TWI741183B - Colored resin composition, color filter and display device - Google Patents

Abstract

The present invention provides a coloring resin composition that can form a color filter and a display device with excellent contrast and heat resistance. The coloring resin composition of the present invention is characterized by comprising a coloring agent and a resin, and the coloring agent includes a compound represented by formula (I), the compound having a maximum absorption at 500 nanometers or more and less than 700 nanometers Wavelength compound.

[式(I)中，環T¹表示可具有取代基的碳數6至20的芳香族烴環或可具有取代基的芳香族雜環。

[In formula (I), ring T ¹ represents an optionally substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic ring.

The ring T ² represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and contains N ^{+ in the constituent atoms of the ring.}

L ¹ and L ² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms that may have a substituent.

M ⁿ⁺ represents any cation. n represents an integer of 1 or more and 5 or less. ]

Description

Colored resin composition, color filter and display device

The present invention relates to a colored resin composition, a color filter, and a display device.

Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, plasma displays, and solid-state imaging elements such as CCD and CMOS sensors are made of colored resin compositions. As such a colored resin composition, a composition containing a compound represented by formula (x) as a coloring agent is known (Patent Document 1).

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2015-98589

However, the color filter formed from the above-mentioned colored resin composition known so far may not sufficiently satisfy the requirement for contrast, and may not endure the heat during post-baking, and the color may change significantly. Therefore, the present invention provides a coloring resin composition that can form a color filter excellent in contrast and heat resistance.

The present invention includes the following inventions.

[1] A colored resin composition comprising a colorant and a resin, and the colorant includes a compound represented by formula (I), which is a compound having a maximum absorption wavelength at 500 nm or more and less than 700 nm.

[式(I)中，環T¹表示可具有取代基的碳數6至20的芳香族烴環或可具有取代基的芳香族雜環。

[In formula (I), ring T ¹ represents an optionally substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic ring.

The ring T ² represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and contains N ^{+ in the constituent atoms of the ring.}

L ¹ and L ² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms that may have a substituent.

M ⁿ⁺ represents any cation.

n represents an integer of 1 or more and 5 or less. ]

[2] The colored resin composition according to [1], which further contains a polymerizable compound and a polymerization initiator.

[3] A color filter formed of the colored resin composition as described in [1] or [2].

[4] A display device including the color filter as described in [3].

According to the present invention, there is provided a coloring resin composition that can form a color filter excellent in contrast and heat resistance.

<Colored resin composition>

The coloring resin composition of the present invention includes a colorant (A) and a resin (B). As the colorant (A), it contains a maximum absorption wavelength at 500 nm or more and less than 700 nm and is represented by formula (I) compound of.

The colored resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).

The coloring resin composition of the present invention may further include a polymerization initiator (D1), a solvent (E), and a leveling agent (F).

In this specification, the compound exemplified as each component can be used singly or in combination of multiple types unless otherwise specified.

<Colorant (A)>

In the coloring resin composition of the present invention, a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)) is contained as a colorant (A). Compound (I) has a maximum absorption wavelength above 500 nanometers and less than 700 nanometers.

It should be noted that the formula (I) is an example of a resonance structure, and the compound represented by the formula (I) is defined as including all structures having a resonance relationship with the formula (I).

[式(I)中，環T¹表示可具有取代基的碳數6至20的芳香族烴環或可具有取代基的芳香族雜環。

[In formula (I), ring T ¹ represents an optionally substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic ring.

The ring T ² represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and contains N ^{+ in the constituent atoms of the ring.}

L ¹ and L ² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms that may have a substituent.

M ⁿ⁺ represents any cation.

n represents an integer of 1 or more and 5 or less. ]

Compound (I) is a green to red coloring agent having a maximum absorption wavelength at 500 nm or more and less than 700 nm. The maximum absorption wavelength of compound (I) can be confirmed by measuring the absorption spectrum of compound (I). Compound (I) is preferably 530 nm or more, more preferably 580 nm or more, and even more preferably 600 nm or more. , And preferably have a maximum absorption wavelength below 690 nm.

In the present invention, the maximum absorption wavelength of the compound (I) is measured with a spectrophotometer, and as a measurement sample, a solution in which the compound (I) is dissolved in a measurement solvent can be used. Examples of the above-mentioned measurement solvent include N-methylpyrrolidone, N,N-dimethylformamide, and dimethylsulfene.

(chrysene)、稠四苯(tetracene)等；及其他。該芳香族烴環的碳數較佳為6至16，更佳為6至10。 The aromatic hydrocarbon ring formed by T ¹ represents a ring of 6 to 20 carbon atoms include a monocyclic aromatic hydrocarbons, such as: benzene, toluene, xylene, mesitylene, cumene, cymene (cymene), etc.; and fused polycyclic hydrocarbons, such as: pentalene, indene, naphthalene, azulene, heptalene, biphenylene, asymmetric-indacene , Symmetry-indene, acenaphthylene, stilbene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene , Pyrene,

(chrysene), tetracene, etc.; and others. The carbon number of the aromatic hydrocarbon ring is preferably 6-16, more preferably 6-10.

The aromatic heterocyclic ring represented by the ring T ¹ contains at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a constituent element of the ring. The aromatic heterocyclic ring may be monocyclic or polycyclic. The carbon number of the aromatic heterocyclic ring is preferably 3-30, more preferably 3-20, and particularly preferably 3-15. The aromatic heterocyclic ring represented by the ring T ¹ is more preferably a nitrogen-containing aromatic heterocyclic ring containing a nitrogen atom as a constituent element of the ring and the nitrogen atom is >N-.

Regarding the ring T ¹ , the hydrogen atom bonded to any atom constituting the ring in the above-mentioned ring is removed, and the hydrogen atom is bonded to L ¹ and the carbon atom, respectively.

Examples of the nitrogen-containing aromatic heterocyclic ring in the ring T ¹ include the ring represented by the formula (T ¹ -A) and the formula (T ¹ -B), and the like.

[式(T¹-A)及式(T¹-B)中，X¹表示-C(R^a3)(R^a4)-、-N(R^a5)-、-O-或-S-，較佳為-C(R^a3)(R^a4)-。

[In formula (T ¹ -A) and formula (T ¹ -B), X ¹ represents -C(R ^a3 )(R ^a4 )-, -N(R ^a5 )-, -O- or -S-, which is more Preferably, it is -C(R ^a3 )(R ^a4 )-.

R ^a3 , R ^a4 and R ^a5 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

Ring T ⁵ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent.

i is 1 or 2. ]

^{The nitrogen-containing aromatic heterocyclic ring containing N +} in the constituent atoms of the ring represented by the ring T ² is a nitrogen-containing aromatic heterocyclic ring containing a nitrogen atom as a constituent element of the ring, and the nitrogen atom is >N ⁺ <. The nitrogen-containing aromatic heterocyclic ring ^{containing N +} in the constituent atoms of the ring represented by the ring T ^{2 preferably contains >C=N +} <as a constituent element of the ring.

Regarding the ring T ² , the hydrogen atom bonded to any atom constituting the ring in the above-mentioned ring is removed, and the hydrogen atom is bonded to L ² and a carbon atom, respectively.

Examples of the nitrogen-containing aromatic heterocyclic ring in the ring T ² include the ring represented by the formula (T ² -A) and the formula (T ² -B), and the like.

[式(T²-A)及式(T²-B)中，X²表示-C(R^a6)(R^a7)-、-N(R^a8)-、-O-或-S-，較佳為-C(R^a6)(R^a7)-。

[In formula (T ² -A) and formula (T ² -B), X ² represents -C(R ^a6 )(R ^a7 )-, -N(R ^a8 )-, -O- or -S-, more Preferably, it is -C(R ^a6 )(R ^a7 )-.

R ^a6 , R ^a7 and R ^a8 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

Ring T ⁶ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent.

j is 0 or 1. ]

The aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by ^Ra3 to ^{Ra8 may be linear, branched, and cyclic.}

Examples of the linear or branched aliphatic hydrocarbon group include linear aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc.; and Branched chain aliphatic hydrocarbon groups, such as: isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 5, and particularly preferably 1 to 4.

The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The carbon number of the cyclic aliphatic hydrocarbon group is preferably 3-8, more preferably 3-6.

The aliphatic hydrocarbon groups having 1 to 8 carbons represented by ^Ra3 to ^Ra8 are each independently preferably a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 6 carbons, more preferably a hydrogen atom or The linear alkyl group having 1 to 4 carbon atoms is particularly preferably a methyl group or an ethyl group.

、稠四苯等；及其他。該芳香族烴環的碳數較佳為6至16，更佳為6至10。 As the aromatic hydrocarbon ring with 6 to 20 carbon atoms represented by ring T ⁵ and ring T ⁶ , aromatic monocyclic hydrocarbons such as benzene, toluene, xylene, mesitylene, cumene, Cumene, etc.; and condensed polycyclic hydrocarbons, such as: pentene, indene, naphthalene, azulene, heptene, biphenyl, asymmetric-indene, symmetric-indene, acenaphthylene, stilbene , Vine, phenanthrene, anthracene, fluoranthene, acephenanthrene, aceanthrene, triphenylene, pyrene,

, Thick tetrabenzene, etc.; and others. The carbon number of the aromatic hydrocarbon ring is preferably 6-16, more preferably 6-10.

Ring T ⁵ and ring T ⁶ are each independently preferably benzene, naphthalene, anthracene, or anthracene, more preferably benzene or naphthalene.

The ring T ⁵ and the ring T ⁶ may be the same or different.

Aromatic hydrocarbon ring T ¹ represents a carbon number of 6 to 20 by the aromatic heterocyclic ring ^represented by T, and the cycle T ² represents a N ⁺ nitrogen-containing aromatic heterocyclic ring-constituting atoms in the And the aromatic hydrocarbon ring having 6 to 20 carbons represented by the rings T ⁵ and T ^{6 may have a substituent.} Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, bromine atom, etc.; nitro group; cyano group; -N(R ^a1 )(R ^a2 ) group; hydroxyl group; Alkoxy for 6, such as methoxy, ethoxy, etc.; sulfhydryl; alkylsulfhydryl having 1 to 6 carbon atoms, such as methylsulfhydryl, ethylsulfhydryl, etc.; carboxy; Carboxamide; alkoxycarbonyl groups having 1 to 6 carbons, such as methoxycarbonyl, ethoxycarbonyl, etc.; sulfonic acid groups; sulfamsulfonyl groups; and alkoxy sulfonates having 1 to 6 carbons Groups, such as: methoxysulfonyl, ethoxysulfonyl, etc.; and others.

^Ra1 and ^Ra2 in the above-N(R ^a1 )(R ^a2 ) group each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. The aliphatic hydrocarbon group having 1 to 8 carbon atoms may be linear, branched, and cyclic.

Examples of the linear or branched aliphatic hydrocarbon group include linear aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc.; and Branched chain aliphatic hydrocarbon groups, such as: isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc.; and others. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 5, and particularly preferably 1 to 4.

The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The carbon number of the cyclic aliphatic hydrocarbon group is preferably 3-8, more preferably 3-6.

The ring T ¹ and the ring T ² may be the same or different.

The divalent hydrocarbon group having 1 to 8 carbons represented by L ¹ and L ² is a divalent group derived by removing two arbitrary hydrogen atoms from a hydrocarbon having 1 to 8 carbons, and the number of carbons can be exemplified A divalent aliphatic hydrocarbon group of 1 to 8 or a divalent aromatic hydrocarbon group of 6 to 8 carbons.

Examples of the above-mentioned divalent aliphatic hydrocarbon group include a divalent chain hydrocarbon group having 1 to 8 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms.

The divalent chain aliphatic hydrocarbon groups include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1 Alkanediyl such as ,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.

Examples of the divalent alicyclic hydrocarbon group include cyclopropane-1,1-diyl, cyclopropane-1,2-diyl, cyclobutane-1,1-diyl, and cyclobutane-1,2- Diyl, cyclobutane-1,3-diyl, cyclopentane-1,1-diyl, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl, cyclohexane -1,1-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl and from formula (L-a1) to formula (L-a6) and the like.

Examples of the divalent aromatic monocyclic hydrocarbon group include ortho-phenylene, meta-phenylene, para-phenylene, and groups represented by formulas (L-b1) to (L-b6).

The divalent hydrocarbon group having 1 to 8 carbons represented by L ¹ and L ² is preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbons, more preferably a divalent chain hydrocarbon group having 1 to 8 carbons, and particularly preferred It is an alkanediyl group having 1 to 8 carbons, and a linear alkanediyl group having 1 to 8 carbons is particularly preferred.

In addition, the carbon number of the divalent hydrocarbon group is preferably 1 to 6, and more preferably 1 to 4.

The ^{divalent hydrocarbon group having 1 to 8 carbon atoms in L 1} and L ² may have a substituent, and examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; nitro group; cyano group; Amino; hydroxyl; alkoxy with 1 to 6 carbons, such as methoxy, ethoxy, etc.; hydrogen thio; alkyl with 1 to 6 hydrogen thio, such as methyl thio Ethyl hydrogensulfanyl group, etc.; carboxyl group; carboxamide group; alkoxycarbonyl group having 1 to 6 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, etc.; sulfonic acid group; aminosulfonyl group; and carbon number Alkoxysulfonyl groups from 1 to 6, such as methoxysulfonyl, ethoxysulfonyl, etc.; and others.

The divalent hydrocarbon group preferably does not have a substituent.

L ¹ and L ² are each independently preferably methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, or from formula (L-b1) to formula (L The group represented by -b6) is more preferably methylene, ethylene, propane-1,3-diyl or butane-1,4-diyl. It should be noted that L ¹ and L ² may be the same or different, but are preferably the same.

M ^{n+ is} preferably a hydrogen ion, an n-valent metal ion, or a substituted or unsubstituted ammonium ion.

As the n-valent metal ion represented by Mn ⁺ , alkali metal ions, such as lithium ion, sodium ion, potassium ion, etc.; alkaline earth metal ions, such as magnesium ion, calcium ion, strontium ion, barium ion, etc. ; Transition metal ions, such as: titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, etc.; and main group metal ion, such as: zinc ion, cadmium ion, aluminum ion, indium Ion, tin ion, lead ion, bismuth ion, etc.; and others.

In addition, examples of the substituted or unsubstituted ammonium ion represented ^{by M n+ include quaternary ammonium ions such as tetraalkylammonium ions.}

M ^{n+ is} preferably hydrogen ion or n-valent metal ion, more preferably hydrogen ion, alkali metal ion or alkaline earth metal ion, particularly preferably hydrogen ion, sodium ion, potassium ion, magnesium ion or barium ion, particularly preferably Hydrogen ion or barium ion.

n is preferably 4 or less, more preferably 3 or less, and particularly preferably 1 or 2.

The compound (I) is preferably a compound having a valence of 0, that is, an electrically neutral compound.

Compound (I) is preferably a compound represented by formula (II) (hereinafter sometimes referred to as compound (II)).

[式(II)中，L¹、L²、Mⁿ⁺及n係與前文相同。

[In formula (II), L ¹ , L ² , M ⁿ⁺ and n are the same as above.

Ring T ³ represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent.

The ring T ⁴ represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and contains N ^{+ in the constituent atoms of the ring.} ]

The nitrogen-containing aromatic heterocyclic ring represented by the ring T ³ is a nitrogen-containing aromatic heterocyclic ring containing a nitrogen atom as a constituent element of the ring and the nitrogen atom is >N-, preferably by the formula (T ³ -A) or (T ³ -B) represents the ring.

^{The nitrogen-containing aromatic heterocyclic ring containing N +} in the constituent atoms of the ring represented by ring T ⁴ is a nitrogen-containing aromatic heterocyclic ring containing a nitrogen atom as a constituent element of the ring and the nitrogen atom is >N ⁺ <, preferably It is a ring represented by formula (T ⁴ -A) or formula (T ^{4 -B).}

The rings T ³ and T ⁴ may be the same or different.

[式(T³-A)、式(T³-B)、式(T⁴-A)及式(T⁴-B)中，X¹、X²、環T⁵、環T⁶係與前文相同。

[In formula (T ³ -A), formula (T ³ -B), formula (T ⁴ -A), and formula (T ⁴ -B), X ¹ , X ² , ring T ⁵ , ring T ⁶ are the same as the preceding same.

*L means ^{the bonding terminal to L 1} or L ² and *C means the bonding terminal to a carbon atom. ]

Ring T ¹ and ring T ^{3 are more} preferably rings represented by formula (R ³ -1) to formula (R ³ -6), and particularly ^{preferably are represented by formula (R 3} -1) to formula (R ³ -3) Of the ring. The ring T ² and the ring T ^{4 are more} preferably a ring represented by the formula (R ⁴ -1) to the formula (R ⁴ -6), and particularly preferably are represented by the formula (R ⁴ -1) to the formula (R ⁴ -3) Of the ring.

Compound (I) and compound (II) are more preferably compounds represented by formula (III) (hereinafter sometimes referred to as compound (III)).

[式(III)中，環T⁵、環T⁶、L¹、L²、Mⁿ⁺及n係與前文相同。]

[In formula (III), ring T ⁵ , ring T ⁶ , L ¹ , L ² , M ⁿ⁺ and n are the same as above. ]

As the compound (I), the compounds represented by formula (I-1) to formula (I-63) shown in Table 1, and the like can be cited.

Compound (I) is preferably a compound represented by formula (I-1) to formula (I-42), more preferably a compound represented by formula (I-1) to formula (I-12), and a compound represented by formula (I-1) to formula (I-12), and Compounds represented by formula (I-22) to formula (I-33) are particularly preferably compounds represented by formula (I-22) to formula (I-33).

In Table 1, ring T ¹ represents a ring represented by formula (R ³ -a1) to formula (R ³ -a3), ring T ² represents a ring represented by formula (R ⁴ -a1) to formula (R ⁴ -a3) ring. In formula (R ³ -a1) to formula (R ³ -a3) and formula (R ⁴ -a1) to formula (R ⁴ -a3), *L and *C are the same as the foregoing.

In Table 1, L ¹ and L ² represent divalent hydrocarbon groups represented by formula (L-1) to formula (L-7). In formulas (L-1) to (L-7), *n means a bonding terminal to a nitrogen atom, and *s means a bonding terminal to a sulfur atom.

>N⁺=C<以外為相同的由式(I)所示的化合物(其中，Mⁿ⁺=H⁺)係能夠藉由使式(pt1)所示的化合物與式(pt2)所示的化合物反應而製造。在本反應中，相對於由式(pt2)表示的化合物1莫耳，由式(pt1)表示的化合物的使用量較佳為1.5至2.5莫耳。 L ¹ is the ^{same as L 2} and ring T ¹ and ring T ² are divided by >N-CH<

Except for >N ⁺ =C<, the same compound represented by formula (I) (where M ⁿ⁺ =H ⁺ ) can be obtained by combining the compound represented by formula (pt1) with the compound represented by formula (pt2) Manufactured by reaction. In this reaction, the usage amount of the compound represented by the formula (pt1) is preferably 1.5 to 2.5 mol relative to 1 mol of the compound represented by the formula (pt2).

In addition, the compound represented by the formula (I) (wherein M ⁿ⁺ ≠H ⁺ ) can be obtained by combining the compound represented by the formula (I) (wherein, M ⁿ⁺ =H ⁺ ) with an n-valent metal ion It is produced by reacting halide (preferably chloride), acetate, phosphate, sulfate, silicate, or cyanide.

[式(pt1)及式(I)中，環T¹、環T²、L¹、L²、Mⁿ⁺及n係與前文相同。]

[In formula (pt1) and formula (I), ring T ¹ , ring T ² , L ¹ , L ² , M ⁿ⁺ and n are the same as the above. ]

With respect to the content of the compound (I), relative to 100 parts by mass of the resin (B), it is preferably 0.1 to 150 parts by mass, more preferably 1 to 100 parts by mass, and particularly preferably 5 to 80 parts by mass.

In the coloring resin composition of the present invention, as the colorant (A), in addition to the compound (I), a dye (A1) and a pigment (A2) may be contained.

The dye (A1) is not particularly limited, and conventional dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. As a dye, for example, a compound that is classified as having a hue in addition to a pigment in the Color Index (published by The Society of Dyers and Colourists), or a compound having a hue in the dyeing notes (color Dyesha) The conventional dyes described in. In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, Methylene dyes, methine azo dyes, squarylium dyes (but not compound (I)), acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes Wait. Among these, dyes having organic solvent solubility are preferred.

The pigment (A2) is not particularly limited, and conventional pigments can be used. For example, pigments classified as pigments in the color index (published by the British Association of Dyestuffs and Colorists) can be cited.

Examples of pigments include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, Orange pigments such as 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other cyan pigments; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Brown 23, 25 and other brown pigments; CI Pigment Black 1, 7 and other black pigments.

The content rate of the coloring agent (A) is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and particularly preferably 1 to 50% by mass relative to the total amount of solid components.

In the total amount of the colorant (A), the content of the compound (I) is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

Here, the "total amount of solid content" in this specification refers to the amount after removing the solvent content from the total amount of the colored resin composition. The total amount of solid content and the content of each component relative to it can be measured by conventional analysis means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride (a) (hereinafter sometimes referred to as "(a) ") The resin of the structural unit. Furthermore, the resin (B) preferably has at least one structural unit selected from the following structural units: derived from a monomer (b) having a cyclic ether structure with a carbon number of 2 to 4 and an ethylenically unsaturated bond (the following Sometimes referred to as "(b)"), derived from the monomer (c) that can be copolymerized with (a) (but different from (a) and (b)) (hereinafter sometimes referred to as "(c)") The structural unit and the structural unit having an ethylenically unsaturated bond in the side chain.

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and succinic acid mono[2-(formaldehyde). (Yl)acryloyloxyethyl]ester, etc., preferably acrylic acid, methacrylic acid, and maleic anhydride.

(b) It is preferably a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth)acryloyloxy group monomer.

In addition, in this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

Examples of (b) include glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate , 3-ethyl-3-(meth)acryloyloxymethyloxycyclobutane, tetrahydrofurfuryl (meth)acrylate, etc., preferably glycidyl (meth)acrylate, (meth) 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane.

As (c), for example, methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, (methyl) ) Tricyclo [5.2.1.0 ^2,6 ]decane-8-yl acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N -Cyclohexyl maleimide, N-benzyl maleimide, styrene, vinyl toluene, etc., preferably, styrene, vinyl toluene, 2-hydroxyethyl (meth)acrylate , N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, etc.

Resins having structural units with ethylenically unsaturated bonds in the side chain can be added to the copolymer of (a) and (c) by (b) or (a) to (b) and (c). ) Copolymers. The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c), and further reacting carboxylic anhydride.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 5,000 to 30,000.

The degree of dispersion [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) in terms of solid content is preferably 20 to 170 mg-KOH/g, more preferably 30 to 150 mg-KOH/g, and particularly preferably 40 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 gram of the resin (B), and it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and particularly preferably 17 to 55% by mass relative to the total amount of solid content.

The colored resin composition of the present invention may contain a polymerizable compound (C) and a polymerization initiator (D). Hereinafter, the colored resin composition containing a polymerizable compound (C) and a polymerization initiator (D) may be referred to as a "colored curable resin composition".

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized using living radicals and/or an acid generated by the polymerization initiator (D). For example, a compound having a polymerizable ethylenic unsaturated bond, etc., is preferred, and ( Meth)acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dixin Pentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, etc.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2900 or less, more preferably 250 or more and 1500 or less.

In the case where the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and particularly preferably, relative to the total solid content. 17 to 55 mass%.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating living radicals, acids, etc. by the action of light or heat, and conventional polymerization initiators can be used. Examples of polymerization initiators that generate living radicals include N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N-benzene Formyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl) )-3-cyclopentylpropan-1-one-2-imine, 2-methyl-2-morpholinyl-1-(4-methylsulfanylphenyl)propane-1-one, 2 -Dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4-bis(trichloromethyl )-6-Sunflower-1,3,5-triazine, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4 ,4',5,5'-tetraphenylbiimidazole and so on.

When the polymerization initiator (D) is included, the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), and more Preferably, it is 1 to 20 parts by mass. If the content of the polymerization initiator (D) is within the above-mentioned range, the sensitivity increases and the exposure time tends to be shortened, so the productivity of the color filter increases.

The colored resin composition of the present invention may contain a polymerization initiation assistant (D1).

<Polymerization initiator (D1)>

The polymerization initiation auxiliary (D1) is a compound or sensitizer used in order to promote polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).

As the polymerization initiator (D1), 4,4'-bis(dimethylamino)benzophenone (commonly known as Michlerone), 4,4'-bis(diethylamino) Benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone (thioxanthone), N-phenylglycine, etc.

In the case of using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) 1 to 20 parts by mass. If the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and there is a tendency to improve the productivity of the color filter.

The colored resin composition of the present invention may contain a solvent (E).

<Solvent (E)>

The solvent (E) is not particularly limited, and solvents generally used in this field can be used. For example, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether ester solvents (solvents that contain -O- and no -COO- in the molecule) Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH and no -O-, -CO in the molecule) -And -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc.

Examples of solvents include ester solvents (solvents containing -COO- and no -O- in the molecule), such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, Ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetylacetate, cyclohexanol acetate and γ-butyrolactone, etc.; ether solvent (contains -O- in the molecule and does not contain -COO -Solvent), such as: ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, Diethylene glycol methyl ethyl ether, etc.; ether ester solvents (solvents containing -COO- and -O- in the molecule), such as: methyl 3-methoxypropionate, ethyl 3-ethoxypropionate Ester, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.; ketone solvent (in Solvents containing -CO- and no -COO- in the molecule), such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, cyclohexanone, etc.; Alcohol solvents (solvents that contain OH in the molecule and do not contain -O-, -CO- and -COO-), such as butanol, cyclohexanol, propylene glycol, etc.; amide solvents, such as: N,N-dimethyl Methyl methamide, N,N-dimethylacetamide and N-methylpyrrolidone, etc.; and others.

As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and ethyl 3-ethoxypropionate are more preferred.

When the solvent (E) is included, the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass relative to the total amount of the coloring resin composition of the present invention. In other words, the total solid content of the colored resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. If the content of the solvent (E) is within the above range, the flatness at the time of application becomes good, and the color density is not insufficient when the color filter is formed, so there is a tendency for the display characteristics to become good.

The colored resin composition of the present invention may contain a leveling agent (F).

<Leveling Agent (F)>

Examples of the leveling agent (F) include organosilicon surfactants, fluorine surfactants, organosilicon surfactants having fluorine atoms, and the like. These may have a polymerizable group in the side chain.

Examples of the organosilicon-based surfactant include surfactants having siloxane bonds in the molecule, and the like. Specific examples include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Industry Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Advanced Materials Japan Co., Ltd.), etc.

Examples of the above-mentioned fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, FLUORAD (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.); MEGAFAC (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K ( (Made by DIC Co., Ltd.); EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electron Chemicals Co., Ltd.); SURFLON (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) ; And E5844 (made by Daikin Institute of Fine Chemicals (Co., Ltd.)), etc.

Examples of the above-mentioned organosilicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, MEGAFAC (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Co., Ltd.), etc. can be cited.

When the leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.1% by mass relative to the total amount of the colored resin composition. It should be noted that this content does not contain the content of the pigment dispersant. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

The colored resin composition of the present invention may contain fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other additives known in the art as needed.

<Manufacturing Method of Colored Resin Composition>

The colored resin composition of the present invention can be obtained by combining the colorant (A) and the resin (B), as well as the polymerizable compound (C), polymerization initiator (D), polymerization initiator (D1), and The solvent (E), the leveling agent (F), and other ingredients are mixed and prepared.

<Method of Manufacturing Color Filter>

As a method of producing a colored pattern from the colored resin composition of the present invention, a photolithography method, an inkjet method, a printing method, and the like can be cited. Among them, photolithography is preferred.

The colored resin composition contains the compound (I) as a colorant, so that a color filter having particularly excellent contrast and heat resistance can be produced. This color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Example

Hereinafter, the colored resin composition of the present invention will be described in more detail with examples. The "%" and "parts" in the examples are mass% and parts by mass unless otherwise specified.

[Synthesis Example 1]

3.5 parts of the compound represented by formula (1-1), 0.57 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione, 201 parts of 1-butanol, and 134 parts of toluene were mixed. The obtained mixture was stirred at 125°C for 16 hours while removing the generated water using a Dean-Stark tube. The crystals produced after cooling were filtered, washed twice with 80 parts of hexane, and the crystals were dried under reduced pressure at 60°C to obtain 3.3 parts of the compound represented by formula (I-10).

Dissolve 5.9 mg of the compound represented by formula (I-10) in N-methylpyrrolidone to make the volume 50 ml, dilute 2 ml of it with N-methylpyrrolidone to make the volume 100 ml, and use spectroscopy A photometer (V-650; manufactured by JASCO; optical path length of the quartz cell: 1 cm) is used to measure the absorption spectrum. The compound showed an absorbance of 5.0 (arbitrary units) at λmax=656 nm.

[Synthesis Example 2]

7.7 parts of the compound represented by the formula (I-10) was added to 100 parts of water to prepare a solution (aqueous solution 1) in which the compound represented by the compound (I-10) was dissolved. In addition, a solution (aqueous solution 2) in which 4.9 parts of barium chloride dihydrate was dissolved in 40 parts of water was prepared, and the aqueous solution 2 was dropped into the aqueous solution 1 at 40° C. for 2 hours, and then stirred for 4 hours. After cooling, it was filtered, washed twice with 100 parts of ion-exchanged water, and the crystals were dried under reduced pressure at 100°C to obtain 15 parts of a compound represented by formula (I-31).

Dissolve 7.5 mg of the compound represented by formula (I-31) in N-methylpyrrolidone to make the volume 50 ml, dilute 2 ml of it with N-methylpyrrolidone to make the volume 100 ml, and use spectroscopy A photometer (V-650; manufactured by JASCO; optical path length of the quartz cell: 1 cm) is used to measure the absorption spectrum. The compound showed an absorbance of 3.8 (arbitrary units) at λmax=656 nm.

[Resin Synthesis Example 1]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was introduced to make it into a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 80°C while stirring. Next, in the flask, the following solution was dropped using a dropping pump for about 5 hours: 38 parts of acrylic acid and acrylic acid-3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8- 289 parts of a mixture of acrylic acid 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester (trade name "E-DCPA"; manufactured by Daicel Co., Ltd.) A solution obtained in 125 parts of propylene glycol monomethyl ether acetate. On the other hand, the following solution was dropped into the flask using a separate drip pump for about 6 hours: 33 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in propylene glycol mono A solution obtained in 235 parts of methyl ether acetate. After the dripping was completed, it was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) with a solid content of 35.1%. The weight average molecular weight Mw of the obtained copolymer was 9,200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg KOH/g. The resin (B-2) has the following structural unit.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene of the resin was carried out under the following conditions using gel permeation chromatography (GPC method).

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: THF

Flow rate: 1.0 ml/min

Solid content concentration of the liquid to be tested: 0.001 to 0.01% by mass

Injection volume: 50 microliters (μL)

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio (Mw/Mn) of the weight average molecular weight in terms of polystyrene obtained above and the number average molecular weight (Mw/Mn) was defined as the degree of dispersion.

Example 1

[Production of colored resin composition (P-1)]

Weigh 10 parts of the compound represented by formula (I-10), 4 parts of solid content (60% propylene glycol monomethyl ether acetate solution) of dispersant BYK-LP N6919 (manufactured by BYK), resin (B-2) ) After 5 parts of the solution (in terms of solid content) and 181 parts of propylene glycol monomethyl ether acetate, 300 parts of 0.4 micron zirconia beads are placed, and shaken for 6 hours using a paint conditioner (manufactured by LAU). The zirconia beads were removed by filtration to prepare a colored resin composition (P-1).

Example 2

[Production of colored resin composition (P-2)]

A colored resin composition (P-2) was produced in the same manner as in Example 1, except that the compound represented by formula (I-10) was replaced with the compound represented by formula (I-31).

Example 3 to Example 4

[Production of colored curable resin composition]

Each component was mixed so that it might become a composition shown in Table 2, and the colored curable resin composition was obtained.

Comparative example 1

Except having changed the colored resin composition (P-1) into the coloring agent (A-1), it carried out similarly to Example 3, and obtained the colored curable resin composition.

In Table 2, each component represents the following compound.

Coloring agent (A-1): compound represented by formula (x)

Resin (B-2): Resin (B-2) (in terms of solid content)

Polymerizable compound (C-1): Dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D-1): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; (Made by BASF)

Solvent (E-1): propylene glycol monomethyl ether acetate

<Production of Color Filter (Colored Coating Film)>

After coating the colored curable resin composition on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by a spin coating method, it was pre-baked at 100° C. for 3 minutes to obtain a colored composition layer. After leaving to cool, use an exposure machine (TME-150RSK; made by Topcon Co., Ltd.) in an atmospheric atmosphere with ^{an exposure amount of 150 millijoules/cm² (mJ/cm 2} ) (365nm standard) to combine the coloring The object layer is irradiated with light. The coloring composition layer irradiated with light is immersed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds. After washing with water, it is carried out at 200°C in an oven It was baked after 120 minutes to obtain a color filter (colored coating film).

<Evaluation of heat resistance>

In the production of the above-mentioned color filter, the xy chromaticity coordinates (x, y) and Y are measured before and after post-baking, and the measured values are determined by the method described in JIS Z 8730:2009 (7. Color difference calculation method) The color difference ΔEab* was calculated, and the results are shown in Table 3. The smaller the △Eab*, the smaller the color change.

<Contrast Evaluation>

For the color filters obtained in Examples 3 to 4 and Comparative Example 1, a contrast meter (CT-1, manufactured by Kosaka Electric Co., Ltd.; color difference meter BM-5A, manufactured by Topcon Co., Ltd.; light source) , F-10; Polarizing film, manufactured by Kosaka Electric Co., Ltd.), set the blank value to 30000, and measure the contrast. The results are shown in Table 3.

Industrial availability

With the colored resin composition of the present invention, a color filter with excellent contrast and heat resistance can be produced.

Claims (4)

A coloring resin composition comprising a coloring agent and a resin, the coloring agent comprising a compound represented by formula (II), the compound being a compound having a maximum absorption wavelength above 500 nanometers and less than 700 nanometers:

In formula (II), ring T ³ represents a nitrogen-containing aromatic heterocyclic ring ^{which may have a substituent, ring T 4} represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and contains N ⁺ in the constituent atoms of the ring, L ¹ And L ² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms, which may have a substituent, M ⁿ⁺ represents an arbitrary cation, and n represents an integer of 1 or more and 5 or less. The colored resin composition according to claim 1, which further contains a polymerizable compound and a polymerization initiator. A color filter formed of the coloring resin composition as described in claim 1 or 2. A display device including the color filter according to claim 3.