JP6331939B2 - Coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a color liquid crystal display device, a color composition for a color filter used for producing a color filter used for a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Increasing demands are being made.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  Quality items required for the color filter include brightness and contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend. Furthermore, as described above, since the color liquid crystal device has been used for televisions, personal computer monitors, and the like, the demand for high reliability and high lightness and contrast for color filters has also increased.

In recent years, attention has been focused on dye-based coloring materials in order to achieve a high contrast ratio and high brightness that cannot be achieved with pigments. Among them, xanthene dyes such as rhodamine dyes and eosin dyes, diarylmethane dyes such as diphenylmethane, and triarylmethanemethane dyes such as triphenylmethane are superior in color characteristics, and are therefore materials that achieve high brightness. As expected. In addition, since the dye is present in a dissolved state, not in a particulate state like a pigment, in a solvent, light scattering or the like does not occur, and as a result, the contrast ratio is higher than a coloring composition in which conventional pigments are combined. A color filter is expected to be obtained.

  However, depending on the type of dye, there is a problem that the contrast ratio is low because it exhibits fluorescence emission characteristics. In addition, as a general characteristic of dyes, it tends to be inferior in fastness such as heat resistance and light resistance as compared with pigments, and tends to be inferior in solubility in organic solvents suitable as colored products for color filters (Patent Documents). 1-3). Therefore, in using a dye, a technique for imparting organic solvent solubility, imparting fastness, and a technique for suppressing fluorescence emission is required for a dye having fluorescence.

JP 2010-32999 A Japanese Patent Laid-Open No. 6-222059 JP 2011-102841 A

The problems to be solved by the present invention are to impart solubility in organic solvents to luminescent pigments (for example, dyes), to provide fastness, and to suppress fluorescence emission to pigments that emit fluorescence. In other words, it is possible to provide a coloring composition for a color filter having a high brightness and a high contrast ratio.

That is, the present invention is a color filter coloring composition comprising a luminescent dye (S), a quencher (D), and a binder resin (C),
Highest occupied molecular orbital of the luminescent dye (S); the difference between the energy levels HOMO _S, the energy level HOMO _D of the highest occupied molecular orbital of the quencher (D) of the (Highest Occupied Molecular Orbital HOMO) is,
−2.0 <| HOMO _D | − | HOMO _S | <0.0 (eV)
It is related with the coloring composition for color filters characterized by satisfy | filling the relational expression of these.

Further, the present invention is lowest unoccupied molecular orbital of the luminescent dye (S); the difference between the energy levels LUMO _S, the energy level LUMO _D of the lowest unoccupied molecular orbital of the quencher (D) of (Lowest Unoccupied Molecular Orbital LUMO) But,
| LUMO _D | − | LUMO _S | <0.0 (eV)
It is related with the said coloring composition for color filters characterized by satisfy | filling the relational expression of this.

Further, the present invention is a color filter coloring composition comprising a luminescent dye (S), a quencher (D), and a binder resin (C),
The quencher (D) is any one of compounds represented by the following general formulas (1) to (4), and relates to a coloring composition for a color filter.

General formula (1)
[In general formula (1),
X ^{1 to} X ⁴ each independently represents a direct bond, a substituted or unsubstituted carbon atom, a sulfur atom, or a selenium atom.
R ^{1 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group Represents an aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{1 to} R ⁴ are adjacent groups. May combine with each other to form a ring. ]

General formula (2)
[In general formula (2),
X ⁵ represents a direct bond, a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, or a sulfur atom.
R ^{5 to} R ¹³ each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group , An aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{5 to} R ¹³ are adjacent groups. May combine with each other to form a ring. ]

General formula (3)
[In general formula (3),
R ^{14 to} R ²¹ each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group , An aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{14 to} R ²¹ are adjacent groups. May combine with each other to form a ring. ]

General formula (4)
[In general formula (4),
R ^{22 to} R ³³ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group Represents an aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{22 to} R ³³ are adjacent groups. May combine with each other to form a ring. ]

  The present invention also relates to the color composition for a color filter, wherein the luminescent dye (S) is a xanthene dye, a cyanine dye, or an azo dye.

  The present invention further relates to the color composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also relates to a color filter comprising a filter segment formed on the substrate from the color filter coloring composition.

  According to the present invention, it is possible to provide a coloring composition for a color filter which imparts solvent solubility and fastness (heat resistance, light resistance) of a luminescent dye and suppresses fluorescence emission. A color filter having a high brightness and a high contrast ratio can be formed by preparing a color filter using the color filter coloring composition of the present invention.

Hereinafter, the present invention will be described in detail.
In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ".
Further, “CI” in this specification means a color index (CI).

<Quencher (D)>
The coloring composition for a color filter of the present invention is characterized by containing a quencher (D).
When the luminescent dye (S) absorbs light, the electrons transition from the binding orbitals to the antibonding orbitals, and the molecules change from the ground state to the excited state. After a slight relaxation from the excited state, it emits fluorescence and returns to the ground state. This fluorescence is the main factor that lowers the contrast of a color filter produced using the luminescent dye (S).
Here, the fluorescence wavelength generally corresponds to the energy band gap ΔE between the highest occupied orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).
When the quencher (D) used in the present invention is added, intermolecular energy transfer by the Dexter mechanism occurs from the HOMO of the quencher (D) to the HOMO of the luminescent dye (S) in an excited state. Fluorescence emission from the luminescent dye (S) is suppressed. Thereafter, the luminescent dye (S) returns to the ground state by non-radiation deactivation. Thereby, the contrast fall of the color filter produced using the luminescent pigment | dye (S) can be suppressed.

In order to establish the mechanism, the difference between the energy levels HOMO _S of HOMO, the HOMO energy level HOMO _D quencher (D) of the luminescent dye (S) is, -2.0 <| HOMO _The condition is that _D | − | HOMO _S | <0.0 (eV) is satisfied. If this relational expression is not satisfied, intermolecular energy transfer is unlikely to occur, and thus fluorescence emission from the luminescent dye (S) cannot be suppressed.
In addition, in order to suppress reverse energy transfer from the LUMO of the luminescent dye (S) in the excited state to the LUMO of the quencher (D), the LUMO energy level LUMO _{S of the} luminescent dye (S) , the difference between the energy level LUMO _D of LUMO of quencher (D) _{is, | LUMO D | - | LUMO} S | < it is preferable to satisfy the relational expression of 0.0 (eV).
Furthermore, if the energy level difference is too large or too small, intermolecular energy transfer is unlikely to occur. Therefore, it is preferable that the relational expression −1.0 <| HOMO _D | − | HOMO _S | <−0.05 (eV) is satisfied, more preferably −0.5 <| HOMO _D | − | HOMO _S. It is desirable to satisfy the relational expression of | <−0.1 (eV).

Examples of the quencher (D) include compounds represented by the following general formulas (1) to (4).

(Compound represented by the general formula (1))
General formula (1)
In general formula (1),
X ^{1 to} X ⁴ each independently represents a direct bond, a substituted or unsubstituted carbon atom, a sulfur atom, or a selenium atom.
R ^{1 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group Represents an aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{1 to} R ⁴ are adjacent groups. May combine with each other to form a ring.

Here, examples of the aliphatic hydrocarbon group represented by R ^{1 to} R ⁴ in the general formula (1) include an alkyl group, an alkenyl group, and an alkynyl group.

  Here, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group And alkyl groups such as nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group.

  Examples of the alkenyl group include an ethylenyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, Examples include alkenyl groups such as a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, and an icocenyl group.

  The alkynyl group includes ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group, hexadecynyl group. Alkenyl groups such as a group, heptadecinyl group, octadecynyl group, nonadecynyl group, icosinyl group.

Examples of the alicyclic hydrocarbon group represented by R ^{1 to} R ⁴ in the general formula (1) include a cycloalkyl group, a cycloalkenyl group, a decahydronaphthyl group, an adamantyl group, and the like.

  Here, examples of the cycloalkyl group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononanyl group, and a cyclodecanyl group.

Examples of the cycloalkenyl group include cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclononenyl group, and a cyclodecenyl group.

Moreover, as an aromatic hydrocarbon group of R < ¹ > -R < ⁴ > in General formula (1), a monocyclic aromatic hydrocarbon group, a condensed ring aromatic hydrocarbon group, and a ring assembly aromatic hydrocarbon group are mentioned.

Here, the monocyclic aromatic hydrocarbon group includes a monocyclic aromatic group such as a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,4-xylyl group, a p-cumenyl group, and a mesityl group. Group hydrocarbon group.

  The condensed ring aromatic hydrocarbon group includes 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group. And condensed ring aromatic hydrocarbon groups such as a group, 2-azurenyl group, 1-pyrenyl group, 2-triphenylyl group, and 2-indeno group.

  Examples of the ring-aggregated aromatic hydrocarbon group include ring-aggregated aromatic hydrocarbon groups such as o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group.

Examples of the aliphatic heterocyclic group represented by R ^{1 to} R ⁴ in the general formula (1) include aliphatic heterocyclic groups such as a 2-pyrazolino group, a piperidino group, a morpholino group, and a 2-morpholinyl group.

In addition, as the aromatic heterocyclic group represented by R ^{1 to} R ⁴ in the general formula (1), a triazolyl group, a 3-oxadiazolyl group, a 2-furanyl group, a 3-furanyl group, a 2-furyl group, and a 3-furyl group. 2-thienyl group, 3-thienyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazyl group Group, 2-oxazolyl group, 3-isoxazolyl group, 2-thiazolyl group, 3-isothiazolyl group, 2-imidazolyl group, 3-pyrazolyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group Group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 2-quinoxalinyl group, 2-benzofuryl group, 2-benzothienyl group, N-indolyl group, N-carbazolyl group , N- acridinyl group, 2-thiophenyl group, 3-thiophenyl group, bipyridyl group, phenanthrolyl group, an aromatic heterocyclic group such as.

Moreover, as a halogen atom of R < ¹ > -R < ⁴ > in General formula (1), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

Moreover, as an alkoxy group of R < ¹ > -R < ⁴ > in General formula (1), alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxy group, a tert-octyloxy group Is mentioned.

In addition, as the aryloxy group of R ^{1 to} R ⁴ in the general formula (1), a phenoxy group, 4-tert-butylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group And aryloxy groups.

In addition, as the alkylcarbonyl group of R ^{1 to} R ⁴ in the general formula (1), a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, an isopropylcarbonyl group, a butylcarbonyl group, an isobutylcarbonyl group, a sec-butylcarbonyl group Alkylcarbonyl groups such as tert-butylcarbonyl group, pentylcarbonyl group, and hexylcarbonyl group.

The arylcarbonyl group of R ^{1 to} R ⁴ in the general formula (1) includes a phenylcarbonyl group, a 4-tert-butylphenylcarbonyl group, a 1-naphthylcarbonyl group, a 2-naphthylcarbonyl group, and 9-anthryl. An arylcarbonyl group such as a carbonyl group can be mentioned.

In addition, as the alkoxycarbonyl group of R ^{1 to} R ⁴ in the general formula (1), a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, an isobutyloxycarbonyl group, sec Examples include alkoxycarbonyl groups such as -butyloxycarbonyl group, tert-butyloxycarbonyl group, pentyloxycarbonyl group, and hexyloxycarbonyl group.

In addition, as the aryloxycarbonyl group of R ^{1 to} R ⁴ in the general formula (1), a phenyloxycarbonyl group, a 4-tert-butylphenyloxycarbonyl group, a 1-naphthyloxycarbonyl group, and a 2-naphthyloxycarbonyl group And aryloxycarbonyl groups such as 9-anthryloxycarbonyl group.

Examples of the alkylthio group of R ^{1 to} R ⁴ in the general formula (1) include alkylthio groups such as methylthio group, ethylthio group, propylthio group, butylthio group, tert-butylthio group, pentylthio group, and hexylthio group.

In addition, examples of the arylthio group represented by R ^{1 to} R ⁴ in the general formula (1) include arylthio groups such as phenylthio group, 4-tert-butylphenylthio group, 1-naphthylthio group, 2-naphthylthio group, and 9-anthrylthio group. A ruthio group.

Moreover, as an amino group of R < ¹ > -R < ⁴ > in General formula (1), unsubstituted amino group, N-methylamino group, N-ethylamino group, N, N-diethylamino group, N, N-diisopropyl Amino group, N, N-dibutylamino group, N-benzylamino group, N, N-dibenzylamino group, N-phenylamino group, N-phenyl-N-methylamino group, N, N-diphenylamino group, N, N-bis (m-tolyl) amino group, N, N-bis (p-tolyl) amino group, N, N-bis (p-biphenylyl) amino group, bis [4- (4-methyl) biphenylyl] Examples thereof include amino groups such as amino group, N-α-naphthyl-N-phenylamino group, and N-β-naphthyl-N-phenylamino group.

In addition, as the silyl group of R ^{1 to} R ⁴ in the general formula (1), an unsubstituted silyl group, a monoalkylsilyl group, a monoarylsilyl group, a dialkylsilyl group, a diarylsilyl group, a trialkylsilyl group, tria Examples thereof include a silyl group such as a reel silyl group.

  Here, the monoalkylsilyl group includes a monoalkylsilyl group such as a monomethylsilyl group, a monoethylsilyl group, a monobutylsilyl group, a monoisopropylsilyl group, a monodecanesilyl, a monoicosanesilyl group, and a monotriacontanesilyl group. Is mentioned.

  Examples of the monoarylsilyl group include monoarylsilyl such as monophenylsilyl group, monotolylsilyl group, mononaphthylsilyl group, and monoanthrylsilyl group.

  Examples of the dialkylsilyl group include dialkylsilyl groups such as dimethylsilyl group, diethylsilyl group, dimethylethylsilyl group, diisopropylsilyl group, dibutylsilyl group, dioctylsilyl group, and didecanesilyl group.

  Examples of the diarylsilyl group include diarylsilyl such as diphenylsilyl group and ditolylsilyl group.

  Examples of the trialkylsilyl group include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, dimethylethylsilyl group, triisopropylsilyl group, tributylsilyl group, and trioctylsilyl group.

  Examples of the triarylsilyl group include triarylsilyl groups such as triphenylsilyl group and tolylsilylsilyl group.

Moreover, as phosphino group of R < ¹ > -R < ⁴ > in General formula (1), phosphino such as unsubstituted phosphino group, monoalkyl phosphino group, monoaryl phosphino group, dialkyl phosphino group, diaryl phosphino group Groups.

  Here, examples of the monoalkylphosphino group include monoalkylphosphino groups such as a monomethylphosphino group, a monoethylphosphino group, a monobutylphosphino group, a monoisopropylphosphino group, and a monodecanophosphino group.

  Examples of the monoarylphosphino group include monoarylphosphino groups such as a monophenylphosphino group, a monotolylphosphino group, a mononaphthylphosphino group, and a monopyrenylphosphino group.

  Examples of the dialkylphosphino group include dimethylphosphino group, diethylphosphino group, dimethylethylphosphino group, diisopropylphosphino group, dibutylphosphino group, dioctylphosphino group, didecanephosphino group, and the like. Groups.

  Examples of the diarylphosphino group include diarylphosphino groups such as diphenylphosphino group, ditolylphosphino group, dinaphthylphosphino group, and pyrenylphenylphosphino group.

Here, in X < ¹ > -X < ⁴ > in General formula (1), Preferably they are a sulfur atom and a selenium atom.
Moreover, in R < ¹ > -R < ⁴ > in General formula (1), Preferably, they are an aliphatic hydrocarbon group, an alkylthio group, an aldehyde group, and an aromatic heterocyclic group, More preferably, an aliphatic hydrocarbon group, alkylthio Group, an aromatic heterocyclic group, and more preferably an aliphatic hydrocarbon group and an alkylthio group. This is because the higher the electron donating property of the substituent, the better the donor property of the molecule and the easier the intermolecular energy transfer occurs.

(Compound represented by the general formula (2))
General formula (2)
In general formula (2),
X ⁵ represents a direct bond, a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, or a sulfur atom.
R ^{5 to} R ¹³ each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group , An aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{5 to} R ¹³ are adjacent groups. May combine with each other to form a ring.

Here, the R ⁵ to R ^13, an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group, an aromatic heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group , An alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, an amino group, a silyl group and a phosphino group, respectively, in R ^{1 to} R ⁴ of the general formula (1), Aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group, aromatic heterocyclic group, halogen atom, alkoxy group, aryloxy group, alkylcarbonyl group, arylcarbonyl group, alkoxy Carbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, amino group, silyl group, phosphino group It is synonymous.

Here, X ⁵ in the general formula (2) is preferably a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably a nitrogen atom, an oxygen atom, or a sulfur atom, and still more preferably. Is a nitrogen atom or a sulfur atom.
R ^{6 to} R ¹³ in the general formula (1) are preferably a halogen atom, an alkoxy group, an alkylthio group, or an aromatic hydrocarbon group, and more preferably an alkoxy group, an alkylthio group, or an aromatic hydrocarbon. More preferably an alkoxy group or an aromatic hydrocarbon group. This is because the higher the electron donating property of the substituent, the better the donor property of the molecule and the easier the intermolecular energy transfer occurs.

(Compound represented by the general formula (3))
General formula (3)
In general formula (3),
R _{14 to} R ₂₁ each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group , An aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{14 to} R ²¹ are adjacent groups. May combine with each other to form a ring.

Here, in R ^{14 to} R ²¹ , an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic heterocyclic group, an aromatic heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group , An alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, an amino group, a silyl group and a phosphino group, respectively, in R ^{1 to} R ⁴ of the general formula (1), Aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group, aromatic heterocyclic group, halogen atom, alkoxy group, aryloxy group, alkylcarbonyl group, arylcarbonyl group, alkoxy Carbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, amino group, silyl group, phosphino group It is synonymous.

Here, in R < ¹⁸ > -R < ²¹ > in General formula (3), Preferably, they are an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group, and an amino group, More preferably, an aromatic hydrocarbon group, An alkoxy group and an amino group are more preferable, and an aromatic hydrocarbon group and an amino group are more preferable. This is because the higher the electron donating property of the substituent, the better the donor property of the molecule and the easier the intermolecular energy transfer occurs.

(Compound represented by the general formula (4))
General formula (4)
In general formula (4),
R ^{22 to} R ³³ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group Represents an aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{22 to} R ³³ are adjacent groups. May combine with each other to form a ring.

Here, in R ^{22 to} R ³³ , an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic heterocyclic group, an aromatic heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group , An alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, an amino group, a silyl group, and a phosphino group, respectively, in R ^{1 to} R ⁴ of the general formula (1), Aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group, aromatic heterocyclic group, halogen atom, alkoxy group, aryloxy group, alkylcarbonyl group, arylcarbonyl group, alkoxy Carbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, amino group, silyl group, phosphino group It is synonymous.

Here, in R < ²⁶ > -R < ³³ > in General formula (4), Preferably, they are an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group, and an amino group, More preferably, an aromatic hydrocarbon group, An alkoxy group and an amino group are more preferable, and an aromatic hydrocarbon group and an amino group are more preferable. This is because the higher the electron donating property of the substituent, the better the donor property of the molecule and the easier the intermolecular energy transfer occurs.

Further, the aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group, and aromatic heterocyclic group in the general formulas (1) to (2) are substituted. May be. In this case, examples of the substituent include aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group, aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy Group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, thiol group, alkylthio group, arylthio group, nitro group, amino group, sulfo group, cyano group, silyl group, boronyl Group, phosphino group, and the like.

Here, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group, aromatic heterocyclic group, halogen atom, alkoxy group, aryloxy group, alkylcarbonyl group, arylcarbonyl Examples of the group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, amino group, silyl group, and phosphino group include those described above.

Representative examples of the compounds represented by the general formulas (1) to (4) used in the present invention are shown in the following Table 1, but the present invention is not limited to these representative examples.

  As the addition amount of the quencher (D) of the present invention, the weight ratio (D) / (S) of the quencher (D) and the luminescent dye (S) is in the range of 0.005 to 1.0. In particular, it is most preferably in the range of 0.01 to 0.2. Below 0.005, the fluorescence quenching effect is poor and the contrast ratio improving effect is poor. If it is 1.0 or more, it may cause a decrease in brightness and a decrease in sensitivity.

<Luminescent dye (S)>
The luminescent dye (S) is not limited as long as it is a fluorescent dye. That is, any dye having fluorescence or pigment having fluorescence can be used.
Xanthene compounds (xanthene dyes, xanthene lake pigments),
Cyanine dyes (cyanine dyes),
Azo dyes (azo dyes, azo pigments),
Triphenylmethane dyes (triphenylmethane dyes, triphenylmethane lake pigments),
Diphenylmethane dyes (diphenylmethane dyes, diphenylmethane lake pigments), quinophthalone dyes (quinophthalone dyes, quinophthalone pigments),
Thiazine dyes, thiazole dyes, diketopyrrolopyrrole pigments, anthraquinone dyes, and the like can be used.
Of these, xanthene dyes, cyanine dyes, and azo dyes are preferably used.
In particular, when a dye that emits fluorescence in the visible light region is used, the color filter having a high contrast ratio is excellent.

When the luminescent pigment (S) that can be preferably used in the present invention is in the form of a dye, any of various dyes such as an oil-soluble dye, an acid dye, a direct dye, a basic dye, a mordant dye, and an acid mordant dye It is preferable that it has such a form.
Examples of the pigment form include a pigment having fluorescence and a lake pigment obtained by lake- ing the dye. When the dye (S) is a dye, it is preferable to use an oil-soluble dye, an acid dye, a direct dye, or a basic dye because of excellent hue.

Oil-soluble dyes are classified as color indexes, C.I. Examples of basic dyes classified as I. Solvent are the same as C.I. Examples of acid dyes that are classified as I. basic are the same as those described in C.I. Examples of the dyes classified as I. Acid and direct dyes include C.I. I. It is classified as direct. Here, the direct dye has a sulfonic acid group (—SO ₃ H, —SO ₃ Na) in the structure, and in the present invention, the direct dye is regarded as an acid dye.
Hereinafter, the luminescent dye (S) will be specifically described.

(Xanthene dyes: xanthene dyes, xanthene lake pigments)
In the case of xanthene dyes, the transmittance is 90% or more in the region of 650 nm in the transmission spectrum, the transmittance is 75% or more in the region of 600 nm, the transmittance is 5% or less in the region of 500 to 550 nm, and the region of 400 nm. And a transmittance of 70% or more is preferable. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500 to 550 nm, and the transmittance is 75% in the region of 400 nm. That's it. Among them, xanthene basic dyes and xanthene acid dyes have spectral characteristics having high transmittance at 400 to 450 nm.

  Of the xanthene dyes, rhodamine dyes are preferred because of their excellent color developability and resistance.

[Forms of xanthene dyes as oil-soluble dyes]
Specifically, as the xanthene oil-soluble dye, CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red Red 44, CI Solvent Red 45, CI Solvent Red 46, CI Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72 CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, C CI Solvent Violet 2, CI Solvent Violet 10 and the like.
Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

[Forms of xanthene dyes as acidic dyes]
Examples of the acid dyes of xanthene dyes (xanthene acid dyes) include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

[Forms of xanthene dyes as basic dyes]
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B), C.I. I. Basic violet 11 and the like. Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10, C.I. I. Basic violet 11 is preferably used.

[Forms of xanthene dyes as xanthene lake pigments]
Xanthene-based lake pigments include CI Pigment Red 81, CI Pigment Red 81: 1, CI Pigment Red 81: 2, CI Pigment Red 81: 3, and CI Pigment. Red 81: 4, CI Pigment Red 81: 5, CI Pigment Red 169, CI Pigment Violet 1, CI Pigment Violet 1: 1, CI Pigment Violet 1: 2 CI Pigment Violet 2 and the like.

(Cyanine dyes: Cyanine dyes)
A known or commercially available cyanine dye can be used. For example, C.I. I. Basic Yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52, 53, C.I. I. Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. I. Basic violet 7, 15, 16, 20, 21, 39, 40, C.I. I. Basic orange 27, 42, 44, 46, C.I. I. Basic blue 62, 63, etc. may be mentioned. Among these, C.I. has a good solubility and good color development. I. Basic Yellow 11, 13, C.I. I. Basic Red 12, 13, 14, 15, 37, C.I. I. Basic violet 15, 16, etc. can be used suitably.

(Azo dyes: azo pigments, azo dyes)
[Azo pigments]
An azo pigment is a pigment made of a compound having an azo bond, and is roughly classified into a soluble azo lake pigment, an insoluble azo pigment, and a condensed azo pigment. Broadly divided into azo pigments. Specifically, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 49, 55, 60, 61, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 111, 113, 114, 116, 120, 124, 126, 127, 128, 130, 133, 150, 151, 152, 154, 155, 165, 167, 168, 169, 170, 172, 174, 175, 176, 180, 181, 182, 183, 191, 194, 205, 206, 209, 212, 214, 219, C.I. I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 24, 31, 34, 36, 38, 46, 60, 62, 64, 67, 72, 74, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 38, 41, 48, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 52, 52: 1, 52: 2, 53: 1, 54, 57: 1, 58, 60: 1, 63, 64: 1, 68, 95, 112, 114, 119, 136, 144, 146, 147, 150, 164, 166, 170, 171, 175, 176, 178, 183, 184, 185, 187, 188, 193, 200, 208, 210, 211, 213, 214, 220, 221, 237.238, 239, 242, 245, 247, 248, 251, 253, 256, 258, 262, 266, 268, 269, C.I. I. Violet 25, 50, etc. are mentioned. Among these, Pigment Yellow 150 and Pigment Red 242, 269 are preferable from the viewpoint of color developability.

[Azo dyes]
Azo dyes are roughly classified into azo acid dyes and azo basic dyes.
Examples of azo acid dyes include CI Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108. 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 254, 257, 266, 296, 337;
CI Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127;
CI Acid Violet 11, 56, 58;
CI Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151;
CI Acid Brown 2, 4, 13, 248;
CI Acid Blue 92, 102, 113, 117 and the like.
Examples of azo basic dyes include Basic Red 22, Basic Red 76, Basic Yellow 57, Basic Brown 16, and Basic Brown 17. Among these, Acid Red 254 and 266 are preferable from the viewpoint of color developability.

(Triphenylmethane and diphenylmethane dyes: triphenylmethane dyes, triphenylmethane lake pigments, diphenylmethane dyes, diphenylmethane lake pigments)
In the case of diphenyl and triphenylmethane dyes, blue (blue) triarylmethane basic dyes have spectral characteristics with high transmittance at 400 to 440 nm.

[Forms of diphenyl and triphenylmethane dyes as acid dyes]
As acid dyes of diphenyl and triphenylmethane dyes, food blue 101 (CI Acid Blue 1), Acid Pure Blue (CI Acid Blue 3), Lake Blue I (CI Acid Blue 1) 5), Lake Blue II (CI Acid Blue 7) Edible Blue No. 1 (CI Acid Blue 9), C.I. I. Acid Blue 22, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Acid Blue 103, C.I. I. Acid Blue 104, C.I. I. It is preferable to use Acid Blue 109.

[Forms of diphenyl and triphenylmethane dyes as basic dyes]
The triphenylmethane basic dye and the diphenylmethane basic dye are colored when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, a triaminotriphenylmethane-based basic dye is preferable in terms of good blue, red and green coloring. .
a) Diaminotriphenylmethane basic dye b) Triaminotriphenylmethane basic dye c) Rosolic acid basic dye having OH group Triaminotriphenylmethane basic dye, diaminotriphenylmethane basic dye The dye has a clear color tone and is excellent in sunlight fastness than the other dyes and is preferable. Further, diphenylnaphthylmethane basic dye and / or triphenylmethane basic dye are preferable.

  Specifically, C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 25 (Basic Blue GO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green), C.I. I. Basic violet 1 (methyl violet), 3 (crystal violet), 14 (Magenta) and the like.

[Forms of diphenyl and triphenylmethane dyes as lake pigments]
Specific examples of diphenylmethane lake pigments and triphenylmethane lake pigments include C.I. I. Pigment Blue 1, C.I. I. Pigment Blue 2, C.I. I. Pigment Blue 9, C.I. I. Pigment Blue 10, C.I. I. Pigment Blue 14, C.I. CI pigment blue 62, CI pigment violet 3, CI pigment violet 27, CI pigment violet 39, and the like.
More specifically, C.I. I. Pigment Blue 1, C.I. I. Basic Blue 26, C.I. I. Basic Blue 7 was raked with phosphotungsten molybdate, C.I. I. Pigment Violet 3, C.I. I. Basic violet 1 was raked with phosphotungsten molybdate, C.I. Pigment Violet 39, C.I. I. Basic violet 3 (crystal violet) was raked with phosphotungsten / molybdic acid. I. Pigment Blue 1 is preferably used.

(Quinophthalone dyes: quinophthalone dyes, quinophthalone pigments)
Examples of the quinophthalone dye include dyes commercially available with color indexes such as Solvent Yellow 33, Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, Disperse Yellow 160, and Acid Yellow 3.
Examples of the quinophthalone pigment include C.I. I. Pigment Yellow 138 (Pariotor Yellow K0961-HD, manufactured by BFS).
Of these, Acid Yellow 3, C.I. I. Pigment Yellow 138 (Parisol Yellow K0961-HD manufactured by BAS F) is preferable.

(Thiazine dye)
As thiazine-based dyes, Lath's Violet obtained by oxidizing P-phenylenediamine in the presence of hydrogen sulfide under FeCl ₂ , methylene blue, methylene green B, C.I. basic blue 9, 17, 24, 25, Solvent Blue 8, CI Basic Green 5, CI Direct Red 70, and the like.

(Thiazole dye)
As the thiazole dye, a dye having a thiazole ring is a thiazole dye. Specifically, CI basic yellow 1, CI basic violet 44, 46, CI basic blue 116, CI Acid Yellow 186, Direct Yellow 7, 8, 9, 14, 17, 18, 22, 28, 29, 30, 54, 59, 165, CI Direct Orange 18, CI Direct Red 11, etc. are mentioned.

(Diketopyrrolopyrrole pigment)
The diketopyrrolopyrrole pigment is a red to orange pigment having a structure represented by the following general formula (7). Specific examples of the diketopyrrolopyrrole pigment represented by the following general formula (7) include C.I. I. Pigment Red254, 255, 264, 272 and C.I. I. Pigment Orange 71, 73, 81. From the viewpoint of color development, C.I. I. Pigment Red254 is preferred.

General formula (7)
In the formula, X and Y each independently represent CN, C (CH ₃ ) ₃ , CH ₃ , Cl, C ₆ H ₅ , or H.

(Anthraquinone dye)
Specific examples of the anthraquinone dyes include the following acidic dyes and oil-soluble dyes, but are not limited thereto.
[Forms of anthraquinone dyes as acidic dyes]
As an anthraquinone acid dye, CI Acid Blue 23, 25, 27, 35, 40, 41, 43, 45, 47, 49, 51, 53, 55, 56, 62, 68, 69, 78, 80 81: 1, 11, 124, 127, 127: 1, 140, 150, 175, 215, 230, 277, 344, CI Acid Violet 41, 42, 43, CI Acid Green 25, 27 Or direct violet 17 and the like.

[Forms of anthraquinone dyes as oil-soluble dyes]
Examples of anthraquinone oil-soluble dyes include CI Solvent Red 172, 222, CI Solvent Violet 60, and the like.

<Salt-forming compound of luminescent dye (S), sulfonic acid amide compound>
The luminescent dye (S) that can be preferably used in the present invention must have a certain level of heat resistance and solvent resistance when used as a coloring composition for a color filter. However, the luminescent dye (S) generally has good spectral characteristics and excellent color developability, but has poor heat resistance and solvent resistance, and lacks solubility in organic solvents, so it is used for color filters. Many pigments cannot be used as a coloring composition.
Therefore, when the luminescent dye (S) has a cationic group, it is salted with a compound having an anionic group, and when the luminescent dye (S) has an anionic group, the cationic group By making a salt with a compound having the above, heat resistance, solvent resistance, and solubility in organic solvents can be remarkably improved. Further, in order to improve these disadvantages, when the luminescent dye (S) is in the form of an acid dye or a direct dye, it is sulfonamidated and used as a sulfonic acid amide compound, so that heat resistance, light resistance, solvent resistance Can be improved.

(When the luminescent dye (S) is a dye having an anionic group)
When the luminescent dye is a dye having an anionic group, examples of the anionic group contained in the dye having an anionic group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a base thereof. From the viewpoints of properties and solvent resistance, sulfonic acid groups, phosphoric acid groups, and their bases are preferable. The dye having an anionic group (having fluorescence) is not particularly limited as long as it is a dye having at least one anionic group. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 254, C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. Acid Violet 9, Edible Blue No. 101 (CI Acid Blue 1), Acid Pure Blue (CI Acid Blue 3), Lake Blue I (CI Acid Blue 5), Lake Blue II (C.I. I. Acid Blue 7) Edible Blue No. 1 (C.I. Acid Blue 9), C.I. I. Acid Blue 22, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Acid Blue 103, C.I. I. Acid Blue 104, C.I. I. Acid Blue 109, CI Direct Red 70, CI Acid Yellow 186, Direct Yellow 7, 8, 9, 14, 17, 18, 22, 28, 29, 30, 54, 59, 165, C CI Direct Orange 18, CI Direct Red 11 and the like. C. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, C.I. I. Acid Red 254 is more preferable in terms of hue and color developability.

  When the luminescent dye (S) is a dye having an anionic group, it can be used as a salt-forming compound by salt formation with a compound having a cationic group.

(When the luminescent dye (S) is a dye having a cationic group)
The dye having a cationic group having fluorescence can be selected from known dye compounds as long as the dye has at least one cationic group. As an example, C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B), C.I. I. Basic violet 11, C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 25 (Basic Blue GO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green), C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), Lauth's Violet, Methylene Blue, Methylene Green B, C.I. Basic Blue 9, 17, 24, 25 C.I. Basic Yellow 1, C.I. Basic Violet 44, 46, C.I. Basic Blue 116, C.I. I. Basic Yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52, 53, C.I. I. Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. I. Basic violet 7, 15, 16, 20, 21, 39, 40, C.I. I. Basic orange 27, 42, 44, 46, C.I. I. Basic blue 62, 63 and the like can be mentioned. C. I. Basic violet 10 (Rhodamine B), C.I. I. Basic violet 11, C.I. I. Basic Red 12, C.I. I. Basic Blue 7 is more preferable from the viewpoints of hue and color developability.

When the luminescent dye (S) is a dye having a cationic group, it can be used as a salt-forming compound by salt formation with a compound having an anionic group.
In that case, as the compound having an anionic group, a vinyl resin having an anionic group represented by the following general formula (6), a fluorine group-containing phosphorus anion, a fluorine group-containing boron anion, a cyano group-containing nitrogen anion, a sulfone Those having an acid group-containing nitrogen anion, a conjugate base of an organic acid having a halogenated hydrocarbon group, an organic acid, or an inorganic acid are preferred.
Among these, it is preferable to use a fluorine group-containing boron anion. Moreover, it is also preferable to salt-form using an organic acid and an inorganic acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid, and it is particularly preferable to use naphthalenesulfonic acid. Tobias acid is particularly preferable. As the inorganic acid, it is particularly preferable to use perchloric acid.

[Fluorine group-containing boron anion]
Fluorine group-containing boron anions include BF ₄ ⁻ , (CF ₃ ) ₄ B ⁻ , (CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ ⁻ , (CF ₃ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₄ B ⁻ , (C ₂ F ₅ ) ₃ BF ⁻ , (C ₂ F ₅ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₂ BF ₂ ⁻ , (CF ₃ ) (C ₂ F ₅ ) ₂ BF ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , ( C ₆ F ₅ ) BF ₃ ⁻ , (C ₆ H ₃ F ₂ ) ₄ B ⁻ , B (CN) ₄ ⁻ , B (CN) F ₃ ⁻ , B (CN) ₂ F ₂ ⁻ , B (CN) ₃ F ⁻ , (CF ₃ ) ₃ B (CN) ⁻ , (CF ₃ ) ₂ B (CN) ₂ ⁻ , (C ₂ F ₅ ) ₃ B (CN) ⁻ , (C ₂ F ₅ ) ₂ B (CN) ^{_{2 -, (n-C 3}} F 7) 3 B (CN) -, (n-C 4 F 9) 3 B (CN) -, (n-C 4 F 9) 2 B (CN) 2 - _{(N-C 6 F 3)} 3 B (CN) -, (CHF 2) 3 B (CN) -, (CHF 2) 2 B (CN) 2 -, (CH 2 CF 3) 3 B (CN) - , (CH ₂ CF ₃ ) ₂ B (CN) ₂ ⁻ , (CH ₂ C ₂ F ₅ ) ₃ B (CN) ⁻ , (CH ₂ C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CH _{2 C 3 F 7) 2 B} (CN) 2 -, (n-C 3 F 7 CH 2) 2 B (CN) 2 -, (C 6 H 5) 3 B (CN) - , and the like. Among these, BF ₄ ⁻ , B (CN) ₃ F ⁻ , (CF ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , and [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ are preferable.

[Fluorine group-containing phosphorus anion]
Fluorine group-containing phosphorus anions include PF ₆ −, (CF ₃ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF ^{_{] 2 PF 4 -, [(}} CF 3) 2 CF] 3 PF 3 _{over, (n-C 3 F 7} ) 2 PF 4 -, (n-C 3 F 7) 3 PF 3 -, (n-C 4 F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , (N-C ₄ F ₉ ) ₂ PF ₄ ⁻ , (n-C ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₄ H) (CF ₃ ) ₂ PF ₃ ⁻ , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ^{— and the} like. Among ^{_{them, PF 6 -, (C 2}} F 5) 2 PF 4 -, (C 2 F 5) 3 PF 3 -, (n-C 3 F 7) 3 PF 3 -, (n-C 4 F 9) 3 PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ^- is preferred.

[Cyano group-containing nitrogen anion]
Cyano group-containing nitrogen anions include [(CN) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , [(FSO ₂ ) N (CF ^{_{3 CF 2 SO 2)] -}} , [(FSO 2) N {(CF 3) 2 CFSO 2}] -, [(FSO 2) N (CF 3 CF 2 CF 2 SO 2)] -, [(FSO 2 ) N (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ⁻ , [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^{− and the} like. Of _{these, [(CN) 2 N]} - it is particularly preferred.

[Conjugate base of organic acid having halogenated hydrocarbon group]
The conjugate base of the organic acid having a halogenated hydrocarbon group is not particularly limited, but examples of the organic acid having a halogenated hydrocarbon group include sulfonic acid having a halogenated hydrocarbon group (-SO ₃ H), sulfonimide acid (—SO ₂ NHSO ₂ —) and the like, and specifically, compounds shown below can be mentioned.

[Vinyl resin having an anionic group represented by the general formula (6)]
As the compound having an anionic group, a vinyl resin containing a structural unit represented by the following general formula (6) can be suitably used. Of these, acrylic resins are preferably used.

General formula (6)

In the general formula (6), R ₅₆ represents a hydrogen atom or a substituted or unsubstituted alkyl group. T represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, —CONH—R ₅₇ —, or —COO—R ₅₇ —, and R ₅₇ represents a substituted or unsubstituted alkylene group. S ^- it is, -SO ₃ ^-, or -COO ^- represents a. U ⁺ represents an inorganic or organic cation.

Examples of the alkyl group for R ₅₆ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ₅₆ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group. Among the above, R ₅₆ is most preferably a hydrogen atom or a methyl group.

S ⁻ in the general formula (6) represents —SO ₃ ^— or —COO ^— , and —SO ₃ ^— is more preferable from the viewpoint of heat resistance.

In the general formula (6), acrylic moiety and S ^- component of T linking the alkylene group, an arylene _{group, -CONH-R 57 -, -} COO-R 57 - represents, but R ₅₇ represents an alkylene group, Among these, —CONH—R ₅₇ — and —COO—R ₅₇ — are preferable because of polymerizability and availability. R ₅₇ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The U ⁺ component in the general formula (6) represents an inorganic or organic cation, and any known one can be used without limitation. Specific examples of U include hydrogen, alkali metals, alkaline earth metals, and ammonium compounds. At that time, the alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium. The ammonium compound is NH ⁴⁺ or a compound in which H is substituted with a hydrocarbon group or the like.

  In order to obtain a vinyl resin containing a structural unit represented by the following general formula (6) which is a preferred embodiment of the present invention, a method of copolymerizing monomers having a sulfonic acid group and / or a carboxyl group as a monomer component Is mentioned.

  Below, the specific example of the ethylenically unsaturated monomer which has a sulfonic acid group or carboxyl group which can be used in order to obtain the vinyl resin containing the structural unit represented by General formula (6) is shown.

[Carboxyl group-containing ethylenically unsaturated monomer]
Examples of the ethylenically unsaturated monomer having a carboxyl group include, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid, and examples of the monomer having a carboxyl group include Further, a monomer having a carboxylic acid anhydride group is also included, and examples of the monomer having a carboxylic acid anhydride group include maleic anhydride and itaconic anhydride.

[Sulphonic acid group-containing ethylenically unsaturated monomer]
Monomers having sulphonic acid groups are monomers of the formula (IV) and their water-soluble salts, in particular alkali metal salts, such as potassium and very particularly preferably sodium and ammonium salts.
Formula (IV)
R ₅₈ (R ₅₉ ) C═C (R ₆₀ ) —X—SO ₃ H
[In the formula (IV), R ₅₈ , R ₅₉ and R ₆₀ are independently of each other -H, a linear or branched alkyl group having 1 to 12 C atoms, a linear or branched C atom 2 A monounsaturated or polyunsaturated alkenyl group having ˜12, wherein the latter two groups are unsubstituted or substituted by one or more groups —NH ₂ , —OH or —COOH -COOH or -COOR ₆₁ and R ₅₈ is XSO ₃ H; R ₆₁ is a hydrocarbon having 1 to 12 saturated or unsaturated linear or branched C atoms X represents a single bond, — (CH ₂ ) n— wherein n = 1 to 4, phenylene, preferably 1,4-phenylene, —CH ₂ —O-phenylene (preferably 1,4), —CH _{2. -O-CH 2 -CH (OH)} -CH 2 -, -C a k = 1 to 6 OO— (CH ₂ ) k—, —CO—NH—, —CO—NH—CR′R ″ — (CH ₂ ) m in which m = 0 to 3 or —CO—NH—CH ₂ —CH (OH ) —CH ₂ —; R ′ is —H, —CH ₃ or —C ₂ H ₅ and R ″ is —H or —CH ₃ . ]

Particularly advantageous among the monomers having sulfonic acid groups are the monomers of formula (IVa), (IVb) and / or (IVc).
_{H 2 C = CH-X-} SO 3 H (IVa)
_{H 2 C = C (CH 3} ) -X-SO 3 H (IVb)
HO ₃ S—X— (R ₆₂ ) C═C (R ₆₃ ) —X—SO ₃ H (IVc)
[Wherein R ₆₂ and R ₆₃ independently of one another are —H, —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ or —CH (CH ₃ ) ₂ , and X is a single group. bond, n = 1 to 4 of the - (CH ₂₎ n-, phenylene, preferably 1,4-phenylene, -CH ₂ -O- phenylene (preferably _{1,4), - CH 2 -O-} CH 2 - CH (OH) —CH ₂ —, k = 1 to 6 —COO— (CH ₂ ) k—, —CO—NH—, m = 0 to 3 —CO—NH—CR′R ″ — (CH ₂ ) m- or —CO—NH—CH ₂ —CH (OH) —CH ₂ —; R ′ is —H, —CH ₃ or —C ₂ H ₅ and R ″ is —H or -CH _3. ]

  Very advantageous sulfonic acid group-containing monomers are 1-acrylamide-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-acrylamide-2- Methylpropanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, 3-methacrylamide-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid (2-methyl-2-propene- 1-sulfonic acid), allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, styrenesulfonic acid, p-styrenesulfonic acid, vinylsulfonic acid, isoprene Sulfonic acid, 3-sulfopropyla Lilate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts and esters of the acids mentioned, alkali metal salts and alkaline earth metal salts It is advantageous to be in the form of Na salts and K salts.

  Particularly preferred monomers having sulfonic acid groups are 2-acrylamido-2-methyl-1-propanesulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid or 2-sodium sulfoethyl methacrylate.

[Other copolymerizable ethylenically unsaturated monomers]
Other examples of monomers that can be used include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

  Specific examples of such a monomer include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn -Butyl acryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl. Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  Preferred are methyl (meth) acrylate, lauryl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, or benzyl (meth) acrylate, 2-Methyl (meth) acrylate, methyl (meth) acrylate, lauryl (meth) acrylate or styrene is more preferable from the viewpoint of the storage stability of the colored composition using the salt-forming compound.

[Other ethylenically unsaturated monomers containing copolymerizable thermally crosslinkable functional groups]
By copolymerizing an ethylenically unsaturated monomer containing a heat-crosslinkable functional group, a cross-linking with an acrylic resin having a heat-crosslinkable functional group or a binder resin is formed in the heating step in the production of the color filter. . Thereby, a strong film is formed, color change of the film can be prevented, that is, heat resistance can be improved, and solvent resistance is also improved.

The preferred structure of the thermally crosslinkable functional group is not particularly limited. For example, a hydroxyl group, a primary or secondary amino group, an imino group, an oxetanyl group, a t-butyl group, an epoxy group, a mercapto group, an isocyanate group, An allyl group, a (meth) acryl group, etc. are mentioned.
Of these, hydroxyl group, oxetanyl group, t-butyl group, isocyanate group, and (meth) acryl group are preferable from the viewpoint of storage stability and reactivity with other materials in use as a color filter coloring composition, and particularly hydroxyl group. It is preferable to have.

  One method for introducing a thermally crosslinkable functional group in a vinyl resin having an anionic group into a vinyl resin having an anionic group used in the present invention is to use an ethylenically unsaturated monomer having a thermally crosslinkable functional group. This is a method of copolymerizing the product with an ethylenically unsaturated monomer corresponding to the anionic group represented by the general formula (6).

  Examples of the ethylenically unsaturated monomer having a hydroxyl group are not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples thereof include glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or caprolactone adducts of these monomers (addition mole number is preferably 1 to 5).

  Examples of the ethylenically unsaturated monomer having an oxetanyl group include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (Methacryloyloxymethyl) 3-hexyloxetane and the like.

  Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl acrylate and t-butyl methacrylate.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate, and the like.

  The isocyanate group in the present invention includes a blocked isocyanate group and can be preferably used. Under normal conditions, the blocked isocyanate group can protect the isocyanate group with other functional groups to suppress the reactivity of the isocyanate group, and can be deprotected by heating to regenerate the active isocyanate group. The isocyanate block body is shown.

  Examples of commercially available ethylenically unsaturated monomers having such a blocked isocyanate group include 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Karenz MOI-BP, Showa Denko); Examples include 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM, manufactured by Showa Denko).

  Moreover, as an ethylenically unsaturated monomer which has a block isocyanate group, a commercial item can be used, and it can also prepare and use by a well-known method. For example, an isocyanate compound having an ethylenically unsaturated bond and a blocking agent are stirred in a solvent at a temperature of about 0 to 200 ° C., and known separation and purification means such as concentration, filtration, extraction, crystallization and distillation are performed. It can obtain by separating using.

  Another method for introducing the heat-crosslinkable functional group in the vinyl resin having an anionic group used in the present invention into the acrylic resin is to obtain the acrylic resin and then add the functional group of the acrylic resin to the functional group. This is a method of reacting a functional group capable of reacting with a compound having a thermally crosslinkable functional group. For example, by reacting a glycidyl group of an ethylenically unsaturated monomer having a glycidyl group with a carboxyl group in an acrylic resin having a carboxyl group, an acrylic resin having a (meth) acryloyl group as a thermally crosslinkable functional group is obtained. Can be obtained.

  At least one kind of the heat-crosslinkable functional group needs to be contained in the resin, and two or more kinds may be contained.

  Examples of a method for obtaining a vinyl resin containing a structural unit represented by the following general formula (6) suitable for the present invention include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. A known method can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

  Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the following references 1 to 8 and the like.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

  It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

  The total of structural units having a sulfonic acid group and a carboxyl group present in a vinyl resin containing a structural unit represented by the following general formula (6) suitable for the present invention is 100% by weight of the total copolymer composition. A copolymer containing 2 to 50% by weight is preferable, and a copolymer containing 5 to 35% by weight is more preferable.

  Although the molecular weight of the vinyl resin containing the structural unit represented by the following general formula (6) used in the present invention is not particularly limited, the converted weight average measured by gel permeation chromatography (GPC). The molecular weight is preferably 1,000 to 500,000, and more preferably 3,000 to 15,000.

  Moreover, it is preferable that the vinyl-type resin containing the structural unit represented by following General formula (6) suitable for this invention has the characteristic melt | dissolved in the solvent widely used for the coloring composition for color filters. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is preferable to dissolve in glycol acetates, especially propylene glycol monomethyl ether acetate.

(Salt formation of luminescent dye (S))
The salt-forming compound of the present invention comprises an aqueous solution in which a dye having a fluorescent anionic group is dissolved and an aqueous solution of a dye having a cationic anionic group that is stirred or vibrated, or has a fluorescent anionic group. A salt-forming compound can be easily obtained by mixing an aqueous solution of a compound having a cationic group with stirring or vibration.
In the aqueous solution, the anionic group of the dye having an anionic group and the cationic group of the compound having a cationic group are ionized, these are ionically bonded, the ion-bonded portion becomes water-insoluble, and a salt-forming compound is precipitated. If it does not precipitate, a precipitate can be obtained by dropping the reaction solution (mixture of an aqueous solution of a dye having an anionic group and an aqueous solution of a compound having a cationic group) into a poor solvent while stirring. it can.
In addition, since a salt composed of a counter anion of a compound having a cationic group and a counter cation of a dye having an anionic group is water-soluble, it can be removed by washing or the like. As for the compound having a cationic group and the dye having an anionic group having fluorescence, only a single kind or a plurality of kinds having different structures may be used.

Further, the salt-forming compound of the present invention is prepared by stirring or vibrating an aqueous solution in which a dye having a fluorescent cationic group is dissolved, and a compound having an anionic group, or a dye having a fluorescent cationic group. A salt-forming compound can be easily obtained by mixing an aqueous solution of the above and an aqueous solution of a compound having an anionic group under stirring or vibration.
In the aqueous solution, the cationic group of the dye having a cationic group and the anionic group of the compound having an anionic group are ionized, these are ionically bonded, the ion-bonded portion becomes water-insoluble, and the salt-forming compound is precipitated. If it does not precipitate, a precipitate can be obtained by dropping the reaction liquid (mixture of a dye aqueous solution having a cationic group and an aqueous solution of a compound having an anionic group) into a poor solvent while stirring. it can. In addition, since a salt composed of a counter cation of a compound having an anionic group and a counter anion of a dye having a cationic group is water-soluble, it can be removed by washing or the like. The compound having an anionic group and the dye having a cationic group having fluorescence may be used alone or in a plurality of types having different structures.

  The salt-forming compound of the present invention is prepared by mixing a compound having a cationic group and a dye having an anionic group having fluorescence in an aqueous solution so that a counter anion of the compound having a cationic group and an anionic group (having fluorescence) can be obtained. A compound obtained by removing a salt composed of a counter cation of a dye having a dye, or a compound having an anionic group and a dye having a cationic group having fluorescence in an aqueous solution, From the viewpoint of heat resistance and storage stability, a compound formed by removing a salt composed of a counter cation of the compound having a counter ion and a counter anion of a dye having a fluorescent cationic group is preferable. When a by-product (for example, NaCl) generated by salt formation exists in the salt-forming compound, the heat resistance of the salt-forming compound may deteriorate in the colored composition.

  In order to dissolve a compound having a cationic group and a dye having an anionic group having fluorescence as an aqueous solution used at the time of salt formation, or a compound having an anionic group and a dye having a cationic group having fluorescence A mixed solution of water and a water-soluble organic solvent may be used as a solvent for dissolution. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 90% by weight, and most preferably 5 to 20% by weight, based on the total weight (100% by weight) of the aqueous solution.

The ratio of the compound having a cationic group to the dye having a fluorescent anionic group is the ratio between the total cationic unit of the compound having a cationic group and the total anionic group of the dye having a fluorescent anionic group. If the molar ratio is in the range of 10/1 to 1/4, the salt-forming compound of the present invention can be suitably adjusted, and more preferably in the range of 2/1 to 1/2.
The ratio of the compound having an anionic group and the dye having a cationic group having fluorescence is such that the total anionic unit of the compound having an anionic group and the total cationic group of the dye having a cationic group having fluorescence If the molar ratio is in the range of 10/1 to 1/4, the salt-forming compound of the present invention can be suitably adjusted, and more preferably in the range of 2/1 to 1/2.

(Sulphonic acid amide compound of acid dye)
A sulfonic acid amide compound of an acidic dye that can be preferably used for the luminescent dye (S) is obtained by chlorinating an acidic dye having —SO ₃ H and —SO ₃ Na by a conventional method, and converting —SO ₃ H into —SO _2. Cl and this compound can be prepared by reacting with an amine having a —NH ₂ group.
Specific examples of amine compounds that can be preferably used in sulfonamidation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine or the like.
For example, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 289 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 289. In addition, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 52 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 52.

When the luminescent dye (S) is a dye having an anionic group, it can be used as a salt-forming compound by salt formation with a compound having a cationic group. In that case, as the compound having a cationic group, a compound represented by the following general formula (7) can be used.

General formula (7)

In General Formula (7), R _{1 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. , R _{1 to} R ₃ may be bonded to each other to form a ring. Y ^- is representative of an inorganic or organic anion.
The substituent, alkyl group, alkenyl group, and aryl group mentioned here are the same as those described in the section of <Substituent group A>.

  A preferred form of the compound represented by the general formula (7) (quaternary ammonium salt compound) is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is. That is, it is necessary not to inhibit color development of the dye component and to cause no color change.

The molecular weight of the cation moiety serving as a counter for the quaternary ammonium salt compound is preferably in the range of 190 to 900. Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) ⁺ moiety in the following general formula (1). When the molecular weight is smaller than 190, light resistance and heat resistance are lowered, and the solubility in a solvent may be further lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the coloring component in the molecule is lowered, so that the color developability is lowered and the lightness is also lowered. More preferably, the molecular weight of the cation moiety is in the range of 240 to 850, and particularly preferably in the range of 350 to 800.
Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

Formula (7) in the R ¹ to R by ⁴ in which at least two or more the number of C in the side chain and 5 to 20, solubility in solvents is improved. When R ^{1 to} R ⁴ have 3 or more alkyl groups having a C number smaller than 5, the solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Further, if an alkyl group having a C number exceeding 20 is present in the side chain, the color forming property of the salt-forming compound may be impaired.

  The Y-component constituting the anion of the quaternary ammonium salt compound may be an inorganic or organic anion, but is preferably a halogen, more preferably chlorine.

Specific examples of such quaternary ammonium salt compounds include tetramethylammonium chloride (with a molecular weight of the cation moiety of 74), tetraethylammonium chloride (with a molecular weight of the cation moiety of 122), and monostearyltrimethylammonium chloride (with a molecular weight of the cation moiety). 312), distearyldimethylammonium chloride (cation part molecular weight 550), tristearyl monomethylammonium chloride (cation part molecular weight 788), cetyltrimethylammonium chloride (cation part molecular weight 284), trioctylmethylammonium chloride ( The molecular weight of the cation moiety is 368), dioctyldimethylammonium chloride (the molecular weight of the cation moiety is 270), monolauryltrimethyla Monium chloride (cation part molecular weight 228), dilauryldimethylammonium chloride (cation part molecular weight 382), trilaurylmethylammonium chloride (cation part molecular weight 536), triamylbenzylammonium chloride (cation part molecular weight 318), trihexylbenzylammonium chloride (cation part molecular weight 360), trioctylbenzylammonium chloride (cation part molecular weight 444), trilaurylbenzylammonium chloride (cation part molecular weight 612), benzyldimethylstearylammonium chloride (Molecular weight of the cation moiety is 388) and benzyldimethyloctyl ammonium chloride (molecular weight of the cation moiety is 248) , Or dialkyl (alkyl C ₁₄ -C ₁₈₎ dimethyl ammonium chloride (hydrogenated tallow) (molecular weight of the cationic moiety is from 438 to 550) is preferably used and the like.

As products, Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50, etc. manufactured by Kao Corporation, Lion Corporation's Arcade 210-80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75 or 2HP flakes and the like, among others QUARTAMIN D86P (distearyldimethylammonium chloride), or Arquad 2HT-75 (di (alkyl C ₁₄ -C ₁₈₎ dimethyl ammonium chloride) Etc. are preferable.

  Moreover, you may use the acrylic resin containing cationic group structural units, such as a quaternary ammonium salt, as a compound which has a cationic group. The acrylic resin containing a cationic group structural unit is an acrylic resin prepared by copolymerizing an ethylenically unsaturated monomer having an ammonium base or an ethylenically unsaturated monomer having an amino group as a monomer component.

  The ethylenically unsaturated monomer suitable for preparing the acrylic resin containing the cationic group structural unit of the present invention is shown below. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

[Ethylenically unsaturated monomer having ammonium base]
Examples of the ethylenically unsaturated monomer having an ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, and (meth) acryloyl. Alkyl (meth) acrylate quaternary ammonium salts such as oxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride Alkyl (meth) acryloylamide quaternary ammonium salts such as dimethyl Allyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

[Ethylenically unsaturated monomer having amino group]
Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl Examples include (meth) acrylic acid esters having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide, and styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

[Other copolymerizable ethylenically unsaturated monomers]
Other examples of monomers that can be used include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

The amount of the ammonium base present in the acrylic resin containing the cationic group structural unit is not particularly limited, but the ammonium salt value of the resin is preferably 10 to 200 mgKOH / g, and 20 to 130 mgKOH / g. More preferably.
In order for the ammonium salt value of the resin to satisfy the above range, the preferred content of the structural unit having a quaternary ammonium base is 2-50% by weight out of a total of 100% by weight of the structural units constituting the resin. It is preferable that it is a polymer, More preferably, it is a copolymer containing 10 to 40 weight%.

  The molecular weight of the acrylic resin containing a cationic group structural unit used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000 to 500,000. It is preferable that it is 3,000 to 15,000.

  Moreover, it is preferable that the acrylic resin containing a cationic group structural unit suitable for the present invention has a property of being dissolved in a solvent widely used for a color filter coloring composition. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is preferable to dissolve in glycol acetates, especially propylene glycol monomethyl ether acetate.

<Other colorants>
In addition to the luminescent dye (S), the color composition for color filter of the present invention may be used in combination with other colorants. Other colorants are dyes or organic pigments.

(Organic pigment (G))
When used in combination with other colorants, it is preferable to use the organic pigment (G) in order to adjust the hue and improve resistance. When the luminescent dye (S) and the organic pigment (G) are used in combination, the usage ratio of the luminescent dye (S) and the organic pigment (G) is luminescent dye (G) with respect to 100 parts by weight of the organic pigment (G). S) is preferably 1 to 80 parts by weight. More preferably, it is 5 to 60 parts by weight. When the addition amount of the luminescent dye (S) is within this range, the hue and the reproducible chromaticity region can be excellent.

  As the pigment used in combination, the following are used for each color filter segment.

[Pigment forming red filter segment]
As the red pigment forming the red filter segment, the red pigment or red dye described below can be used in combination.
Examples of red pigments include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 268, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used. Among them, C.I. I. Pigment Red 177, 242, 254, and 269 are preferably used.

  In order to form a red filter segment, a yellow or orange pigment may be used in combination. Examples of yellow or orange pigments include yellow pigments and orange pigments described below.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213,214,218,219,220, or 221, or the like is used. Examples of the orange pigment include C.I. I. Pigment Orange 38, 43, 71, 73 or the like is used.

  These pigments can be used alone or in admixture of two or more at any ratio as required.

  When used in combination with an organic pigment (G) as a colorant used in the red filter segment in the present invention, a red pigment or an orange pigment and a luminescent dye (S) are used in combination from the viewpoint of color gamut and durability. It is preferable. As the red pigment or orange pigment used in the present invention, C.I. I. Pigment red 254, 177, 242, 269 or C.I. I. Pigment Orange 38 is particularly preferred. By using these organic pigments and the luminescent dye (S) in combination, it is possible to provide a red coloring composition having excellent brightness, contrast ratio, and resistance.

[Pigment forming blue filter segment]
Examples of the pigment forming the blue filter segment include blue pigments such as C.I. I. Pigment Blue 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 18, 19, 22, 24, 24: 1, 53, 56, 56: 1, 57, 58, 59, 60, 61, 62, 64, etc. And / or C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

  When used in combination with the organic pigment (G) as the colorant used in the blue filter segment in the present invention, it is preferable to use the blue pigment and the luminescent dye (S) in combination from the viewpoint of color gamut and resistance. . The blue pigment used in the present invention includes C.I. from the viewpoint of brightness and contrast ratio. I. Pigment Blue 15: 1 and 15: 6 are particularly desirable, and it is preferable to use a rhodamine dye or a triphenylmethane dye as the luminescent dye (S). By using these organic pigments and the luminescent dye (S) in combination, it is possible to provide a blue coloring composition having excellent brightness, contrast ratio, and resistance.

[Pigment forming green filter segment]
Examples of the pigment forming the green filter segment include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, 37, and 58 can be used. Among them, C.I. I. It is preferable to use pigment green 36 or 58.
The green coloring composition includes C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination.
Among these, C.I. I. Pigment Yellow 138, 150 or the like is preferably used.

  When used in combination with the organic pigment (G) as the colorant used in the green filter segment in the present invention, it is preferable to use the green pigment and the luminescent dye (S) in combination from the viewpoint of color gamut and resistance. . The green pigment used in the present invention includes C.I. from the viewpoint of brightness and contrast ratio. I. Pigment Green 36 and 58 are particularly desirable, and the luminescent dye (S) is preferably a yellow dye, and particularly preferably a quinoline dye. By using these organic pigments in combination with the luminescent dye (S), it is possible to provide a green coloring composition having excellent brightness, contrast ratio, and resistance.

  In the coloring composition for a color filter of the present invention, the concentration of the coloring agent with respect to all the non-volatile components is preferably 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of obtaining sufficient color reproducibility. Most preferably, it is 20 to 80% by weight. When the concentration of the colorant component is less than 10% by weight, sufficient color reproducibility may not be obtained. When the concentration exceeds 90% by weight, the concentration of the colorant carrier such as a binder resin is lowered, and the color composition May become unstable.

(Miniaturization of pigment)
The organic pigment (G) that may be used together in the present invention is preferably used after being refined. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the total weight of the pigment from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the total weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the total weight of the pigment.

  It is also preferable to add the luminescent dye (S) of the present invention at the same time when the salt is milled (miniaturized). When the pigment is refined, a good colorant can be obtained by adding it together.

(dye)
A dye may be further used as a colorant of the color filter coloring composition of the present invention. It does not specifically limit as dye which can be used for a coloring agent, A well-known dye can be used. Examples thereof include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. The dye species can be selected in accordance with the target spectrum.

Examples of the dyes include compounds classified as dyes by Color Index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (Color dyeing company).
Specifically, C.I. I. Solvent Yellow 4 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 162, C.I. I. Solvent Red 45, 49, 125, 130, C.I. I. Solvent Orange 2, 7, 11, 15, 26, 56, 62, C.I. I. Solvent Blue 35, 37, 59, 67, C.I. I. Solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 etc. are mentioned.

  In addition, C.I. I. As an acid dye, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, C.I. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, C.I. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, C.I. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340, C.I. I. Acid Violet 6B, 7, 9, 17, 19, C.I. I. And dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109.

  In addition, C.I. I. As a direct dye, C.I. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141, C.I. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250, C.I. I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, C.I. I. Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, C.I. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, C.I. I. Examples include direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82.

  Furthermore, C.I. I. As a modern dye, C.I. I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, C.I. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95, C.I. I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, C.I. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83, 84, C.I. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, C.I. I. Modern dyes 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like can be mentioned.

  Suitable dyes for use in the colorant include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, squarylium dyes, and phthalocyanine dyes. And dyes.

<Binder resin (C)>
The binder resin in the present invention disperses a colorant, and examples thereof include a thermoplastic resin and a thermosetting resin. The resin is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type photosensitive coloring composition, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic substituent containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

  In order to disperse the colorant preferably, the weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  In addition, from the viewpoint of dispersibility, stability, developability, and heat resistance of the colorant, a carboxyl group that functions as a colorant adsorption group and an alkali-soluble group during development, an aliphatic group that functions as an affinity group for the colorant carrier and the solvent. The balance between the group and the aromatic group is important for the dispersibility of the pigment, the permeability of the developer in the coating film, the solubility of the developer in the uncured part, and the durability, and a resin having an acid value of 20 to 300 mgKOH / g. It is preferable to use it. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 500 parts by weight or less. More preferably, it is 100-400 weight part. More preferably, it is 160-320 weight part. The chromaticity region can be expanded by such a composition ratio of the pigment.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, -Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for a color filter because the brightness and sensitivity are good.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Of these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention comprises a coloring agent in a dye carrier such as a binder resin [C] and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal type. It can be produced by finely dispersing (pigment dispersion) using various dispersing means such as a sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, the luminescent dye (S), the quencher (D), and other colorants may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. . In addition, when the colorant has high solubility, specifically, it is highly soluble in the solvent used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to manufacture by finely dispersing as described above. There is no.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, additives, and the like. Can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -P104, P104S, 220S, 6919, 21116 or LACTIMON, LACTIMON-WS or BYKUMEN et al., SOLPERSE-3000, 9000, 13000, 13240, 13650, 1394, manufactured by Japan Lubrizol Corporation 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by BASF 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500 7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When adding a resin-type dispersant and a surfactant, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is a color filter comprising at least one filter segment formed from the coloring composition for a color filter of the present invention. The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one red filter segment is a coloring composition for a color filter of the present invention. It is preferable to form using. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  The green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. It is a composition obtained by using a green pigment such as CI Pigment Green 7, 10, 36, 37, or 58. Green coloring compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213, or a yellow pigment 214 and the like can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or the like is used.

  In addition, C.I. I. Purple pigments such as CI Pigment Violet 23, C.I. I. A metal lake pigment of a rhodamine dye such as CI Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5 can be used in combination. Further, a basic dye or a salt forming compound of an acidic dye that exhibits blue or purple can be used.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

(Resin polymerization average molecular weight (Mw))
Polymerization average molecular weight (Mw) of the resin is TSKgel column (manufactured by Tosoh Corporation), GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and measured in terms of polystyrene measured using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Resin acid value)
To 0.5 to 1.0 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant and an automatic titrator (“COM-555”). Titration using Hiranuma Sangyo) and the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Binder resin production method>
(Adjustment of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acrylic resin solution 1 was prepared by adding ether acetate.

<Method for producing resin having anionic group>
(Resin having an anionic group: JA)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 20.0 parts of 2-acrylamido-2-methylpropanesulfonic acid, 12.5 parts of methyl methacrylate, 20.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 3.0 parts of methacrylic acid, 2 -16.5 parts of hydroxyethyl methacrylate, 6.5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were made uniform and charged into a dropping funnel. It was attached to a separable flask and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 3240, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. In this way, a resin JA having 47% by weight of the resin component was obtained.

<Method for producing resin having cationic group>
(Resin having a cationic group: JK)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 5.0 parts of dimethylaminoethyl methyl chloride methacrylate, 27.5 parts of methyl methacrylate, 20.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 3.0 parts of methacrylic acid, 2-hydroxy After uniformizing 16.5 parts of ethyl methacrylate, 6.5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone, they were charged into a dropping funnel and separable into four necks. The flask was attached to the flask and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 3330, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. In this way, a resin JK in which the resin component had 47% by weight of a cationic group was obtained.

<Production method of fine pigment>
(Production of refined PR254 pigment (PR254-1))
Diketopyrrolopyrrole pigment C.I. I. 200 parts of Pigment Red 254 (“B-CF” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a refined diketopyrrolopyrrole pigment (PR254-1) was obtained.

(Production of refined PR177 pigment (PR177-1))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Anthraquinone-based fine red pigment (PR177-1) was obtained.

(Production of refined green pigment (PG58-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG58-1) was obtained.

(Production of refined yellow pigment (PY150-1))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY150-1) was obtained.

(Production of refined blue pigment (PB15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd., specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 80 The mixture was kneaded at 6 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine blue pigment (PB15: 6-1) was obtained.

(Production of refined purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A purple refined purple pigment (PV23-1) was obtained.

<Preparation of resin-type dispersant solution>
A resin type dispersant solution 1 was prepared by using a commercially available resin type dispersant, EFKA4300 manufactured by BASF, and ethylene glycol monomethyl ether acetate to prepare a 40 wt% nonvolatile content solution.

<Method for producing pigment dispersion>
(PR254 / Pigment dispersion (GP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (GP-1) whose non-volatile component is 20 weight% was produced.
Refined PR254 pigment (PR254-1): 11.0 parts Acrylic resin solution 1: 17.5 parts Propylene glycol monomethyl ether acetate: 66.5 parts Resin-type dispersant solution 1: 5.0 parts

(PR177 / Pigment dispersion (GP-2))
PR177 / Pigment Dispersion (GP-1) in the same manner as Pigment Dispersion (GP-1) except that the refined PR254 Pigment (PR254-1) pigment in the manufacturing method of Pigment Dispersion (GP-1) was changed to PR177-1. GP-2) was produced.

(PG58 pigment dispersion (GP-3))
PG58 / Pigment Dispersion (PG-1) was prepared in the same manner as Pigment Dispersion (GP-1) except that the refined PR254 Pigment (PR254-1) pigment was changed to PG58-1 in the production method of Pigment Dispersion (GP-1). GP-3) was produced.

(PY150 / Pigment dispersion (GP-4))
PY150 / Pigment dispersion (PY150) in the same manner as the pigment dispersion (GP-1) except that the refined PR254 pigment (PR254-1) pigment was changed to PY150-1 in the production method of the pigment dispersion (GP-1). GP-4) was produced.

(PB15: 6, pigment dispersion (GP-5))
PB15: 6 · PB15: 6 · Pb15: 6 · In the same manner as the pigment dispersion (GP-1), except that the refined PR254 pigment (PR254-1) pigment was changed to PB15: 6-1 in the production method of the pigment dispersion (GP-1). A pigment dispersion (GP-5) was produced.

(PV23 / pigment dispersion (GP-6))
PV23 / Pigment Dispersion (GP-1) in the same manner as Pigment Dispersion (GP-1), except that the refined PR254 Pigment (PR254-1) pigment was changed to PV23-1 in the production method of Pigment Dispersion (GP-1). GP-6) was produced.

(PR269 / Pigment dispersion (GP-7))
PR269 / Pigment Dispersion (GP-) in the same manner as Pigment Dispersion (GP-1) except that the refined PR254 Pigment (PR254-1) pigment was changed to PR269 in the production method of Pigment Dispersion (GP-1). 7) was produced.

(PR242, pigment dispersion (GP-8))
PR242 / Pigment Dispersion (GP-) in the same manner as Pigment Dispersion (GP-1), except that the refined PR254 Pigment (PR254-1) pigment in the manufacturing method of Pigment Dispersion (GP-1) was changed to PR242. 8) was produced.

<Method for producing colored composition for color filter>
Example 001
(Production of colored composition (RP-001))
After mixing various materials according to the following, a colored composition (RP-001) was obtained by performing ultrasonic irradiation for 1 hour.
Luminescent dye (S) Basic Violet 10: 3.8 parts Salt-forming compound [B (C ₆ F ₅ ) ₄ ] Na: 5.0 parts Quenching agent (D) D-01: 0.2 part Acrylic resin solution 1 : 25.0 parts Cyclohexanone: 16.0 parts Total: 50.0 parts

[Examples 002 to 080, Comparative Examples 1 to 10]
(Production of colored compositions RP-002 to 080 and RPH-1 to 10)
Except for changing the luminescent dye (S), quencher (D), and salt-forming compound in the production of the colored composition (RP-001) to the materials described in Tables 6 to 7, the colored composition ( In the same manner as in the case of RP-001), colored compositions (RP-002 to 080, RPH-1 to 10) were obtained.

[Example 081]
(Production of colored composition (RP-081))
After mixing various materials according to the following, a colored composition (RP-081) was obtained by performing ultrasonic irradiation for 1 hour.
Luminescent dye (S) PR269 / Pigment paste GP-7: 3.8 parts Quencher (D) D-01: 0.2 parts Acrylic resin solution 1: 30.0 parts Cyclohexanone: 16.0 parts Total: 50. 0 copies

[Examples 082 to 120, Comparative Examples 11 to 15]
(Production of colored compositions RP-082 to 120, RPH-11 to 15)
The same as in the case of the colored composition (RP-081), except that the luminescent dye (S) and the quencher (D) in the production of the colored composition (RP-081) were changed to the materials described in Table 8, respectively. The coloring composition (RP-082-120, RPH-11-15) was obtained by the method of.

It shows in Tables 9-14 about the luminescent pigment | dye (S) and quencher (D) which were used in Tables 6-8. The HOMO of the luminescent dye (S) and the quencher (D) was measured using an ionization potential measuring device PYS-202 manufactured by Sumitomo Heavy Industries, Ltd. Moreover, the absorption spectrum was measured using the ultraviolet visible near infrared spectrophotometer V-570 by JASCO Corporation, and LUMO was computed.

<Evaluation of coloring composition for color filter>
Using the obtained colored compositions (RP-001 to 120, RPH-1 to 15), the contrast ratio (CR) and heat resistance of the coating film were evaluated by the following methods. Tables 15 to 17 show the evaluation results.

(Evaluation of contrast ratio (CR) of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

The coloring composition is applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 60 minutes and allowed to cool. A membrane substrate was prepared. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C.
The contrast ratio was determined according to the following criteria.
◎: 9000 or more ○: 6000 or more, less than 9000 △: 3000 or more, less than 6000 ×: less than 3000

(Heat resistance evaluation)
The coloring composition is applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 60 minutes and allowed to cool. A membrane substrate was prepared. The prepared coating film substrate was adjusted so that the film thickness of the obtained coating film became 1.5 μm after the heat treatment at 230 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 220 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and determined according to the following criteria.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
A: ΔEab * is less than 3.0 ○: ΔEab * is 3.0 or more and less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

  As shown in Tables 15 to 17, all of the coloring compositions for color filters of the present invention were excellent in heat resistance and had a high contrast ratio. High contrast is achieved by combining the luminescent dye (S) and the quencher (D) of the present invention.

<Production of photosensitive coloring composition for color filter>
[Example 121]
(Red photosensitive coloring composition (RR-001))
The following mixture (100 parts in total) was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain a red photosensitive coloring composition (RR-001).
Coloring composition (RP-001): 37.5 parts PR254 / Pigment dispersion (GP-1): 25.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (“Aronix manufactured by Toagosei Co., Ltd.) M-402 "): 2.0 parts photopolymerization initiator (" Irgacure OXE-02 "manufactured by BASF): 1.5 parts methoxypropyl acetate: 26.5 parts

[Examples 122 to 240, Comparative Examples 16 to 30]
(Red photosensitive coloring composition (RR-002 to 120, RRH-16 to 30))
The red photosensitive coloring composition (RR-002 to 120, 120) was the same as the red photosensitive coloring composition (RR-001) except that the coloring composition and the pigment dispersion were changed to the types shown in Tables 12 to 14. RRH-16 to 30) were obtained. In each photosensitive coloring composition, a total of 62.5 parts of the total of the coloring composition and the pigment dispersion is obtained. When the coating film substrate for evaluating the brightness of each coloring composition is C = 0. The ratio was adjusted so that y = 0.325, and 100 parts of a red photosensitive coloring composition was prepared.

[Comparative Example 31]
(Red photosensitive coloring composition (RRH-31))
The following mixture (100 parts in total) was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain a red photosensitive coloring composition (RRH-31).
PR254 / Pigment dispersion (GP-1): 27.0 parts PR177 / Pigment dispersion (GP-2): 23.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd.) "Aronix M-402"): 2.0 parts photopolymerization initiator ("Irgacure OXE-02" manufactured by BASF): 1.5 parts methoxypropyl acetate: 39.0 parts

<Evaluation of photosensitive coloring composition for color filter>
Using the obtained red photosensitive coloring composition (RR-001 to 120, RRH-16 to 31), the contrast ratio and brightness of the produced red coating film were evaluated by the following methods. Tables 18 to 20 show the evaluation results.

(Contrast ratio evaluation)
The photosensitive coloring composition is applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 60 minutes and allowed to cool. Thus, a coated substrate was produced. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted so that x = 0.658 and y = 0.325 using a C light source after heat treatment at 230 ° C.
The contrast ratio was determined according to the following criteria.
◎: 16000 or more ○: 14000 or more, less than 16000 Δ: 12000 or more, less than 14000 ×: less than 12000

(Lightness evaluation)
The photosensitive coloring composition was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that x = 0.658 and y = 0.325 using a C light source. This was exposed to ultraviolet light at an exposure amount of 50 mJ / cm ² , spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, and baked in an oven at 230 ° C. for 60 minutes for photosensitive coloring. A cured coated substrate of the composition was prepared. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.
A: 19.2 or more O: 19.0 or more, less than 19.2 Δ: 18.8 or more, less than 19.0 ×: less than 18.8

  As shown in Tables 18 to 20, the colored composition for a color filter of the present invention was excellent in brightness as compared with the pigment system. Moreover, the high contrast ratio was able to be achieved by combining a luminescent pigment | dye (S) and a quencher (D).

<Production of color filter>
(Green photosensitive coloring composition (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition (GR-1).
PG58 / pigment dispersion (GP-3): 32.0 parts PY150 / pigment dispersion (GP-4): 18.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd.) "Aronix M-402"): 2.0 parts Dipentaerythritol hexaacrylate Photopolymerization initiator ("Irgacure OXE-02" manufactured by BASF): 1.5 parts Etanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-
Carbazol-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition (BR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to produce a blue photosensitive coloring composition (BR-1).
PB15: 6 / Pigment dispersion (GP-5): 45.0 parts PV23 / Pigment dispersion (GP-6): 5.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (Toagosei Co., Ltd.) "Aronix M-402"): 2.0 parts Photopolymerization initiator ("Irgacure OXE-02" manufactured by BASF): 1.5 parts Cyclohexanone: 39.0 parts

The red photosensitive coloring composition (RR-001) of the present invention was applied to a glass substrate on which a black matrix was previously formed by spin coating, and then prebaked at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp.
Thereafter, this substrate was spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and air-dried. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
Next, the green photosensitive coloring composition (GR-1) is used to form a green coloring pixel layer in the same manner as the red coloring pixel layer, and further, the blue photosensitive coloring composition (BR-1) is used. In the same manner as the red colored pixel layer, a blue colored pixel layer was formed to obtain a color filter (CF-1). The formed film thickness of each colored pixel layer was 2.0 μm.

  The color filter using the red coloring composition of the present invention has high brightness and excellent contrast ratio, and the effect of the present invention has been proved.

Claims (6)

A coloring composition for a color filter comprising a luminescent dye (S), a quencher (D), and a binder resin (C),
Highest occupied molecular orbital of the luminescent dye (S); the difference between the energy levels HOMO _S, the energy level HOMO _D of the highest occupied molecular orbital of the quencher (D) of the (Highest Occupied Molecular Orbital HOMO) is,
−2.0 <| HOMO _D | − | HOMO _S | <0.0 (eV)
The coloring composition for color filters characterized by satisfying the following relational expression: Lowest unoccupied molecular orbital of the luminescent dye (S); the difference between the energy levels LUMO _S, the energy level LUMO _D of the lowest unoccupied molecular orbital of the quencher (D) of (Lowest Unoccupied Molecular Orbital LUMO) is,
| LUMO _D | − | LUMO _S | <0.0 (eV)
The coloring composition for a color filter according to claim 1, wherein the following relational expression is satisfied. A coloring composition for a color filter comprising a luminescent dye (S), a quencher (D), and a binder resin (C),
The coloring composition for a color filter, wherein the quencher (D) is any one of compounds represented by the following general formulas (1) to (4).

General formula (1)
[In general formula (1),
X ^{1 to} X ⁴ each independently represents a direct bond, a substituted or unsubstituted carbon atom, a sulfur atom, or a selenium atom.
R ^{1 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group Represents an aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{1 to} R ⁴ are adjacent groups. May combine with each other to form a ring. ]

General formula (2)
[In general formula (2),
X ⁵ represents a direct bond, a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, or a sulfur atom.
R ^{5 to} R ¹³ each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group , An aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{5 to} R ¹³ are adjacent groups. May combine with each other to form a ring. ]

General formula (3)
[In general formula (3),
R ^{14 to} R ²¹ each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group , An aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{14 to} R ²¹ are adjacent groups. May combine with each other to form a ring. ]

General formula (4)
[In general formula (4),
R ^{22 to} R ³³ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, substituted or Unsubstituted aliphatic heterocyclic group, substituted or unsubstituted aromatic heterocyclic group, halogen atom, hydroxy group, alkoxy group, aryloxy group, aldehyde group, alkylcarbonyl group, arylcarbonyl group, carboxy group, alkoxycarbonyl group Represents an aryloxycarbonyl group, a thiol group, an alkylthio group, an arylthio group, a nitro group, an amino group, a sulfo group, a cyano group, a silyl group, a boronyl group, or a phosphino group, and R ^{22 to} R ³³ are adjacent groups. May combine with each other to form a ring. ]   The coloring composition for a color filter according to any one of claims 1 to 3, wherein the luminescent dye (S) is a xanthene dye, a cyanine dye, or an azo dye.   Furthermore, the coloring composition for color filters in any one of Claims 1-4 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a filter segment formed from the colored composition for color filter according to claim 1 on a substrate.