CN104880910B - Coloring composition, colored cured film, and display element - Google Patents

Abstract

The invention relates to a coloring composition, a coloring cured film and a display element, and provides a coloring composition suitable for forming a coloring cured film with excellent heat resistance and high contrast. The coloring composition contains (A) a coloring agent and (C) a polymerizable compound, wherein the coloring agent contains a polymer having a site that generates fluorescence and a site that absorbs the fluorescence.

Description

Coloring composition, colored cured film, and display element

Technical Field

The present invention relates to a coloring composition, a colored cured film, and a display device, and more particularly, to a coloring composition used for forming a colored cured film used for a transmissive or reflective color liquid crystal display device, a solid-state imaging device, an organic EL display device, an electronic paper, or the like, a colored cured film formed using the coloring composition, and a display device provided with the colored cured film.

Background

In the production of color filters using colored radiation-sensitive compositions, there is known a method in which a pigment-dispersed colored radiation-sensitive composition is applied to a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape (hereinafter referred to as "exposure") and developed to obtain pixels of each color (see, for example, patent documents 1 to 2). Further, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is known (for example, see patent document 3). Further, a method of obtaining pixels of each color by an ink jet method using a pigment dispersion type 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 achieve these demands, techniques using dyes as colorants have been studied. However, generally, when a dye is used, a problem often occurs in heat resistance and the like, as compared with the case of using a pigment as a colorant. Under such circumstances, as a coloring composition capable of forming a colored pattern excellent in heat resistance and the like, for example, patent document 5 proposes a coloring composition containing a dye multimer as a colorant.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2-144502

Patent document 2: japanese laid-open patent publication No. 3-53201

Patent document 3: japanese laid-open patent publication No. 6-35188

Patent document 4: japanese patent laid-open No. 2000-310706

Patent document 5: japanese patent laid-open publication No. 2013-28764

Disclosure of Invention

However, according to the studies of the present inventors, it has been found that a colored pattern formed using the colored composition 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.

Accordingly, an object of the present invention is to provide a coloring composition suitable for forming a colored cured film having excellent heat resistance and high contrast. Another object of the present invention is to provide a colored cured film formed using the colored composition, and a display device including the colored cured film.

The present inventors have conducted extensive studies and as a result, have found that the above-mentioned problems can be solved by using, as a colorant, a polymer having a site that generates fluorescence and a site that absorbs the fluorescence.

That is, the present invention provides a coloring composition containing (a) a colorant and (B) a polymerizable compound, wherein the colorant (a) contains a polymer having a site that generates fluorescence and a site that absorbs the fluorescence (hereinafter referred to as "polymer (a 1)").

The present invention also provides a coloring composition comprising (a) a coloring agent and (B) a polymerizable compound, wherein the coloring agent (a) comprises a polymer having at least 1 chromophore selected from the group consisting of a xanthene chromophore and a cyanine chromophore and at least 1 chromophore selected from the group consisting of a triarylmethane chromophore and an anthraquinone chromophore.

The present invention also provides a colored cured film formed using the colored composition, and a display element provided with the colored cured film. Here, the "colored cured film" refers to pixels of each color, a black matrix, a black spacer, and the like used in a display element and a solid-state imaging element.

When the coloring composition of the present invention is used, a colored cured film having excellent heat resistance and high contrast can be formed.

Therefore, the coloring composition of the present invention can be very suitably used for producing display devices such as color liquid crystal display devices, organic EL display devices, and electronic paper, and solid-state imaging devices such as CMOS image sensors.

Detailed Description

The present invention will be described in detail below.

Coloring composition

The constituent components of the coloring composition of the present invention will be described in detail below.

- (A) coloring agent-

The coloring composition of the present invention contains the polymer (a1) as a colorant.

The polymer (a1) is not particularly limited as long as it has a site that generates fluorescence and a site that absorbs the fluorescence, and is preferably a copolymer containing an ethylenically unsaturated monomer having a site that generates fluorescence (hereinafter referred to as "unsaturated monomer (a 1)") and an ethylenically unsaturated monomer having a site that absorbs the fluorescence (hereinafter referred to as "unsaturated monomer (a 2)"). Here, the copolymer containing the unsaturated monomer (a1) and the unsaturated monomer (a2) means a polymer having the unsaturated monomer (a1) and the unsaturated monomer (a2) as structural units.

Examples of the site that generates fluorescence include xanthene chromophore and cyanine chromophore. Examples of the site that absorbs fluorescence include triarylmethane chromophore and anthraquinone chromophore.

Examples of the unsaturated monomer (a1) include compounds represented by the following formula (1-1). Examples of the unsaturated monomer (a2) include compounds represented by the following formula (1-2).

(in the formula (1-1),

R¹independently of one another, represents a hydrogen atom or a methyl group.

X¹Independently of each other, a 2-valent hydrocarbon group directly bonded, substituted or unsubstituted, or a 2-valent group in which the 2-valent hydrocarbon group and 1 or more linking groups containing atoms other than carbon atoms and hydrogen atoms are combined.

P represents a site where fluorescence is generated.

g represents an integer of 1 or more. )

(in the formula (1-2),

R²represents a hydrogen atom or a methyl group.

X²Represents a 2-valent hydrocarbon group directly bonded, substituted or unsubstituted, or a 2-valent group in which the 2-valent hydrocarbon group and 1 or more linking groups containing atoms other than carbon atoms and hydrogen atoms are combined.

Q represents a site that absorbs fluorescence.

h represents an integer of 1 or more. )

R¹And R²A hydrogen atom or a methyl group can be appropriately selected.

As X¹And X²Examples of the 2-valent hydrocarbon group of (2) include a 2-valent aliphatic hydrocarbon group, a 2-valent alicyclic hydrocarbon group, and a 2-valent aromatic hydrocarbon group. In the present specification, the term "alicyclic hydrocarbon group" means a concept excluding aliphatic hydrocarbon groups having no cyclic structure. The 2-valent aliphatic hydrocarbon group may be either a straight chain or a branched chain, and the 2-valent aliphatic hydrocarbon group and the 2-valent alicyclic hydrocarbon group may be saturated hydrocarbon groups or unsaturated hydrocarbon groups. In the present specification, "alicyclic hydrocarbon group" and "aromatic hydrocarbon group" mean a concept including not only a group consisting of only a ring structure but also a group in which the ring structure is further substituted with a 2-valent aliphatic hydrocarbon group, and the structure may include at least an alicyclic hydrocarbon or an aromatic hydrocarbon.

Examples of the 2-valent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 2 to 12, and further preferably 2 to 6. Specific examples thereof include methylene, ethane-1, 1-diyl, ethane-1, 2-diyl, propane-1, 1-diyl, propane-1, 2-diyl, propane-1, 3-diyl, propane-2, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, 2-methylpropane-1, 2-diyl, 2-dimethylpropane-1, 3-diyl, ethylene-1, 1-diyl and ethylene-1, 2-diyl, propylene-1, 3-diyl, propylene-2, 3-diyl, 1-butene-1, 2-diyl, 1-butene-1, 3-diyl, 1-butene-1, 4-diyl, 2-pentene-1, 5-diyl, 3-hexene-1, 6-diyl, and the like.

Examples of the 2-valent alicyclic hydrocarbon group include a cycloalkylene group and a cycloalkenylene group, and the number of carbon atoms thereof is preferably 3 to 20, and more preferably 3 to 12. Specific examples thereof include monocyclic hydrocarbon ring groups such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclobutenyl, cyclopentenylene and cyclohexenylene, norbornyl groups such as 1, 4-norbornylene and 2, 5-norbornylene, bridged hydrocarbon groups such as 1, 5-adamantylene and 2, 6-adamantylene, and the like.

The 2-valent aromatic hydrocarbon group includes, for example, an arylene group, preferably a monocyclic to 3-membered arylene group having 6 to 14 carbon atoms. Specific examples thereof include phenylene, biphenylene, naphthylene, phenanthrene, anthracenylene, and the like.

Further, as the linking group, for example, a 2-valent group in which a 2-valent hydrocarbon group and 1 or more linking groups containing atoms other than carbon atoms and hydrogen atoms are combined may be mentioned-O-, -S-, -SO₂-、-CO-、-COO-、-OCO-、-CONR³-(R³Hydrogen atom or alkyl group having 1 to 6 carbon atoms), -NR³-(R³The same as the above meaning), 1 species or 2 or more species may be contained. The bonding position of the linking group is arbitrary, and for example, it may be present between the terminal ends of the 2-valent hydrocarbon group or the C-C bond, and among these, it is preferable to have one terminal end or the C-C bond. The number of carbon atoms mentioned on page 4, line 23 to page 5, line 12 of the specification means the number of carbon atoms divided by the number of constituent atomsThe total number of carbon atoms of the moiety other than carbon atoms of the linking group.

Specific examples of the 2-valent hydrocarbon group having the above-mentioned linking group between C and C bonds include, for example, -CH₂-CH₂-CH₂-COO-CH₂-CH₂-、-CH₂-CH(-CH₃)-CH₂-COO-CH₂-CH₂-、-CH₂-CH₂-CH₂-OCO-CH₂-CH₂-、-CH₂-CH₂-CH₂-CH₂-COO-CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH₂-O-CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₂-、-(CH₂)₅-COO-(CH₂)₁₁-CH₂-、-CH₂-CH₂-CH₂-C-(COO-CH₂-CH₃)₂-、-CH₂-CH₂-O-CH₂-CH₂-、-CH₂-CH₂-CH₂-O-CH₂-CH₂-、-(CH₂-CH₂-O)_n-CH₂- (n is an integer of 1 to 8), - (CH)₂-CH₂-CH₂-O)_m-CH₂- (m is an integer of 1 to 5), -CH₂-CH(CH₃)-O-CH₂-CH₂-、-CH₂-CH-(OCH₃)-、-CH₂-CH₂-COO-CH₂-CH₂-O-CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH₂-O-CO-CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-COO-CH₂-CH₂-O-CH₂-CH₂-O-CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-NH-COO-CH₂-CH₂-、-CH₂-CH₂-OCO-CH₂-and the like, but are not limited to these.

Specific examples of the group having a ring structure in which a 2-valent hydrocarbon group is bonded to the linking group include, but are not limited to, the following groups.

Examples of the substituent having a 2-valent hydrocarbon group include a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxy group may be either a straight chain or a branched chain, and the number of carbon atoms is preferably 1 to 6. Specific examples thereof include methoxy, ethoxy, propoxy and butoxy groups. The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group, a benzyloxy group and the like. Examples of the substituent of the alkoxy group and the aryloxy group include a halogen atom, a nitro group, a hydroxyl group, an amino group, a carboxyl group, and a sulfanyl group. When the 2-valent hydrocarbon group is a 2-valent aromatic hydrocarbon group, the group may be substituted with a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. The number of carbon atoms of the alkyl group and alkenyl group is preferably 1 to 6, specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hexyl and the like, and specific examples of the alkenyl group include vinyl, 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 2-ethyl-2-butenyl and the like. Examples of the substituent for the alkyl group and the alkenyl group include the same substituents as those for the above-mentioned 2-valent hydrocarbon group.

The P is not particularly limited as long as it is a group derived from a compound that generates fluorescence, but a xanthene chromophore or a cyanine chromophore is preferable. The compound represented by the above formula (1-1) is preferably an ethylenically unsaturated monomer having at least 1 chromophore selected from xanthene chromophores and cyanine chromophores. The xanthene chromophore or cyanine chromophore is combined from xantheneThe residue of the substance or cyanine compound, which is obtained by losing g hydrogen atoms, is a residue which is equivalent to g X atoms of the above formula (1-1)¹A linked residue.

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 preferable. As the compound represented by the above formula (1-2), an ethylenically unsaturated monomer having at least 1 chromophore selected from triarylmethane chromophores and anthraquinone chromophores is preferable. The triarylmethane chromophore or the anthraquinone chromophore is a residue obtained by removing h hydrogen atoms from a triarylmethane compound or an anthraquinone compound, and is h X atoms which are similar to those of the above formula (1-2)²A linked residue.

g and h independently of one another represent an integer of 1 or more, preferably 1 or 2.

Examples of The xanthene compound, cyanine compound, triarylmethane compound, and anthraquinone compound include dyes classified as dyes (Dye) in The color index (c.i.; issued by The Society of Dyers and Colourists company). 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, and the like can be used, and from the viewpoint that a compound represented by the above formula (1-1) or a compound represented by the above formula (1-2) having excellent reactivity can be easily produced, acid dyes, oil-soluble dyes, and basic dyes are preferably used.

The acid dye is a dye classified as c.i. acid in the color index, and the direct dye is a dye classified as c.i. direct in the color index. As the oil-soluble dye, a dye classified as c.i. solvent in the color index, and as the basic dye, a dye classified as c.i. basic in the color index.

The xanthene compound, cyanine compound, triarylmethane compound, and anthraquinone compound will be described below.

The xanthene compound is preferably a compound having a structure represented by the following formula (2), and specific examples thereof include xanthene-based basic dyes such as c.i. basic violet 10 (rhodamine B).

In the formula (2), the following reaction conditions are satisfied,

R¹¹、R¹²、R¹³and R¹⁴Independently of each other, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a group having a linking group containing atoms other than carbon and hydrogen atoms between the C-C bonds of the hydrocarbon group, or a substituted or unsubstituted heterocyclic group.

R¹⁵And R¹⁶Independently of each other, represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

R¹⁷represents-SO₃ ^-、-SO₃H、-SO₃M、-SO₃R¹⁸、-CO₂ ^-、-CO₂H、-CO₂M、-CO₂R¹⁹、-SO₂NHR²⁰or-SO₂NR²¹R²²。

R represents an integer of 0 to 5, and when R is an integer of 2 or more, a plurality of R¹⁷May be the same or different.

R¹⁸、R¹⁹And R²⁰Independently represent a substituted or unsubstituted hydrocarbon group or a group having a linking group containing atoms other than carbon and hydrogen between the C-C bonds of the hydrocarbon group.

R²¹And R²²Independently represent a substituted or unsubstituted hydrocarbon group, or a group having a linking group containing atoms other than carbon and hydrogen between the C-C bonds of the hydrocarbon group, or R²¹And R²²And substituted or unsubstituted heterocyclic groups bonded to each other.

M represents a sodium atom or a potassium atom. Angle (c)

As R¹¹～R¹⁶And R¹⁸～R²²Examples of the hydrocarbon group in (3) 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. The aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 8 carbon atoms. The aliphatic hydrocarbon group may be linear or branched. Examples of the alkyl group include heptyl, octyl, nonyl, decyl, undecyl, 1-methyldecyl, dodecyl, 1-methylundecyl, 1-ethyldecyl, tridecyl, tetradecyl, tert-dodecyl, pentadecyl, 1-heptyloctyl, hexadecyl, and octadecyl groups in addition to the above-mentioned specific examples. Examples of the alkenyl group include, in addition to the above-mentioned specific examples, 2-octenyl, (4-vinyl) -5-hexenyl, 2-decenyl and the like. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-pentynyl group, a 3-pentynyl group, a 1-hexynyl group, a 2-ethyl-2-butynyl group, a 2-octynyl group, a (4-ethynyl) -5-hexynyl group, and a 2-decynyl group.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms. The alicyclic hydrocarbon group may be saturated or unsaturated, and examples thereof include a cycloalkyl group, a cycloalkenyl group, a fused polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spiro cyclic hydrocarbon group, and a cyclic terpene hydrocarbon group. More specifically, there may be mentioned cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, tert-butylcyclohexyl, cycloheptyl and cyclooctyl; cycloalkenyl such as 1-cyclohexenyl;

condensed polycyclic hydrocarbon groups such as tricyclodecyl, decahydro-2-naphthyl, and adamantyl; tricyclic [5.2.1.0^2,6]Bridged hydrocarbon groups such as a decane-8-yl group, pentacyclopentadecyl group, isobornyl group, dicyclopentenyl group, tricyclopentenyl group and the like; from spiro [3,4 ]]Heptane, spiro [3,4 ] s]1-valent group or other spirocyclic hydrocarbon group obtained by losing 1 hydrogen atom from octane; from pair

And cyclic terpene hydrocarbon groups such as 1-valent groups obtained by losing 1 hydrogen atom, such as alkane, limonene, carane, and the like. Among the cycloalkyl groups and cycloalkenyl groups, the number of carbon atoms is more preferably 3 to 12.

The aromatic hydrocarbon group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. The "aryl" refers to monocyclic to 3-cyclic aromatic hydrocarbon groups, and examples thereof include phenyl, naphthyl, anthryl, phenanthryl, azulenyl, and 9-fluorenyl groups, and among them, phenyl and naphthyl groups are preferable.

In addition, R¹¹、R¹²、R¹³、R¹⁴、R¹⁸、R¹⁹、R²⁰、R²¹And R²²The hydrocarbon group in (2) may have a linking group containing atoms other than carbon and hydrogen atoms between the C-C bonds, and when having a linking group, a group having the above-mentioned linking group between the C-C bonds of the aliphatic hydrocarbon group is preferable. Specific examples of the linking group include the same groups 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 2 or more hetero atoms (e.g., nitrogen atom, oxygen atom, sulfur atom) of the same kind or different kinds within the ring. The heterocyclic group is preferably a heterocyclic group having 3 to 10 carbon atoms, and examples thereof include nitrogen-containing alicyclic heterocyclic groups such as pyrrolidinyl, imidazolidinyl, pyrazolidinyl, morpholinyl, thiomorpholinyl (テ オ モ ル ホ リ ニ ル yl), piperidinyl, piperidino, piperazinyl, and homopiperazinyl (ホ モ ピ レ ラ ジ ニ ル yl), other alicyclic heterocyclic groups such as 1, 3-dioxolan-2-yl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, phthalazinyl, diazanaphthyl, quinoxalinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, benzothiazolyl, and the like,

Nitrogen-containing aromatic heterocyclic groups such as an oxazolyl group, an indolyl group, an indazolyl group, a benzimidazolyl group and a phthalimidyl group, and other aromatic heterocyclic groups such as a thienyl group, a furyl group, a pyranyl group and a purinyl group.

As R²¹And R²²Examples of the heterocyclic group formed by bonding to each other include the same heterocyclic groups as described above.

As R¹¹～R¹⁶And R¹⁸～R²²Examples of the substituent for the hydrocarbon group in (1) include a halogen atom, a hydroxyl group, a cyano group, a formyl group, a carboxyl group, a nitro group, an amino group and a di (C)_1-8Alkyl) amino, diarylamino, C_1-8Alkoxy radical, C_6-10Aryloxy radical, C_2-8Alkoxycarbonyl group, C_1-8Alkylthio radical, C_6-10Arylthio, tri (C)_1-8Alkyl) silyl, mercapto, allyl, C_1-8Alkylsulfonyl radical, C_1-8Alkylsulfamoyl, heterocyclic group, aromatic hydrocarbon group and the like, and the alicyclic hydrocarbon group, heterocyclic group and aromatic hydrocarbon group may be substituted with aliphatic hydrocarbon group. These substituents may further have a substituent. The position and number of the substituent are arbitrary, and when 2 or more substituents are present, the substituents may be the same or different. R is defined as¹¹～R¹⁴And R is a substituent of a heterocyclic group of²¹And R²²Examples of the substituent of the heterocyclic group bonded to each other include R¹¹～R¹⁶And R¹⁸～R²²The substituents of the hydrocarbon group in (1) are the same.

Wherein, as R¹¹、R¹²、R¹³And R¹⁴Preferably, the alkyl group has 1 to 8 carbon atoms or the aryl group has 6 to 10 carbon atoms.

As R¹⁵And R¹⁶Preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

As R¹⁷preferably-SO₃H、-SO₃R¹⁸、-CO₂H、-CO₂R¹⁹、-SO₂NHR²⁰or-SO₂NR²¹R²²In addition, as R¹⁸、R¹⁹、R²⁰、R²¹And R²²Preferably, an alkyl group having 1 to 8 carbon atoms.

r is preferably 1 or 2.

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

When the structure represented by the formula (2) is cationic, the xanthene compound having the structure has an anion so as to be electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, a methide anion, and a hydroxide ion.

When the structure represented by the formula (2) is anionic, the xanthene compound having the structure has a cation in an electrically neutral manner. Examples of the cation include protons, metal cations, and,Cations, and the like. Examples of the metal cation include a 1-valent metal cation such as a lithium ion, a sodium ion, a potassium ion, a rubidium ion, and a cesium ion, and a 2-valent metal cation such as a magnesium ion, a calcium ion, a strontium ion, and a barium ion. As

Examples of the cation include ammonium cation, and the like,

Cations, and the like. Specific examples of the ammonium cation include cations in the compounds described in paragraph [ 0045 ] of Japanese patent laid-open publication No. 2011-138094, and the like

Specific examples of the cation include those described in paragraphs [ 0038 ] to [ 0040 ] of Japanese patent laid-open publication No. 2013-190776.

The cyanine compound is preferably a compound having a structure represented by the following formula (3), and specific examples thereof include cyanine basic dyes such as c.i. basic red 12.

In the formula (3), the following reaction conditions are satisfied,

R³¹and R³²Independently of one another, represent a substituted or unsubstituted hydrocarbon group.

R³³～R³⁵Independently of each other, represents a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group. Multiple existence of R³³And R³⁴May be the same or different.

Ring Z¹And ring Z²Independently of one another, represent a substituted or unsubstituted aromatic hydrocarbon ring.

G¹And G²Independently of one another represents-O-, -S-or-CR³⁶R³⁷-. Wherein R is³⁶And R³⁷Independently of one another, represent a substituted or unsubstituted hydrocarbon group.

s represents an integer of 1 to 3. Angle (c)

As R³¹～R³⁷Examples of the hydrocarbon group in (3) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Specific examples thereof include the same hydrocarbon groups as those in the formula (2), and the same substituents may be mentioned as the substituents.

Ring Z¹And ring Z²The aromatic hydrocarbon ring in (3) may be a monocyclic aromatic hydrocarbon ring or a polycyclic aromatic hydrocarbon ring, and the number of carbon atoms is preferably 6 to 20, more preferably 6 to 10. Specific examples thereof include benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, tetracene ring, triphenylene ring, and the like. Examples of the substituent of the aromatic hydrocarbon ring include the same substituents as those of the hydrocarbon group in the formula (2).

Wherein, as R³¹And R³²The hydrocarbon group in (1) is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms.

As R³³～R³⁵Preferably a hydrogen atom.

As ring Z¹And ring Z²Preferably a benzene ring.

As G¹And G²preferably-O-, -CR³⁶R³⁷-, as R³⁶And R³⁷The alkyl group has preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

s is preferably 1 or 2, more preferably 1.

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

When the structure represented by the formula (3) is cationic, the cyanine compound having the structure has an anion that is electrically neutral. When the structure represented by the formula (3) is anionic, the cyanine compound having the structure has a cation in a charge-neutral manner. Specific examples of such anions and cations include the same ions as exemplified in the above formula (2).

Examples of the triarylmethane compound include a diaminotriarylmethane dye, a triaminotriarylmethane dye, and an rosolic acid dye having an OH group. Among them, from the viewpoint of excellent color tone and sunlight fastness compared with other dyes, a diaminotriarylmethane dye and a triaminotriarylmethane dye are preferable. More preferred examples of the triarylmethane compound include compounds having a structure represented by the following formula (4). Note that, the structure represented by the following formula (4) includes various resonance structures, and in the present specification, these resonance structures are equivalent to the structure represented by the following formula (4).

In the formula (4), the following reaction conditions are satisfied,

y meterRepresents a hydrogen atom, a substituted or unsubstituted hydrocarbon group or-NR⁵⁹R⁶⁰。

R⁴¹～R⁴⁴And R⁵⁹～R⁶⁰Independently of each other, represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

R⁴⁵～R⁵²Represents a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group, or-COOR'. Wherein R' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

Ar represents a substituted or unsubstituted aromatic hydrocarbon group. Angle (c)

As Y, R⁴¹～R⁵²、R⁵⁹～R⁶⁰Examples of the hydrocarbon group in R' include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include the same hydrocarbon groups as those in the formula (2), and the same substituents may be mentioned as the substituents.

The aromatic hydrocarbon group of Ar preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Specific examples thereof include phenylene, naphthylene, biphenylene, anthracenylene and the like. Examples of the substituent for the aromatic hydrocarbon group include the same substituents as those for the hydrocarbon group in the formula (2), and among them, a halogen atom is preferable.

Wherein, as R⁴¹～R⁴⁴、R⁵⁹～R⁶⁰And R', preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

As R⁴⁵～R⁵²Preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms.

Ar is preferably phenylene or naphthylene.

Y is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

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

[ in the formulae (4-1) and (4-2),

Y¹independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or-NR⁶¹R⁶²。

R⁵³～R⁵⁶And R⁶¹～R⁶²Independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R⁵⁷And R⁵⁸Independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. Angle (c)

As R⁵³～R⁵⁶More preferred is an alkyl group having 1 to 4 carbon atoms, and particularly preferred is a methyl group or an ethyl group.

As R⁵⁷And R⁵⁸Preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

As R⁶¹～R⁶²Preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As Y¹Preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Specific examples of the triarylmethane compound having a 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, the triarylmethane compound having the structure has an anion so as to be electrically neutral. When the structure represented by the formula (4) is anionic, the triarylmethane compound having the structure has a cation in an electrically neutral manner. Specific examples of such anions and cations include the same ions as exemplified in the above formula (2).

The anthraquinone compound is preferably a compound having a structure represented by the following formula (5-1) or (5-2), and specific examples thereof include anthraquinone-based oil-soluble dyes such as C.I. solvent Green 3.

In the formula (5-1),

R⁷¹and R⁷²Independently of each other, represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Angle (c)

In the formula (5-2),

R⁸¹and R⁸²Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

R⁸³Represents a substituted or unsubstituted 2-valent hydrocarbon group. Angle (c)

R⁸⁴、R⁸⁵And R⁸⁶Independently of one another, represent a substituted or unsubstituted hydrocarbon group. Angle (c)

As R⁷¹、R⁷²、R⁸¹、R⁸²And R⁸⁴～R⁸⁶Examples of the hydrocarbon group in (3) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Specific examples thereof include the same groups as those exemplified in formula (2), and the same groups may be mentioned as substituents.

As R⁸³Examples of the 2-valent hydrocarbon group in (1) include a 2-valent aliphatic hydrocarbon group, a 2-valent alicyclic hydrocarbon group, and a 2-valent aromatic hydrocarbon group. Specific examples thereof include the same hydrocarbon groups as exemplified for the 2-valent hydrocarbon groups of the formulae (1-1) and (1-2), and the same substituents may be mentioned for the substituents.

Wherein, as R⁷¹And R⁷²The alkyl group is 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, and more preferably a hydrogen atom, or a substituted or unsubstituted phenyl group. Examples of the substituent for the alkyl group include a halogen atom, a hydroxyl group, a cyano group and the like, and examples of the substituent for the aryl group and the phenyl group include a halogen atom, a hydroxyl group, a cyano group, an alkyl group having 1 to 6 carbon atoms and the like.

As R⁸¹、R⁸²、R⁸⁴、R⁸⁵And R⁸⁶Preferably a hydrogen atom, orThe alkyl group having 1 to 6 carbon atoms is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the substituent for the alkyl group include the same substituents as described above.

As R⁸³The alkanediyl group has preferably 1 to 20 carbon atoms, and more preferably 2 to 8 carbon atoms. Examples of the substituent for the alkanediyl group include X of the formulae (1-1) and (1-2) described above¹And X²The same substituents as in (1).

Specific examples of the anthraquinone compound having a 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, may be used

Xanthene acid dyes such as c.i. acid red 51 (erythrosine), c.i. acid red 52 (acid rhodamine), c.i. acid red 87 (eosin G), c.i. acid red 92 (acid phloxine PB), c.i. acid red 289, c.i. acid red 388, rose bengal B (food red No. 5), acid rhodamine G, and c.i. acid violet 9;

xanthene oil-soluble dyes such as c.i. solvent red 35, c.i. solvent red 36, c.i. solvent red 42, c.i. solvent red 43, c.i. solvent red 44, c.i. solvent red 45, c.i. solvent red 46, c.i. solvent red 47, c.i. solvent red 48, c.i. solvent red 49, c.i. solvent red 72, c.i. solvent red 73, c.i. solvent red 109, c.i. solvent red 140, c.i. solvent red 141, c.i. solvent red 237, c.i. solvent red 246, c.i. solvent violet 2, c.i. solvent violet 10, and the like;

xanthene-based basic dyes such as c.i. basic red 1 (rhodamine 6GCP) and c.i. basic red 8 (rhodamine G).

Further, as the cyanine compound, for example, cyanine-based basic dyes such as c.i. basic red 13, c.i. basic red 14, c.i. basic violet 7, c.i. basic yellow 11, c.i. basic yellow 13, c.i. basic yellow 21, c.i. basic yellow 28, and c.i. basic yellow 51 may be used.

In addition, as triarylmethane compounds, for example, can also be used

C.i. acid blue 1, c.i. acid blue 3, c.i. acid blue 5, c.i. acid blue 7, c.i. acid blue 9, c.i. acid blue 11, c.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: 1. triarylmethane-based acid dyes such as 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. acid blue 147, c.i. acid blue 269, c.i. acid blue 123, c.i. acid blue 213, c.i. direct blue 41, c.i. acid violet 17, c.i. acid violet 19, c.i. 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, and the like;

triarylmethane-based basic dyes such as c.i. basic violet 1 (methyl violet), c.i. basic violet 3 (crystal violet), c.i. basic violet 14 (Magenta), c.i. basic blue 1 (basic cyanine 6G), c.i. basic blue 5 (basic cyanine EX), c.i. basic blue 7 (victoria pure blue BO), c.i. basic blue 26 (victoria blue B conc.), c.i. basic green 1 (brilliant green GX), c.i. basic green 4 (malachite green), and the like;

triarylmethane direct dyes such as c.i. direct blue 41, and the like.

Further, as the anthraquinone compound, for example, it is also possible to use

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. 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: 1. anthraquinone acid dyes such as c.i. acid blue 140, c.i. acid blue 150, c.i. acid blue 175, c.i. acid blue 215, c.i. acid blue 230, c.i. acid blue 277, c.i. acid blue 344, c.i. acid violet 41, c.i. acid violet 42, c.i. acid violet 43, c.i. acid green 25, and c.i. acid green 27;

c.i. direct violet 17 and other direct dyes;

anthraquinone oil-soluble dyes such as c.i. solvent red 172, c.i. solvent red 222, and c.i. solvent violet 60.

The method for synthesizing the compound represented by the above formula (1-1) or the compound represented by the above formula (1-2) is not particularly limited, and conventionally known methods can be used. For example, it can be obtained as follows: the dye is synthesized by introducing a group having an ethylenically unsaturated group into the basic skeleton of the above dye having a functional group by a general organic synthesis method, or after introducing a group having an ethylenically unsaturated group into a raw material for synthesizing the dye. More specifically, reference may be made to the descriptions of Japanese patent application laid-open Nos. 2013-178478, 2013-173850, 2013-210621, and 2013-028764.

Then, the polymer (A1) can be produced by copolymerizing the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2). The copolymerization reaction may be carried out by a conventionally known method, and for example, the same method as that for the binder resin (C) described later can be used.

The ratio of the content of the site that generates fluorescence to the content of the site that absorbs fluorescence in the polymer (A1) is preferably 99/1 to 50/50, more preferably 97/3 to 60/40, still more preferably 95/5 to 70/30, and still more preferably 90/10 to 70/30 in terms of a molar ratio (former/latter). When the polymer (a1) is a copolymer containing an unsaturated monomer (a1) and an unsaturated monomer (a2), the molar ratio (p/q) of the unsaturated monomer (a1) is preferably within the above range, where p is the number of moles of the monomer and q is the number of moles of the monomer (a 2).

In particular, when the polymer (a1) is a copolymer containing an unsaturated monomer (a1) and an unsaturated monomer (a2), the copolymerization ratio (p/q) of the unsaturated monomer (a1) and the unsaturated monomer (a2) is preferably 97/3 to 40/60, more preferably 95/5 to 65/35, and still more preferably 90/10 to 70/30, in terms of mass ratio.

The polymer (a1) may have, as structural units, other copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as "unsaturated monomer (a 3)") than the unsaturated monomer (a1) and the unsaturated monomer (a 2).

Specific examples of the unsaturated monomer (a3) include

Ethylenically unsaturated monomers having a carboxyl group such as (meth) acrylic acid, maleic anhydride, succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester, ω -carboxy polycaprolactone mono (meth) acrylate, p-vinylbenzoic acid;

n-substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide;

aromatic vinyl compounds such as styrene, α -methylstyrene, p-hydroxystyrene, p-hydroxy- α -methylstyrene, p-vinylbenzyl glycidyl ether, and 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 2-10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2-10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclic [5.2.1.0 ] meth) acrylate^2,6](meth) acrylates such as decan-8-yl ester, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of p-cumylphenol, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3- [ (meth) acryloyloxymethyl ] oxetane, and 3- [ (meth) acryloyloxymethyl ] -3-ethyloxetane;

cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0^2,6]Vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane;

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

Among them, the unsaturated monomer (a3) is preferably an ethylenically unsaturated monomer having a carboxyl group, and a (meth) acrylate, from the viewpoints of heat resistance, solvent resistance, migration resistance, and dispersibility.

When the polymer (a1) is a copolymer further containing an unsaturated monomer (A3) as a structural unit, the copolymerization ratio of the unsaturated monomer (A3) in the entire structural units of the polymer (a1) is preferably as follows. 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 constituent units. By copolymerizing the unsaturated monomer (a3) in such a range, a colored composition having excellent heat resistance, solvent resistance, migration resistance and dispersibility can be easily obtained.

The weight average molecular weight (Mw) of the polymer (A1) in terms of polystyrene as measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) is usually 1000 to 100000, preferably 3000 to 50000, and more preferably 3000 to 10000. This configuration can improve contrast, heat resistance, solvent resistance, migration resistance, film properties, electrical properties, pattern shape, and resolution.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (A1) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. The Mn referred to herein is a number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The coloring composition of the present invention may be used by mixing a colorant other than the polymer (a 1). The other colorant is not particularly limited, and the color and material may be appropriately selected according to the application. Examples of the other colorant include pigments and dyes other than the polymer (a1), and the other colorants may be used alone or in combination of 2 or more. Among them, from the viewpoint of obtaining a pixel having high luminance, contrast, and coloring power, an organic pigment is preferable as the pigment, and an organic dye is preferable as the dye. Examples of the organic dye include those described on page 18, line 14 to page 20, line 7 of the specification.

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

C.i. pigment red 166, c.i. pigment red 177, c.i. pigment red 224, c.i. pigment red 242, c.i. pigment red 254, c.i. pigment red 264;

c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 58, c.i. pigment green 59;

c.i. pigment blue 15: 6. c.i. pigment blue 16, c.i. pigment blue 80;

c.i. pigment yellow 14, c.i. pigment yellow 83, c.i. pigment yellow 129, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment yellow 179, c.i. pigment yellow 180, c.i. pigment yellow 185, c.i. pigment yellow 211, c.i. pigment yellow 215;

c.i. pigment orange 38;

c.i. pigment violet 23.

Further, there may be mentioned red pigments represented by the following formulae,

Examples of the pigment include lake pigments described in Japanese patent application laid-open Nos. 2001-081348, 2010-026334, 2010-237384, 2010-237569, 2011-006602, 2011-145346, and the like.

In the present invention, other pigments optionally mixed may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. These pigments can be used by modifying the particle surface with a resin as desired. Examples of the resin for modifying the particle surface of the pigment include a vehicle resin described in japanese patent application laid-open No. 2001-108817 and various commercially available resins for dispersing the pigment. As a method for coating the surface of carbon black with a resin, for example, the methods described in Japanese patent application laid-open Nos. 9-71733, 9-95625, and 9-124969 can be used. The organic pigment can be used by pulverizing the primary particles by a so-called salt mill (ソ ル ト ミ リ ン グ). As a method of salt milling, for example, a method disclosed in Japanese patent laid-open No. 8-179111 can be adopted.

In the present invention, a known dispersant and a dispersing aid may be further contained together with other colorants which may be optionally mixed. Examples of the known dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene alkylphenyl ether-based dispersant, a polyethylene glycol diester-based dispersant, a sorbitan fatty acid ester-based dispersant, a polyester-based dispersant, and an acrylic dispersant, and examples of the dispersing aid include a pigment derivative.

Such a dispersant is commercially available, and examples of the acrylic dispersant include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (BYK-Chemie, BYK), the urethane dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (BYK-Chemie, BYK), Solsperse76500(Lubrizol Chemie), the polyethyleneimine dispersant includes Solsperse24000(Lubrizol Kagaku Co., Ltd.), the polyester dispersant includes Adisper PB, Adisper PB822, Adisper 880, Adisper 24000 (BYK-Chemie, BYK), and the like, (LPBYK-Techn), and the like, (LPYK-Chemie, BYK-881, BYK-24, and the like.

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

When other colorants are contained, the content of the other colorants is preferably 70% by mass or less, more preferably 50 parts by mass or less, based on the total content of the colorants. The lower limit is not particularly limited, and may be 0.01 mass% or more.

The content of the colorant (a) is usually 3 to 70% by mass, preferably 5 to 60% by mass, and more preferably 5 to 30% by mass in the solid content of the coloring composition, from the viewpoint of forming a pixel having excellent heat resistance, solvent resistance, transfer inhibition, and high color purity, or a black matrix or black spacer having excellent light-shielding properties. The solid component herein means a component other than the solvent described later.

(B) polymerizable compound-

The polymerizable compound in the present invention means a compound having 2 or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an ethylene oxide group, a propylene oxide group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having 2 or more (meth) acryloyl groups or a compound having 2 or more N-alkoxymethylamino groups.

Specific examples of the compound having 2 or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, a polyfunctional (meth) acrylate modified with caprolactone, a polyfunctional (meth) acrylate modified with an alkylene oxide, a polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

Here, as the aliphatic polyhydric compound, for example, there can be mentioned 2-valent aliphatic polyhydric compounds such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol; aliphatic polyhydric compounds having a valence of 3 or more such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dimethacrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include dicarboxylic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride and hexahydrophthalic anhydride, and tetracarboxylic acid dianhydrides such as pyromellitic dianhydride, biphenyltetracarboxylic dianhydride and benzophenonetetracarboxylic dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [ 0015 ] to [ 0018 ] of Japanese patent laid-open No. 11-44955. Examples of the above-mentioned alkylene oxide-modified polyfunctional (meth) acrylate include bisphenol A di (meth) acrylate modified with at least 1 kind selected from ethylene oxide and propylene oxide, isocyanuric acid tri (meth) acrylate modified with at least 1 kind selected from ethylene oxide and propylene oxide, trimethylolpropane tri (meth) acrylate modified with at least 1 kind selected from ethylene oxide and propylene oxide, pentaerythritol tri (meth) acrylate modified with at least 1 kind selected from ethylene oxide and propylene oxide, pentaerythritol tetra (meth) acrylate modified with at least 1 selected from ethylene oxide and propylene oxide, dipentaerythritol penta (meth) acrylate modified with at least 1 selected from ethylene oxide and propylene oxide, dipentaerythritol hexa (meth) acrylate modified with at least 1 selected from ethylene oxide and propylene oxide, and the like.

Examples of the compound having 2 or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and benzoguanamine structure are chemical structures having 1 or more triazine rings or phenyl-substituted triazine rings as basic skeletons, and are concepts including melamine, benzoguanamine, or condensates thereof. Specific examples of the compound having 2 or more N-alkoxymethylamino groups include N, N ', N ", N ″ -hexa (alkoxymethyl) melamine, N ' -tetrakis (alkoxymethyl) benzoguanamine, N ' -tetrakis (alkoxymethyl) glycoluril, and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting (meth) acrylic acid with an aliphatic polyhydric compound having a valence of 3 or more, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional urethane (meth) acrylates, polyfunctional (meth) acrylates having a carboxyl group, N ', N ", N ″ -hexa (alkoxymethyl) melamine, and N, N' -tetrakis (alkoxymethyl) benzoguanamine are preferable. Among polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydric compound having a valence of 3 or more with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate are particularly preferable in terms of high strength of the colored layer, excellent surface smoothness of the colored layer, and less generation of dirt and film residue on the substrate and the light-shielding layer in unexposed portions; among the polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, or a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride is particularly preferable.

In the present invention, (B) the polymerizable compound may be used alone or in combination of 2 or more.

The content of the polymerizable compound (B) in the present invention is preferably 10 to 1000 parts by mass, more preferably 20 to 800 parts by mass, still more preferably 100 to 700 parts by mass, and particularly preferably 200 to 400 parts by mass, based on 100 parts by mass of the colorant (A). This makes it possible to improve curability and alkali developability.

- (C) Binder resin-

The coloring composition of the present invention may contain a binder resin (wherein the polymer (a1) is not included). This can improve the alkali solubility of the coloring composition, the adhesion to a substrate, the storage stability, and the like. The binder resin is not particularly limited as long as it is not compatible with the polymer (a1), and 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, and examples thereof include a copolymer of an ethylenically unsaturated monomer having 1 or more carboxyl groups (hereinafter referred to as "unsaturated monomer (c 1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (c 2)").

Examples of the unsaturated monomer (c1) include (meth) acrylic acid, maleic anhydride, succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester, ω -carboxy polycaprolactone mono (meth) acrylate, and p-vinylbenzoic acid.

These unsaturated monomers (c1) may be used alone or in combination of 2 or more.

Examples of the unsaturated monomer (c2) include N-substituted maleimide exemplified for the unsaturated monomer (a3), aromatic vinyl compounds, (meth) acrylic acid esters, vinyl ethers, and macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain, and specific examples thereof include the same groups as described above.

The unsaturated monomer (c2) may be used alone or in combination of 2 or more.

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, and more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (c1) in such a range, a coloring composition having excellent alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2) include copolymers disclosed in, for example, Japanese patent application laid-open Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118 and 2004-101728.

In the present invention, as disclosed in, for example, Japanese patent laid-open Nos. 5-19467, 6-230212, 7-207211, 9-325494, 11-140144, 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in a side chain is used as the binder resin.

The weight average molecular weight (Mw) of the binder resin in the present invention in terms of polystyrene as measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) is usually 1000 to 100000, preferably 3000 to 50000. In this manner, the film remaining rate, pattern shape, heat resistance, electrical characteristics, and resolution of the coating film are further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) to 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. The Mn referred to herein is a number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method, and the structure, Mw/Mn can be controlled by the methods disclosed in, for example, Japanese patent application laid-open Nos. 2003-222717, 2006-259680, and 2007/029871.

In the present invention, (C) the binder resin may be used alone or in combination of 2 or more.

In the present invention, the content of the binder resin (C) is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, based on 100 parts by mass of the colorant (A). In this manner, the alkaline developability, the storage stability of the coloring composition, and the chromaticity characteristics can be further improved.

- (D) photopolymerization initiator

The coloring composition of the present invention may contain a photopolymerization initiator. This can impart radiation sensitivity to the coloring composition. The photopolymerization initiator used in the present invention is a compound which 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, bisimidazole compounds, triazine compounds, O-acyloxime compounds, and,Salt-based compounds, benzoin-based compounds, benzophenone-based compounds, α -diketone-based compounds, polyquinone-based compounds, diazo-based compounds, imide sulfonate (imidosulfonates) -based compounds, and the like.

In the present invention, the photopolymerization initiator may be used alone or in combination of 2 or more. The photopolymerization initiator is preferably at least 1 selected from the group consisting of a thioxanthone compound, an acetophenone compound, a bisimidazole compound, a triazine compound, and an O-acyloxime compound.

Of the photopolymerization initiators preferable in the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, and 2, 4-diisopropylthioxanthone.

Specific examples of the acetophenone-based compound include 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-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 '-bis (2, 4-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, and 2,2 '-bis (2,4, 6-trichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole.

When a bisimidazole compound is used as a photopolymerization initiator, a hydrogen donor is preferably used in combination from the viewpoint of improving sensitivity. The "hydrogen donor" as used herein means a compound capable of binding by exposure to lightA compound in which a radical generated from an azole compound donates a hydrogen atom. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzo

Thiol-based hydrogen donors such as oxazole, and amine-based hydrogen donors such as 4,4 '-bis (dimethylamino) benzophenone and 4,4' -bis (diethylamino) benzophenone. In the present invention, the hydrogen donors may be used alone or in combination of 2 or more, but from the viewpoint of further improving the sensitivity, it is preferable to use 1 or more thiol-based hydrogen donors and 1 or more amine-based hydrogen donors in combination.

Specific examples of the triazine compound include 2,4, 6-tris (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2- [ 2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [ 2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -4, triazine compounds having a halogenated methyl group such as 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, and 2- (4-n-butoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine.

Specific examples of the O-acyloxime-based compound include 1- [ 4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazolyl-3-yl ] -ethanone 1- (O-acetyloxime), 1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuryl methoxybenzoyl) -9H-carbazolyl-3-yl ] -ethanone 1- (O-acetyloxime), 1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl } -9H-carbazolyl-3-yl) -ethanone 1- (O-acetyloxime), and the like. As commercially available O-acyloxime compounds, NCI-831 and NCI-930 (available from ADEKA Co., Ltd.) can be used.

When a photopolymerization initiator other than the biimidazole compound such as a acetophenone compound is used in the present invention, a sensitizer may be used in combination. Examples of such sensitizers include 4,4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminoprophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, and 4- (diethylamino) chalcone.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, and particularly preferably 1 to 100 parts by mass, based on 100 parts by mass of the polymerizable compound (B). This configuration can improve curability and film properties.

-solvent-

The coloring composition of the present invention contains the above-mentioned components (a) and (B) and optionally other components, and is usually prepared as a liquid composition by blending an organic solvent.

The organic solvent may be appropriately selected and used as long as it is a solvent which disperses or dissolves the components (a) and (B) and other components constituting the coloring composition, does not react with these components, and has appropriate volatility.

Among such organic solvents, for example, mention may be made of

(poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-ethyl 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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc.;

alkyl lactate such as methyl lactate and ethyl lactate;

(cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol and cyclohexanol;

ketone alcohols such as diacetone alcohol;

(poly) alkylene glycol monoalkyl ether acetates such as 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, and 3-methyl-3-methoxybutyl acetate;

glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether;

cyclic ethers such as tetrahydrofuran;

ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

diacetates such as propylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate;

alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate;

fatty acid alkyl esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;

aromatic hydrocarbons such as toluene and xylene;

and amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and lactams.

Of these organic solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, and the like are preferable from the viewpoints of solubility, pigment dispersibility, coatability, and the like, Ethyl pyruvate and the like.

In the present invention, the organic solvent may be used alone or in a mixture of 2 or more.

The content of the organic solvent is not particularly limited, and the total concentration of the components other than the organic solvent of the coloring composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. In this manner, a colorant dispersion liquid having good dispersibility and stability and a coloring composition having good coatability and stability can be obtained.

Additives-

The coloring composition of the present invention may contain various additives as required.

Examples of the additive include fillers such as glass and alumina; high molecular weight compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicone-based surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, adhesion promoters such as 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; antioxidants such as 2, 2-thiobis (4-methyl-6-tert-butylphenol) and 2, 6-di-tert-butylphenol; ultraviolet absorbers such as 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; a coagulation inhibitor such as sodium polyacrylate; residue improvers such as 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, and 4-amino-1, 2-butanediol; developability improvers such as mono [ 2- (meth) acryloyloxyethyl ] succinate, mono [ 2- (meth) acryloyloxyethyl ] phthalate and ω -carboxy polycaprolactone mono (meth) acrylate.

Colored cured film and method for forming same

The colored cured film of the present invention is formed using the colored composition of the present invention, and specifically, it refers to pixels of each color, black matrices, black spacers, and the like used in display devices and solid-state imaging devices.

Hereinafter, a colored cured film used for a color filter constituting a display element or a solid-state imaging element and a method for forming the same will be described.

First, the following methods can be mentioned as a method for manufacturing a color filter. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to divide the portion where the pixels are formed, as necessary. Next, a blue liquid composition of the radiation-sensitive coloring composition of the present invention is applied onto the substrate, for example, and then prebaked to evaporate the solvent, thereby forming a coating film. Next, the coating film is exposed through a photomask, and then developed with an alkaline developer to dissolve and remove the unexposed portion of the coating film. Thereafter, a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined array is formed by post-baking.

Next, using the respective radiation-sensitive coloring compositions of green or red, coating, prebaking, exposure, development, and postbaking of the respective radiation-sensitive coloring compositions were performed in the same manner as described above, and a pixel array of green and a pixel array of red were formed in this order on the same substrate. Thus, a color filter in which a pixel array of three primary colors of blue, green, and red is arranged on a substrate is obtained. In the present invention, the order of forming each color pixel is not limited to the above order.

The black matrix may be formed by forming a thin metal film of chromium or the like formed by sputtering or vapor deposition into a desired pattern by photolithography, or may be formed by using a radiation-sensitive coloring composition in which a black coloring agent is dispersed, in the same manner as in the case of forming the pixels.

Examples of the substrate used for forming a color filter include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, and the like.

These substrates may be subjected to appropriate pretreatment such as reagent treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like, as desired.

When the radiation-sensitive coloring composition is applied to a substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coat method (spin coat method), a slit die coating method (slit coating method), a bar coating method, etc. can be used, and the spin coating method and the slit die coating method are particularly preferably used.

The pre-baking is usually carried out at 70-110 ℃ for about 1-10 minutes.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying.

Examples of the light source of the radiation used for forming at least 1 kind selected from the group consisting of the pixels and the black matrix include lamp light sources such as 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 mercury lamp, and laser light sources such as an argon ion laser, a YAG laser, an XeCl excimer laser, and a nitrogen laser. As the exposure light source, an ultraviolet LED may be used. Radiation having a wavelength of 190 to 450nm is preferable.

The exposure amount of the radiation is preferably 10 to 10000J/m²。

Further, as the above-mentioned alkaline developer, for example, an aqueous solution of sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1, 8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene, or the like is preferable.

The alkaline developer may contain an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like. After the alkaline development, washing with water is usually performed.

As the developing method, a shower developing method, a spray developing method, a dip (dip) developing method, a spin-on-immersion (puddle) developing method, or the like can be used. The developing condition is preferably 5 to 300 seconds at normal temperature.

The post-baking is usually carried out at 180 to 280 ℃ for about 10 to 60 minutes.

The thickness of the pixel formed in this way is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

As a second method for manufacturing a color filter, a method of obtaining each color pixel by an ink jet method disclosed in japanese patent application laid-open nos. 7-318723 and 2000-310706 may be adopted. In this method, first, a partition wall having a light shielding function is formed on a surface of a substrate. Next, a liquid composition such as a blue thermosetting coloring composition is discharged into the formed partition wall by an ink jet device, and then, pre-baking is performed to evaporate the solvent. Next, the coating film is exposed to light as necessary, and then cured by post baking to form a blue pixel pattern.

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

The partition walls have a function of not only shielding light but also preventing color mixing of the thermosetting coloring composition of each color discharged into the partition, and have a larger film thickness than the black matrix used in the first method. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

The substrate used for forming the color filter, the light source of the radiation, and the methods and conditions for the pre-baking and the post-baking are the same as those in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately equal to the height of the partition.

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

The radiation-sensitive coloring composition of the present invention can be suitably used for forming any colored cured film of the pixels of each color, the black matrix, the black spacer, and the like used for the color filter.

The color filter including the colored cured film of the present invention thus formed is extremely high in brightness and color purity, and is therefore extremely useful in color liquid crystal display elements, color camera tube elements, color sensors, organic EL display elements, electronic paper, and the like. The display element described later may be provided with at least 1 or more colored cured films formed using the radiation-sensitive coloring composition of the present invention.

Display element

The display element of the present invention includes 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 transmissive or reflective, and may have an appropriate structure. For example, a configuration may be adopted in which a color filter is formed on a substrate different from a driving substrate on which a Thin Film Transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed face each other with a liquid crystal layer interposed therebetween. In addition, a structure may be adopted in which a substrate on which a color filter is formed on a surface of a driving substrate on which a Thin Film Transistor (TFT) is disposed and a substrate on which an ITO (indium oxide doped with tin) electrode or an IZO (mixture of indium oxide and zinc oxide) electrode are formed face each other with a liquid crystal layer interposed therebetween. The latter structure has an advantage that the aperture ratio can be significantly increased and a bright and highly fine liquid crystal display element can be obtained. In the case of the latter structure, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode or IZO electrode is formed.

The color liquid crystal display device including the colored cured film of the present invention may further include a backlight unit using a white LED as a light source, in addition to a Cold Cathode Fluorescent Lamp (CCFL). Examples of the white LED include a white LED in which a red LED, a green LED, and a blue LED are combined and white light is obtained by color mixing; a white LED which combines a blue LED, a red LED and a green phosphor and mixes the colors to obtain white light; a white LED which combines a blue LED, a red light emitting phosphor and a green light emitting phosphor and which obtains white light by color mixing; a white LED for obtaining white light by color mixing of the blue LED and the YAG phosphor; a white LED which combines a blue LED, an orange light-emitting phosphor and a green light-emitting phosphor and which mixes the light to obtain white light; and a white LED which combines an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor and mixes the light to obtain white light.

Suitable liquid crystal modes such as TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, IPS (In-plane switching) mode, VA (Vertical Alignment) mode, and OCB (optically compensated bend Alignment) mode can be applied to the color liquid crystal display element having the colored cured film of the present invention.

The organic EL display device including the colored cured film of the present invention may have any suitable structure, and examples thereof include those disclosed in japanese patent laid-open No. 11-307242.

The electronic paper provided with the colored cured film of the present invention may have any suitable structure, and examples thereof include those disclosed in japanese patent application laid-open No. 2007-41169.

Solid-state image pickup device

The solid-state imaging element of the present invention includes the colored cured film of the present invention. The solid-state imaging element of the present invention may have an appropriate configuration. For example, as one embodiment, by using the coloring composition of the present invention, a solid-state imaging element having excellent color separation and color reproducibility can be obtained by forming colored pixels (colored cured films) on a semiconductor substrate such as a CMOS substrate in the same manner as described above.

Examples

Hereinafter, embodiments of the present invention will be described in further detail with reference to examples. However, the present invention is not limited to the following examples.

< Synthesis of coloring agent >

(Synthesis example 1)

A100 mL three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was fully subjected to nitrogen substitution, 15.0g of cyclohexanone was charged, and the mixture was heated under a nitrogen stream to an internal temperature of 80. + -. 2 ℃. On the other hand, a solution prepared by mixing 4.00g of the following dye monomer (A1), 0.50g of the following dye monomer (A3), 6.00g of methyl methacrylate, 4.50g of methacrylic acid, 2.18g of 2,2' -azobis (2, 4-dimethylvaleronitrile) (trade name V-65, manufactured by Wako pure chemical industries, Ltd.) as a polymerization initiator and 45.0g of cyclohexanone was dropped using a pump for 2 hours while maintaining an internal temperature of 80. + -. 2 ℃. After the end of the dropwise addition, stirring was continued at this temperature for a further 1 hour. Thereafter, the reaction solution was cooled to room temperature, and was added dropwise to a large amount of hexane. The resulting colored solid was dried under reduced pressure at 50 ℃ to obtain 13.9g of a polymer (1). The Mw of the resulting polymer (1) was 5100. The polymer (1) corresponds to the polymer (A1).

Synthesis examples 2 to 10

Polymers (2) to (10) were obtained in the same manner as in synthesis example 1, except that in synthesis example 1, the kind and amount of monomers used in the polymerization were changed as shown in table 1. The structures of the dye monomers (A1) to (A4) are as described above. The polymers (2) to (4) and the polymers (9) to (10) correspond to the polymer (a 1). The polymers (5) to (8) were not the polymer (A1).

The symbols used in table 1 are as follows.

MMA: methacrylic acid methyl ester

MA: methacrylic acid

In Table 1, "p/q" represents a molar ratio where the number of moles of the compound represented by formula (1-1) used in polymerization is represented by p and the number of moles of the compound represented by formula (1-2) is represented by q.

The dye monomers (a1) to (a4) were synthesized by referring to the following publications.

Pigment monomer (a 1): synthesized according to synthetic example 2 described in paragraphs [ 0145 ] to [ 0146 ] of Japanese patent application laid-open No. 2013-178478. Corresponding to ethylenically unsaturated monomers with xanthene chromophores.

Pigment monomer (a 2): synthesized according to example 1-1 described in paragraphs [ 0096 ] to [ 0097 ] of Japanese patent laid-open publication No. 2013-173850. Corresponding to ethylenically unsaturated monomers with cyanine chromophores.

Pigment monomer (a 3): the dye monomer (A1-1) was synthesized according to the methods described in paragraphs [ 0149 ] to [ 0150 ] of Japanese patent application laid-open No. 2013-210621. Corresponding to ethylenically unsaturated monomers with triarylmethane chromophore.

Pigment monomer (a 4): "monomer 1" described in the paragraph [ 0501 ] of Japanese patent laid-open publication No. 2013-028764. Corresponding to an ethylenically unsaturated monomer with an anthraquinone chromophore.

< 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 prepare a colorant solution (A-1).

Preparation examples 2 to 14

In preparation example 1, colorant solutions (a-2) to (a-14) were prepared in the same manner as in preparation example 1, except that the kinds and amounts of the solute and the solvent were changed as shown in table 2. In table 2, propylene glycol monomethyl ether is described as "PGME".

[ Table 2]

< Synthesis of Binder resin >

Synthesis example 1

100 parts by mass of propylene glycol monomethyl ether acetate was charged into a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. Heating to 80 ℃, at this temperature, a mixed solution of 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, 23 parts by mass of 2-ethylhexyl methacrylate, 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) was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ℃ and polymerization was further carried out for 1 hour, thereby obtaining a binder resin solution (solid content concentration 33 mass%). The resulting binder resin had a Mw of 12200 and a Mn of 6500. This binder resin was referred to as "binder resin (C1)".

< preparation and evaluation of coloring composition >

Preparation of coloring composition

Example 1

16.5 parts by mass of a colorant solution (A-1) as a colorant (A), 23.3 parts by mass of a binder resin (C1) solution as a binder resin (C), 9.9 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as a polymerizable compound (B) (product name KAYARAD DPHA, manufactured by Nippon Kabushiki Kaisha), 1.8 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one (product name Irgacure369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator (D), 0.1 part by mass of NCI-930 (manufactured by ADEKA Co., Ltd.), 0.05 part by mass of Megafac F-554 (manufactured by DIC Co., Ltd.) as a fluorine-based surfactant and propylene glycol monomethyl ether acetate as a solvent were mixed, a coloring composition (S-1) having a solid content of 20 mass% was prepared.

Evaluation of contrast

The resulting coloring composition was applied onto a glass substrate using a spin coater, and then prebaked with a hot plate at 80 ℃ for 10 minutes to form a coating film having a thickness of 2.5. mu.m.

Next, the substrate was cooled to room temperature, and then, a high-pressure mercury lamp was used at 2000J/m without a photomask²The exposure amount of (A) is an amount for exposing each coating film to radiation including wavelengths of 365nm, 405nm and 436 nm. Thereafter, the resultant was subjected to development pressure of 1kgf/cm²(nozzle diameter 1mm) the substrate was then sprayed with a developing solution consisting of 0.04 mass% aqueous potassium hydroxide at 23 ℃ for 90 seconds. Thereafter, the substrate was cleaned with ultrapure water, air-dried, and then baked in a clean oven at 200 ℃ for 30 minutes, thereby forming a cured film for evaluation.

The substrate on which the cured film was formed was sandwiched between 2 deflection plates, and the substrate was irradiated from the back side with a fluorescent lamp (wavelength range 380 to 780nm), while the front side deflection plate was rotated, and the maximum and minimum values of transmitted light intensity were measured with a luminance meter LS-100 (manufactured by Minolta corporation). Then, the value obtained by dividing the maximum value by the minimum value is used as the contrast ratio. The evaluation results are shown in table 3. The contrast ratio is higher in value, and is better.

Evaluation of Heat resistance

The coloring composition (S-1) was applied to the SiO film having the surface on which the elution of sodium ions was prevented by using a spin coater₂After the film was formed on the soda glass substrate, it was prebaked with a heating plate at 90 ℃ for 2 minutes to form a coating film having a thickness of 2.5 μm.

Subsequently, the substrate was cooled to room temperature, and then, 400J/m was measured using a high-pressure mercury lamp through a photomask²The exposure amount of (A) is an amount for exposing each coating film to radiation including wavelengths of 365nm, 405nm and 436 nm. Thereafter, these substrates were subjected to a development pressure of 1kgf/cm²(nozzle diameter 1mm) was sprayed with a developing solution comprising 0.04 mass% aqueous potassium hydroxide at 23 ℃ and subjected to 90-second shower development. Thereafter, the substrate was cleaned with ultrapure water, air-dried, and then baked in a clean oven at 200 ℃ for 30 minutes, thereby forming a dot pattern on the substrate.

The obtained dot pattern was measured for chromaticity coordinate values (x, Y) and stimulus value (Y) in the CIE color system with a C light source and a 2-degree visual field using a color analyzer (MCPD 2000, manufactured by luka electronics co., ltd.).

Next, the substrate was additionally baked at 230 ℃ for 90 minutes, and then chromaticity coordinate values (x, Y) and stimulus values (Y) were measured to evaluate the color change before and after the additional baking, i.e., Δ E ab. As a result, the case where the Δ E ab value was less than 3.0 was evaluated as "o", the case where the Δ E ab value was 3.0 or more and less than 5.0 was evaluated as "Δ", and the case where the Δ E ab value was 5.0 or more was evaluated as "x". The evaluation results are shown in table 3. The smaller the Δ E ab value is, the better the heat resistance is.

Examples 2 to 6 and comparative examples 1 to 6

In example 1, coloring compositions (S-2) to (S-12) were prepared in the same manner as in example 1, except that the kinds and amounts of the respective components were changed as shown in table 3. Next, evaluations were carried out in the same manner as in example 1 except that the coloring compositions (S-2) to (S-12) were used in place of the coloring composition (S-1). The results are shown in Table 3.

Claims (12)

1. A coloring composition comprising (A) a coloring agent and (B) a polymerizable compound,

(A) the colorant contains a polymer having at least 1 chromophore selected from the group consisting of xanthene and cyanine chromophores and at least 1 chromophore selected from the group consisting of triarylmethane and anthraquinone chromophores.

2. The coloring composition according to claim 1, wherein the polymer is a copolymer containing an ethylenically unsaturated monomer having at least 1 chromophore selected from a xanthene chromophore and a cyanine chromophore, and an ethylenically unsaturated monomer having at least 1 chromophore selected from a triarylmethane chromophore and an anthraquinone chromophore as a structural unit.

3. The coloring composition according to claim 2, wherein the polymer has, as structural units, other copolymerizable ethylenically unsaturated monomers other than the ethylenically unsaturated monomer having at least 1 chromophore selected from the group consisting of xanthene chromophores and cyanine chromophores, and the ethylenically unsaturated monomer having at least 1 chromophore selected from the group consisting of triarylmethane chromophores and anthraquinone chromophores.

4. The coloring composition according to claim 3, wherein a (meth) acrylate ester is provided as the other copolymerizable ethylenically unsaturated monomer.

5. The coloring composition according to claim 3 or 4, wherein the copolymerization ratio of the other copolymerizable ethylenically unsaturated monomer is 30 to 97% by mass in the entire structural units.

6. The coloring composition according to claim 2, wherein a ratio of a content of the ethylenically unsaturated monomer having at least 1 chromophore selected from a xanthene chromophore and a cyanine chromophore to a content of the ethylenically unsaturated monomer having at least 1 chromophore selected from a triarylmethane chromophore and an anthraquinone chromophore is 99/1 to 50/50 in terms of a molar ratio.

7. The coloring composition according to claim 2, wherein a copolymerization ratio of the ethylenically unsaturated monomer having at least 1 chromophore selected from a xanthene chromophore and a cyanine chromophore to the ethylenically unsaturated monomer having at least 1 chromophore selected from a triarylmethane chromophore and an anthraquinone chromophore is 97/3 to 40/60 in a mass ratio.

8. The coloring composition according to claim 2, wherein the ethylenically unsaturated monomer having at least 1 chromophore selected from the group consisting of xanthene chromophores and cyanine chromophores is a compound represented by formula (1-1), the ethylenically unsaturated monomer having at least 1 chromophore selected from the group consisting of triarylmethane chromophores and anthraquinone chromophores is a compound represented by formula (1-2),

in the formula (1-1),

R¹independently of one another, represents a hydrogen atom or a methyl group,

X¹independently of each other, a 2-valent hydrocarbon group directly bonded, substituted or unsubstituted, or a 2-valent group in which the 2-valent hydrocarbon group and 1 or more linking groups containing atoms other than carbon atoms and hydrogen atoms are combined,

p is a xanthene chromophore or a cyanine chromophore,

g represents an integer of 1 or more;

in the formula (1-2), the metal salt,

R²represents a hydrogen atom or a methyl group,

X²represents a 2-valent hydrocarbon group directly bonded, substituted or unsubstituted, or a 2-valent group in which the 2-valent hydrocarbon group and 1 or more linking groups containing atoms other than carbon atoms and hydrogen atoms are combined,

q is triarylmethane chromophore or anthraquinone chromophore,

h represents an integer of 1 or more.

9. The coloring composition according to claim 1, wherein the weight average molecular weight of the polymer is 1000 to 100000.

10. The coloring composition according to claim 1, further comprising (C) a binder resin.

11. A colored cured film formed by using the colored composition according to any one of claims 1 to 10.

12. A display device comprising the colored cured film according to claim 11.