrogen atoms from a triarylmethane compound or anthraquinone compound, and can be linked to h X ^{2 in} the formula (1-2). Residue.
g and h each independently represent an integer of 1 or more, preferably 1 or 2.

  Examples of xanthene compounds, cyanine compounds, triarylmethane compounds, and anthraquinone compounds include known dyes classified as dyes (Dye) in the color index (CI; issued by The Society of Dyers and Colorists) You can also. As these dyes, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. may be used. Using an oil-soluble dye or a basic dye is excellent in reactivity, and can easily produce a compound represented by the above formula (1-1) and a compound represented by the above formula (1-2). It is preferable in that it can be performed.

Acid dyes include C.I. in the color index. Those classified as I. Acid and direct dyes include C.I. I. It is classified as direct. As the oil-soluble dye, C.I. The basic dye is classified into C.I. Solvent, and the basic dye includes C.I. I. Basically classified.
Hereinafter, a xanthene compound, a cyanine compound, a triarylmethane compound, and an anthraquinone compound will be described.

  As the xanthene compound, a compound having a structure represented by the following formula (2) is preferable, and specific examples thereof include C.I. And xanthene basic dyes such as I. basic violet 10 (rhodamine B).

[In Formula (2),
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and an atom other than a carbon atom and a hydrogen atom between the C—C bonds of the hydrocarbon group. A group having a linking group to be included, or a substituted or unsubstituted heterocyclic group;
R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
R ¹⁷ is —SO ₃ ⁻ , —SO ₃ H, —SO ₃ M, —SO ₃ R ¹⁸ , —CO ₂ ⁻ , —CO ₂ H, —CO ₂ M, —CO ₂ R ¹⁹ , —SO ₂ NHR ²⁰ or an -SO ₂ NR ²¹ R ^22.
r represents an integer of 0 to 5, and when r is an integer of 2 or more, a plurality of R ¹⁷ may be the same or different.
R ¹⁸ , R ¹⁹ and R ²⁰ each independently have a substituted or unsubstituted hydrocarbon group, or a linking group containing an atom other than a carbon atom and a hydrogen atom between the C—C bonds of the hydrocarbon group. Indicates a group.
R ²¹ and R ²² each independently represent a substituted or unsubstituted hydrocarbon group, or a group having a linking group containing an atom other than a carbon atom and a hydrogen atom between the C—C bonds of the hydrocarbon group. Or a substituted or unsubstituted heterocyclic group formed by combining R ²¹ and R ²² with each other.
M represents a sodium atom or a potassium atom. ]

Examples of the hydrocarbon group in R ^{11 to} R ¹⁶ and R ^{18 to} R ²² include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
The aliphatic hydrocarbon group may be saturated or unsaturated, and examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-15 are more preferable, and 1-8 are especially preferable. The aliphatic hydrocarbon group may be linear or branched. Examples of the alkyl group include, in addition to the specific examples described above, heptyl, octyl, nonyl, decyl, undecyl, 1-methyldecyl, dodecyl, 1-methylundecyl, 1-ethyldecyl, tridecyl. Group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyloctyl group, hexadecyl group, octadecyl group and the like. Examples of the alkenyl group include 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group and the like in addition to the specific examples described above. 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.

As an alicyclic hydrocarbon group, a C3-C30 alicyclic hydrocarbon group is preferable. The alicyclic hydrocarbon group may be saturated or unsaturated, and includes, for example, a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon group. 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 the aromatic hydrocarbon group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. Here, the “aryl group” refers to a monocyclic to tricyclic aromatic hydrocarbon group, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an azulenyl group, and a 9-fluorenyl group. Of these, a phenyl group and a naphthyl group are preferable.

The hydrocarbon group in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² includes atoms other than carbon atoms and hydrogen atoms between C—C bonds. The group which may have a connecting group and has a connecting group, when having a connecting group, the group which has the said connecting group between CC bond of an aliphatic hydrocarbon group is preferable. Specific examples of the linking group include the same ones as described above.

  The heterocyclic group may be a monocyclic heterocyclic ring or a polycyclic heterocyclic ring. The heterocyclic group may be an unsaturated ring or a saturated ring, and may have two or more heteroatoms (for example, a nitrogen atom, an oxygen atom, and a sulfur atom) of the same or different types in the ring. The heterocyclic group is preferably a heterocyclic group having 3 to 10 carbon atoms, for example, a nitrogen-containing group such as pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, morpholinyl group, thiomorpholinyl group, piperidyl group, piperidino group, piperazinyl group, homopiperazinyl group, etc. Other alicyclic heterocyclic groups such as alicyclic heterocyclic group, 1,3-dioxolan-2-yl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, quinolyl group, isoquinolyl group, phthalazinyl group, naphthyridinyl group Group, quinoxalinyl group, imidazolyl group, pyrazolyl group, triazoyl group, tetrazolyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, indolyl group, indazolyl group, benzoimidazolyl group, phthalimide group and other nitrogen-containing aromatic heterocyclic groups, thienyl group, Furyl group, Can be exemplified sulfonyl groups, other aromatic heterocyclic groups such as a purinyl group.

Examples of the heterocyclic group formed by combining R ²¹ and R ²² with each other include the same heterocyclic groups as those described above.

Examples of the substituent of the hydrocarbon group in R ^{11 to} R ¹⁶ and R ^{18 to} R ²² include a halogen atom, a hydroxyl group, a cyano group, a formyl group, a carboxy group, a nitro group, an amino group, and di (C _1-8 alkyl). Amino group, diarylamino group, C _1-8 alkoxyl group, C _6-10 aryloxy group, C _2-8 alkoxycarbonyl group, C _1-8 alkylthio group, C _6-10 arylthio group, tri (C _1-8 Alkyl) silyl group, mercapto group, allyl group, C _1-8 alkylsulfonyl group, C _1-8 alkylsulfamoyl group, heterocyclic group, aromatic hydrocarbon group and the like, alicyclic hydrocarbon group, The heterocyclic group and the aromatic hydrocarbon group may be substituted with an aliphatic hydrocarbon group. These substituents can further have a substituent. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different. In addition, examples of the substituent of the heterocyclic group according to R ^{11 to} R ¹⁴ and the substituent of the heterocyclic group formed by combining R ²¹ and R ²² with each other include R ^{11 to} R ¹⁶ and R ^{18 to} R ²² . The thing similar to the substituent of a hydrocarbon group can be mentioned.

Especially, as R < ¹¹ >, R < ¹² >, R <^13> and R < ¹⁴ >, a hydrogen atom, a C1-C8 alkyl group, or a C6-C10 aryl group is preferable.
R ¹⁵ and R ¹⁶ are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ¹⁷ is preferably —SO ₃ H, —SO ₃ R ¹⁸ , —CO ₂ H, —CO ₂ R ¹⁹ , —SO ₂ NHR ²⁰ or —SO ₂ NR ²¹ R ²² , and R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are preferably an alkyl group having 1 to 8 carbon atoms.
r is preferably 1 or 2.

  Specific examples of the xanthene compound having the structure represented by the above formula (2) include compounds having a structure represented by the following formula.

When the structure represented by the above formula (2) is cationic, it has an anion so that the xanthene compound having the structure is electrically neutral. Examples of the anion include halogen ion, boron anion, phosphate anion, carboxylate anion, sulfate anion, organic sulfonate anion, nitrogen anion, metide anion, hydroxide ion and the like.
Moreover, when the structure represented by the said Formula (2) is anionic, it has a cation so that the xanthene compound which has the said structure may become electrically neutral. Examples of cations include protons, metal cations, onium cations and the like. Examples of the metal cation include monovalent metal cations such as lithium ion, sodium ion, potassium ion, rubidium ion and cesium ion, and divalent metal cations such as magnesium ion, calcium ion, strontium ion and barium ion. Can do. Examples of the onium cation include an ammonium cation and a phosphonium cation. Specific examples of the ammonium cation include cations in the compound described in paragraph [0045] of JP2011-138094A, and specific examples of the phosphonium cation include paragraphs [0038] to [0040] of JP2013-19077A. And the like.

  As the cyanine compound, a compound having a structure represented by the following formula (3) is preferable, and specific examples thereof include C.I. I. Cyanine basic dyes such as Basic Red 12 can be mentioned.

[In Formula (3),
R ³¹ and R ³² each independently represent a substituted or unsubstituted hydrocarbon group.
R ³³ to R ³⁵ represents independently of one another, a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group. A plurality of R ³³ and R ³⁴ may be the same or different.
Ring Z ¹ and ring Z ² each independently represent a substituted or unsubstituted aromatic hydrocarbon ring.
G ¹ and G ² each independently represent —O—, —S—, or —CR ³⁶ R ³⁷ —. However, R ³⁶ and R ³⁷ each independently represent a substituted or unsubstituted hydrocarbon group.
s shows the integer of 1-3. ]

Examples of the hydrocarbon group in R ^{31 to} R ³⁷ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include those similar to the hydrocarbon group in formula (2), and the same examples can be given to the substituent.
The aromatic hydrocarbon ring in ring Z ¹ and ring Z ² may be a monocyclic aromatic hydrocarbon ring or a polycyclic aromatic hydrocarbon ring, and preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. preferable. Specific examples include benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, naphthacene ring, and triphenylene ring. Examples of the substituent of the aromatic hydrocarbon ring include the same substituents as those of the hydrocarbon group in formula (2).

Among them, as the hydrocarbon group in R ³¹ and R ^32, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms.
As R < ³³ > -R < ³⁵ >, a hydrogen atom is preferable.
As the ring Z ¹ and the ring Z ² , a benzene ring is preferable.
G ¹ and G ² are preferably —O— and —CR ³⁶ R ³⁷ —, and R ³⁶ and R ³⁷ are preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. A methyl group and an ethyl group are preferable.
s is preferably 1 or 2, and more preferably 1.

  Specific examples of the cyanine compound having the structure represented by the above formula (3) include compounds having a structure represented by the following formula.

  When the structure represented by the above formula (3) is cationic, the cyanine compound having the structure has an anion so as to be electrically neutral. Moreover, when the structure represented by the said Formula (3) is anionic, it has a cation so that the cyanine compound which has the said structure may become electrically neutral. Specific examples of such anions and cations include, for example, those similar to those exemplified in the above formula (2).

  Examples of the triarylmethane compound include diaminotriarylmethane dyes, triaminotriarylmethane dyes, rosic acid dyes having an OH group, and the like. Among these, diaminotriarylmethane dyes and triaminotriarylmethane dyes are preferable in that they are excellent in color tone and more excellent in fastness to sunlight than others. More preferable triarylmethane compounds include compounds having a structure represented by the following formula (4). In addition, although various resonance structures exist in the structure represented by the following formula (4), in this specification, these resonance structures are assumed to be equivalent to the structure represented by the following formula (4).

[In Formula (4),
Y represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or —NR ⁵⁹ R ⁶⁰ .
R ^{41 to} R ⁴⁴ and R ^{59 to} R ⁶⁰ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
R ^{45 to} R ⁵² represent a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group, or —COOR ′. However, R 'shows a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
Ar represents a substituted or unsubstituted aromatic hydrocarbon group. ]

Examples of the hydrocarbon group according to Y, R ^{41 to} R ⁵² , R ^{59 to} R ⁶⁰ and R ′ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include those similar to the hydrocarbon group in formula (2), and the same examples can be given to the substituent.
The aromatic hydrocarbon group according to Ar preferably has 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples include a phenylene group, a naphthylene group, a biphenylene group, an anthrylene group, and the like. Examples of the substituent of the aromatic hydrocarbon group include the same substituents as the substituent of the hydrocarbon group in the formula (2), and among them, a halogen atom is preferable.

Among these, as ^{R 41 ~R 44, R 59 ~R} 60 and R ', a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms preferred.
R ^{45 to} R ⁵² are preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.
Ar is preferably a phenylene group or a naphthylene group.
Y is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

  In the present invention, among the structure represented by the above formula (4), a cation represented by the following formula (4-1) or (4-2) is particularly preferable from the viewpoint of heat resistance and solvent resistance.

[In the formulas (4-1) and (4-2),
Y ¹ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or —NR ⁶¹ R ⁶² .
R ^{53 to} R ⁵⁶ and R ^{61 to} R ⁶² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms. ]

R ^{53 to} R ⁵⁶ are more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
R ⁵⁷ and R ⁵⁸ are preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
R ^{61 to} R ⁶² are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  Specific examples of the triarylmethane compound having the structure represented by the above formula (4) include compounds having a structure represented by the following formula.

  When the structure represented by the above formula (4) is cationic, it has an anion so that the triarylmethane compound having the structure is electrically neutral. Moreover, when the structure represented by the said Formula (4) is anionic, it has a cation so that the triarylmethane compound which has the said structure may become electrically neutral. Specific examples of such anions and cations include, for example, those similar to those exemplified in the above formula (2).

  As the anthraquinone compound, a compound having a structure represented by the following formula (5-1) or (5-2) is preferable, and specific examples include an anthraquinone oil-soluble dye such as CI Solvent Green 3. be able to.

[In Formula (5-1),
R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. ]

[In Formula (5-2),
R ⁸¹ and R ⁸² represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
R ⁸³ represents a substituted or unsubstituted divalent hydrocarbon group. ]
R ⁸⁴ , R ⁸⁵ and R ⁸⁶ each independently represent a substituted or unsubstituted hydrocarbon group. ]

Examples of the hydrocarbon group in R ⁷¹ , R ⁷² , R ⁸¹ , R ⁸² and R ^{84 to} R ⁸⁶ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include the same ones as exemplified in Formula (2), and the same substituents can be exemplified.
Examples of the divalent hydrocarbon group for R ⁸³ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Specific examples thereof include the same ones as exemplified in the divalent hydrocarbon groups according to the formulas (1-1) and (1-2), and the same examples can be given to the substituents. .

Among them, R ⁷¹ and R ⁷² are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydrogen atom, An unsubstituted phenyl group is more preferred. Examples of the substituent of the alkyl group include a halogen atom, a hydroxyl group, a cyano group, and the substituent of the aryl group and the phenyl group include a halogen atom, a hydroxyl group, a cyano group, and an alkyl group having 1 to 6 carbon atoms. Etc.
R ⁸¹ , R ⁸² , R ⁸⁴ , R ^85, and R ⁸⁶ are preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. More preferred are 4 alkyl groups. Examples of the substituent for the alkyl group include the same ones as described above.
R ⁸³ is preferably an alkanediyl group having 1 to 20 carbon atoms, more preferably an alkanediyl group having 2 to 8 carbon atoms. Examples of the substituent of the alkanediyl group include those similar to the substituents of X ¹ and X ^{2 according to} the above formulas (1-1) and (1-2).

  Specific examples of the anthraquinone compound having the structure represented by the above formula (5-1) or (5-2) include compounds having a structure represented by the following formula.

In addition to the above, as the xanthene compound, for example,
C. I. Acid Red 51 (erythrosin), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G), C.I. I. Acid Red 92 (Acid Phloxin PB), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. Xanthene acid dyes such as Acid Violet 9;
CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, CI Solvent Red 45, C.I. CI Solvent Red 46, CI Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72, CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet Xanthene oil-soluble dyes such as 10;
C. I. Basic Red 1 (Rhodamine 6 GCP), C.I. Xanthene basic dyes such as I. Basic Red 8 (Rhodamine G) can also be used.

  Examples of cyanine compounds include C.I. I. Basic Red 13, C.I. I. Basic Red 14, C.I. I. Basic Violet 7, C.I. I. Basic Yellow 11, C.I. I. Basic Yellow 13, C.I. I. Basic Yellow 21, C.I. I. Basic Yellow 28, C.I. I. Cyanine basic dyes such as Basic Yellow 51 can also be used.

Furthermore, as a triarylmethane compound, for example,
CI Acid Blue 1, CI Acid Blue 3, CI Acid Blue 5, CI Acid Blue 7, CI Acid Blue 9, CI Acid Blue 11, C.I. I. Acid Blue 15, C.I. Acid Blue 17, C.I. Acid Blue 19, C.I. Acid Blue 22, C.I. Acid Blue 24, C.I. Acid Blue 38, C.I. Acid Blue 48, C.I. Acid Blue 75, C.I. Acid Blue 83, C.I. Acid Blue 90, C.I. Acid Blue 91, C.I. Acid Blue 93, C.I. Acid Blue 93: 1, C.I. Acid Blue 100, C.I. Acid Blue 103, C.I. Acid Blue 104, C.I. Acid Blue 109, C.I. Acid Blue 110, C.I. Acid Blue 119, C.I. Blue 147, CI Acid Blue 269, CI Acid Blue 123, CI Acid Blue 213, CI Direct Blue 41, CI Acid Violet 17, CI Acid Violet 19 CI Acid Violet 21, C.I. Acid Violet 23, C.I. Acid Violet 25, C.I. Acid Violet 38, C.I. Acid Violet 49, C.I. Acid Violet 72, etc. Triarylmethane acid dyes;
C. I. Basic violet 1 (methyl violet), C.I. I. Basic Violet 3 (Crystal Violet), C.I. I. Basic Violet 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), C.I. I. Basic Blue 5 (Basic Cyanine EX), C.I. I. Basic Blue 7 (Victoria Pure Blue BO), C.I. I. Basic Blue 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), C.I. I. Basic aryl dyes such as basic green 4 (malachite green);
C. I. Triarylmethane-based direct dyes such as Direct Blue 41 can also be used.

Moreover, as an anthraquinone compound, for example,
C.I. Acid Blue 23, C.I. Acid Blue 25, C.I. Acid Blue 27, C.I. Acid Blue 35, C.I. Acid Blue 40, C.I. Acid Blue 41, C.I. I. Acid Blue 43, C.I. Acid Blue 45, C.I. Acid Blue 47, C.I. Acid Blue 49, C.I. Acid Blue 51, C.I. Acid Blue 53, C.I. Acid Blue 55, C.I. Acid Blue 56, C.I. Acid Blue 62, C.I. Acid Blue 68, C.I. Acid Blue 69, C.I. Acid Blue 78, C.I. Acid Blue 80, C.I. Acid Blue 81: 1, C.I. Acid Blue 11, C.I. Acid Blue 124, C.I. Acid Blue 127, C.I. Acid Blue 127: 1, C.I. Acid Blue 140, Acid Blue 150, CI Acid Blue 175, CI Acid Blue 215, CI Acid Blue 230, CI Acid Blue 277, CI Acid Blue 344, CI Anthraquinone acid dyes such as Acid Violet 41, CI Acid Violet 42, CI Acid Violet 43, CI Acid Green 25, CI Acid Green 27, etc .;
Direct dyes such as CI Direct Violet 17;
Anthraquinone oil-soluble dyes such as CI Solvent Red 172, CI Solvent Red 222, and CI Solvent Violet 60 can also be used.

The method for synthesizing monomer α and monomer β is not particularly limited, and a conventionally known method can be used. For example, the compound represented by the formula (1-1) and the compound represented by the formula (1-2) are ethylenically unsaturated by a general organic synthesis technique on the basic skeleton of the dye having a functional group. It can be obtained by introducing a group having a group or by synthesizing a dye after introducing a group having an ethylenically unsaturated group into a dye synthesis raw material. More specifically, descriptions in JP2013-178478A, JP2013-173850A, JP2013-210621A, JP2013-028764A, and the like can be referred to.
And polymer (alpha) and polymer (beta) can each be manufactured by superposing | polymerizing the monomer (alpha) and the monomer (beta). A conventionally known method can be used for the polymerization reaction. For example, a method similar to the binder resin (C) described later can be employed.

  The polymer α and the polymer β are also referred to as other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as “unsaturated monomer (a3)”) other than the monomer α and the monomer β, respectively. ) As a structural unit.

As a specific example of such an unsaturated monomer (a3), for example,
It has a carboxyl group such as (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, and p-vinylbenzoic acid. Ethylenically unsaturated monomers;
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 (degree of polymerization 2 -10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 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.

  Among these, from the viewpoints of heat resistance, solvent resistance, dye transfer control, and dispersibility, the unsaturated monomer (a3) includes an ethylenically unsaturated monomer having a carboxyl group and (meth) acrylic acid ester. preferable.

  When the polymer α and the polymer β are copolymers containing the unsaturated monomer (a3) as a structural unit, the unsaturated monomer (a3) in all the structural units of the polymer α and the polymer β The copolymerization ratio of is preferably the following embodiment. That is, the copolymerization ratio of the unsaturated monomer (a3) is preferably 30 to 97% by mass, more preferably 40 to 95% by mass, and particularly preferably 50 to 90% by mass in all the structural units. By copolymerizing the unsaturated monomer (a3) in such a range, it becomes easy to obtain a colored composition excellent in heat resistance, solvent resistance, dye transfer suppression, and dispersibility.

  The polymer α and the polymer β have a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually from 1,000 to 100, 000, preferably 3,000 to 50,000, more preferably 3,000 to 10,000. By setting it as such an aspect, contrast, heat resistance, solvent resistance, dye transfer suppression, a film characteristic, an electrical property, a pattern shape, and the resolution can be made favorable.

  Moreover, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer α and the polymer β is preferably 1.0 to 5.0, more preferably 1.0. ~ 3.0. In addition, Mn here is the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  In the present invention, the (A) colorant contains a combination of at least one selected from the compound group α and at least one selected from the compound group β. From the viewpoint of contrast, the compound An embodiment in which the group α is a polymer α and the compound group β is a monomer β is preferable. From the viewpoint of heat resistance, the compound group α is the polymer α and the compound group β is the monomer β, or the compound group α is the polymer α and the compound group β is the polymer β. The aspect which is is preferable. Furthermore, from the viewpoint of solvent resistance, an embodiment in which the compound group α is the polymer α and the compound group β is the polymer β is preferable. Among these, from the viewpoint of achieving high levels of contrast, heat resistance and solvent resistance in a balanced manner, an embodiment in which the compound group α is the polymer α and the compound group β is the polymer β is more preferable.

The content ratio (α / β) of the compound group α and the compound group β is preferably 99/1 to 40/60, more preferably 98/2 to 60/40, and 97/3 to 70/30 in terms of molar ratio. More preferably, 96/4 to 80/20 is particularly preferable.
In particular, when the compound group α is the polymer α and the compound group β is the polymer β, the polymer α is overlapped with the polymer α from the viewpoint of achieving a high level of contrast, heat resistance and solvent resistance in a balanced manner. The content ratio (α / β) with the combined β is preferably 93/7 to 75/25, more preferably 92/8 to 80/20, and still more preferably 91/9 to 85/25 in terms of molar ratio.

  The coloring composition of the present invention can also be used by mixing other colorants other than the compound group α and the compound group β. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application. Examples of other colorants include pigments and dyes other than the compound group α and the compound group β. Of course, a compound having a fluorescent site and not having a polymerizable group, for example, a compound having at least one chromophore selected from a xanthene chromophore and a cyanine chromophore and having no polymerizable group, A compound having a site that absorbs fluorescence and having no polymerizable group, for example, having at least one chromophore selected from a triarylmethane chromophore and an anthraquinone chromophore, and having no polymerizable group A compound may be contained. Among them, 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. Examples of organic dyes include those described in paragraphs [0072] to [0075].

  Examples of the organic pigment include the following compounds classified as pigments in the color index.

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. I. Pigment green 59;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 80;
C. I. Pigment yellow 14, C.I. 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, the following formula

Japanese Patent Application Laid-Open Nos. 2001-081348, 2010-026334, 2010-237384, 2010-237369, 2011-006602, The lake pigment described in 2011-145346 gazette etc. can be mentioned.

  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 Laid-Open No. 8-179111 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 a dispersant can be obtained commercially. Examples of acrylic dispersants include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Corporation (BYK)), and the like. Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Corp.) ), Etc., as polyethyleneimine-based dispersants, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc., and as polyester-based dispersants, Azisper PB821, Azisper PB822 AJISPER PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.) In addition to such, and the like BYK-LPN21324 (BYK Chemie (BYK) Co., Ltd.), can be mentioned, respectively.

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

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

  When other colorants are contained, the content of other colorants is preferably 70% by mass or less, and more preferably 50% by mass or less, based on the total content of the colorants. 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 in terms of heat resistance, solvent resistance, dye transfer suppression, and a pixel having high brightness and excellent color purity, or a black matrix and black spacer having excellent light shielding properties. It is 3-70 mass% in solid content of a coloring composition, Preferably it is 5-60 mass%, More preferably, it is 5-30 mass%. Here, solid content is components other than the solvent mentioned later.

-(B) 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 dihydrate. 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 Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and 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, (B) polymeric compound can be used individually or in mixture of 2 or more types.

  The content of the polymerizable compound (B) in the present invention is preferably 10 to 1,000 parts by weight, more preferably 20 to 800 parts by weight, and further 100 to 700 parts by weight with respect to 100 parts by weight of the (A) colorant. preferable. By setting it as such an aspect, sclerosis | hardenability and alkali developability can be made favorable.

-(C) Binder resin-
The colored composition of the present invention may contain a binder resin (excluding polymers α and β). Thereby, the alkali solubility of a coloring composition, the binding property to a board | substrate, storage stability, etc. can be improved. The binder resin is not particularly limited as long as it does not correspond to the polymers α and β, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter 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”). (C1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomer (c2) ").

Examples of the unsaturated monomer (c1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Examples thereof include acrylate and p-vinylbenzoic acid.
These unsaturated monomers (c1) can be used alone or in admixture of two or more.

Examples of the unsaturated monomer (c2) include N-substituted maleimides, aromatic vinyl compounds, (meth) acrylic acid esters, vinyl ethers, and polymer molecular chains exemplified in the unsaturated monomer (a3). Examples thereof include macromonomers having a mono (meth) acryloyl group at the terminal thereof, and specific examples thereof include those described above.
An unsaturated monomer (c2) can be used individually or in mixture of 2 or more types.

  In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), the copolymerization ratio of the unsaturated monomer (c1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (c1) within 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 (c1) and the unsaturated monomer (c2) 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 JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

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

  In this invention, content of (C) 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. By setting it as such an aspect, alkali developability, the storage stability of a coloring composition, and chromaticity characteristic can be improved further.

-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 acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- And morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

  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) -4,4 Examples include ', 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 triazine compounds 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 (trichloromethyl) ) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy) Triazine compounds having a halomethyl group such as styryl) -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 commercially available O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Corporation) and the like can also be used.

  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 (B) polymeric compounds, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be made favorable.

-Solvent-
The coloring composition of the present invention contains the above components (A) and (B) and other components optionally added, but is usually prepared as a liquid composition by blending an organic solvent. .
As an organic solvent, as long as (A) and (B) component and other components which comprise a coloring composition are disperse | distributed or melt | dissolved, and it does not react with these components and has moderate volatility, it is suitably You can choose to use.

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;
Glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether;
Cyclic ethers such as 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-butyrate 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 thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, and lactams.

  Among these organic solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate from the viewpoints of solubility, pigment dispersibility, coatability, etc. 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyrate Propionate, acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.

  In this invention, an organic solvent can be used individually or in mixture of 2 or more types.

  The content of the organic solvent is not particularly limited, but the total concentration of each component excluding the organic solvent of the coloring composition is preferably 5 to 50% by mass, and preferably 10 to 40% by mass. The amount is 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 fluorosurfactants and silicon 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-chloropropi Adhesion promoters such as trimethoxysilane, 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-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And the like, and the like.

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 , Meaning black spacer.

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.

  The 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, the radiation sensitive material in which a black colorant is dispersed is used. 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.

  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, 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 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 colored composition of the present invention can also be suitably used for forming such a black spacer.

  The radiation-sensitive 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 formed in this way has extremely high luminance and color purity, it can be used in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like. Very useful. In addition, the display element mentioned later should just have at least 1 or more of colored cured films formed using the radiation sensitive 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. Can be taken. Also, 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 indium oxide and zinc oxide) electrode It is also possible to adopt a structure in which the formed substrate 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.

Solid-state image sensor The solid-state image sensor of the present invention comprises the colored cured film of the present invention. In addition, the solid-state imaging device of the present invention can take an appropriate structure. For example, as one embodiment, by using the colored composition of the present invention and forming a colored pixel (colored cured film) on a semiconductor substrate such as a CMOS substrate by the same operation as described above, color separation is achieved. And a solid-state imaging device having excellent color reproducibility.

  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 colorant>
(Synthesis Example 1)
A stir bar was added, and a 100 mL three-necked flask equipped with a reflux condenser and a thermometer was sufficiently purged with nitrogen, charged with 15.0 g of cyclohexanone, and heated to an internal temperature of 80 ± 2 ° C. under a nitrogen stream. In contrast, 4.50 g of the dye monomer (A1) represented by the following formula, 6.00 g of methyl methacrylate, 4.50 g of methacrylic acid, and 2,2′-azobis (2,2) as a polymerization initiator A solution prepared by mixing 2.18 g of 4-dimethylvaleronitrile) (trade name V-65, manufactured by Wako Pure Chemical Industries, Ltd.) and 45.0 g of cyclohexanone was maintained at an internal temperature of 80 ± 2 ° C. The solution was added dropwise using a pump over 2 hours. After completion of the dropwise addition, stirring was continued for another hour at the same temperature. Thereafter, the reaction solution was cooled to room temperature and dropped into a large amount of hexane. The obtained colored solid was dried under reduced pressure at 50 ° C. to obtain 14.1 g of the polymer (1). The obtained polymer (1) had an Mw of 4,800. The polymer (1) corresponds to the polymer α.

Synthesis Examples 2-4
In Synthesis Example 1, polymers (2) to (4) were obtained in the same manner as in Synthesis Example 1 except that the type and amount of the monomer used for polymerization were changed as shown in Table 1. The structures of the dye monomers (A1) to (A4) are as described above. The polymer (2) corresponds to the polymer α, and the polymers (3) to (4) correspond to the polymer β.

The symbols used in Table 1 are as follows.
MMA: Methyl methacrylate MA: Methacrylic acid

The dye monomers (A1) to (A4) were synthesized with reference to the following publications.
Dye monomer (A1): synthesized according to Synthesis Example 2 described in paragraphs [0145] to [0146] of JP2013-178478A. It corresponds to the monomer α.
Dye monomer (A2): Synthesized according to Example 1-1 described in paragraphs [0096] to [0097] of JP2013-173850A. It corresponds to the monomer α.
Dye monomer (A3): Synthesized according to the production of dye monomer (A1-1) described in paragraphs [0149] to [0150] of JP2013-210621A. Corresponds to monomer β.
Dye monomer (A4): “Monomer 1” described in paragraph [0501] of JP2013-028764A. Corresponds to monomer β.

<Preparation of colorant solution>
Preparation Example 1
10 parts by weight of the obtained polymer (1) was dissolved in 90 parts by weight of propylene glycol monomethyl ether to obtain a colorant solution (A-1).

Preparation Examples 2 to 10
Colorant solutions (A-2) to (A-10) were prepared in the same manner as in Preparation Example 1, except that the type and amount of the solute and solvent were changed as shown in Table 2 in Preparation Example 1. In Table 2, the dye (A5) is C.I. I. Basic blue 7 (triarylmethane compound), and the dye (A6) is an anthraquinone compound represented by the following formula. Propylene glycol monomethyl ether was described as “PGME”.

<Synthesis of binder resin>
Synthesis example 5
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 (C1)”.

<Preparation and evaluation of coloring composition>
Preparation of coloring composition Example 1
(A) 16.5 parts by mass of a colorant solution (A-1) and 1.0 part by mass of a colorant solution (A-3) as a colorant, (C) 23.3 parts by mass of a binder resin (C1) solution as a binder resin 9.9 parts by weight of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a polymerizable compound, 2-benzyl as a 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 (ADEKA Corporation) 0.1 part by mass), 0.05 part by mass of MegaFac F-554 (manufactured by DIC Corporation) as a fluorosurfactant Propylene glycol monomethyl ether acetate was mixed as a solvent to prepare a colored composition (S-1) having a solid concentration of 20% by mass.

Evaluation of contrast 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 a coating film having a thickness of 2.5 μm.
Next, after cooling the substrate to room temperature, using a high-pressure mercury lamp, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was applied to each coating film at a dose of 2,000 J / m ² without using a photomask. Exposed. 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 200 ° C. for 30 minutes to form a cured film for evaluation.
A substrate on which a cured film is formed is sandwiched between two deflecting plates, and the front deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and a luminance meter LS-100 (Minolta Co., Ltd.) is rotated. The maximum value and the minimum value of the light intensity transmitted through (made by)) were measured. A value obtained by dividing the maximum value by the minimum value was taken as the contrast ratio. The evaluation results are shown in Table 3. Note that the larger the numerical value, the better the contrast ratio.

Evaluation of heat resistance The colored composition (S-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then a hot plate at 90 ° C. Was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 μm.
Next, after cooling the substrate to room temperature, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m ² through a photomask using a 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, the case where the value of ΔE ^* ab was less than 3.0 was evaluated as “◯”, the case of 3.0 or more and less than 5.0 was evaluated as “Δ”, and the case of 5.0 or more was evaluated as “x”. The evaluation results are shown in Table 3. In addition, it can be said that heat resistance is so favorable that (DELTA ⁾ E ^* ab value is small.

Evaluation of color change The coloring composition (S-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then a hot plate at 90 ° C. 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 to the coating film through the photomask using the high pressure mercury lamp with the exposure amount of 400 J / m < ² >. Then, shower development was performed for 90 seconds by discharging the developing solution which consists of 0.04 mass% potassium hydroxide aqueous solution of 23 degreeC with respect to this board | substrate with the developing pressure of 1 kgf / cm < ² > (nozzle diameter of 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.
The substrate was immersed in propylene glycol monomethyl ether acetate at 80 ° C. for 40 minutes. The chromaticity coordinate values (x, y) and stimulus values (Y) before and after immersion were measured, and the color change before and after immersion, that is, ΔE ^* _ab was evaluated. As a result, the case where the value of ΔE ^* _ab was less than 3.0 was evaluated as “◯”, the case of 3.0 or more and less than 5.0 was evaluated as “Δ”, and the case of 5.0 or more was evaluated as “x”. The evaluation results are shown in Table 3. It can be said that the smaller the ΔE ^* _ab value, the better the solvent resistance.

Evaluation of Contrast Change Rate The colored composition (S-1) was applied on a soda glass substrate on the surface of which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then heated at 90 ° C. The plate was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 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. . 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, the substrate was washed with ultrapure water, air-dried, and post-baked in a clean oven at 230 ° C. for 30 minutes to form a colored cured film on the substrate. This is referred to as a substrate (T-1).
Next, polyorganosiloxane, trimellitic anhydride, 2-ethyl-4-methylimidazole, and propylene glycol monomethyl ether acetate obtained according to Example 1 of Japanese Patent No. 4697423 on the substrate (T-1) The resin composition for forming a protective film containing was applied using a spin coater. Thereafter, pre-baking was performed for 5 minutes on a hot plate at 90 ° C., and further post-baking was performed for 30 minutes in a clean oven at 230 ° C., thereby forming a protective film having a thickness of 2.0 μm from the upper surface of the colored cured film. Let the obtained board | substrate be a board | substrate (T-2).
The contrast of the board | substrate (T-1) and the board | substrate (T-2) was each measured by the method similar to the above, and the contrast change rate calculated | required by the following formula was calculated | required. As a result, the case where the contrast change rate was less than 15% was evaluated as “◯”, the case where it was 15% or more and less than 30% was evaluated as “Δ”, and the case where it was 30% or more was evaluated as “X”. The evaluation results are shown in Table 3. It can be said that the smaller the contrast change rate, the better.

  Contrast change rate = ((contrast of substrate (T-2)) − (contrast of substrate (T-1))) × 100 / (contrast of substrate (T-1))

Examples 2-11 and Comparative Examples 1-6
In Example 1, colored compositions (S-2) to (S-17) were prepared in the same manner as in Example 1 except that the type and amount of each component were changed as shown in Table 3. Subsequently, evaluation was performed in the same manner as in Example 1 except that the colored compositions (S-2) to (S-17) were used in place of the colored composition (S-1). The results are shown in Table 3.

  In Table 3, “α / β” indicates the molar ratio between the site that emits fluorescence in the compound group α and the site that absorbs fluorescence in the compound group β.

Claims (7)

A coloring composition comprising (A) a colorant and (B) a polymerizable compound,
(A) The coloring composition in which a coloring agent contains the combination of following (i) or (ii).
(I) a polymer (α4 ) containing, as a structural unit, a monomer (α3 ) having at least one chromophore selected from a xanthene chromophore and a cyanine chromophore and a polymerizable group;
It was Awa set of <br/> a monomer (.beta.3) having at least one chromophore and a polymerizable group selected from triarylmethane chromophores and anthraquinone chromophores
(Ii) a monomer (α3) having at least one chromophore selected from a xanthene chromophore and a cyanine chromophore and a polymerizable group;
A polymer (β4) comprising, as a structural unit, a monomer (β3) having at least one chromophore selected from a triarylmethane chromophore and an anthraquinone chromophore and a polymerizable group;
Combination   The coloring composition according to claim 1, wherein the monomer (β3) is an ethylenically unsaturated monomer having at least one chromophore selected from a triarylmethane chromophore and an anthraquinone chromophore.   The coloring composition according to claim 1 or 2, wherein the monomer (α3) is an ethylenically unsaturated monomer having at least one chromophore selected from a xanthene chromophore and a cyanine chromophore. A coloring composition comprising (A) a colorant and (B) a polymerizable compound,
(A) The coloring composition in which a coloring agent contains the combination of following (iii) or (iv).
(Iii) a polymer (α2 ) containing a monomer (α1 ) having a fluorescent site and a polymerizable group as a structural unit;
A combination of a monomer (β1 ) having a site that absorbs fluorescence and a polymerizable group
(Iv) a monomer (α1) having a fluorescent site and a polymerizable group;
A polymer (β2) containing, as a structural unit, a monomer (β1) having a site that absorbs fluorescence and a polymerizable group;
Combination Furthermore, the coloring composition of any one of Claims 1-4 containing (C) binder resin. The colored cured film formed using the coloring composition of any one of Claims 1-5 . A display element comprising the colored cured film according to claim 6 .