TWI711672B - Colored curable resin composition, color filter and display device - Google Patents

Abstract

The object of the present invention is to provide a coloring curable resin composition capable of producing a color filter having a fast development speed, high brightness, and good linearity when forming a colored pattern. The colored curable resin composition of the present invention contains a colorant (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) is composed of a pigment skeleton The coloring agent of the compound (Aa) composed of a cation and an anion of a compound containing at least one element selected from tungsten, molybdenum, silicon and phosphorus and oxygen, as the polymerizable compound (C), includes two or more olefins The first polymerizable compound (C1) which is an unsaturated bond and the second polymerizable compound (C2) which has more ethylenically unsaturated bonds than the first polymerizable compound (C1).

Description

Colored curable resin composition, color filter and display device Invention field

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

Background of the invention

A color filter formed of a coloring curable resin composition is used in a liquid crystal display device and the like, a solid-state imaging element, and the like. For example, Patent Document 1 describes a coloring curable resin composition containing C.I. Pigment Blue 15:6 and a xanthene-based dye.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2013-50693

Summary of the invention

In the present invention, an object is to provide a coloring curable resin composition capable of producing a color filter having a fast development speed, high brightness, and good linearity when forming a colored pattern.

The present invention includes the following inventions.

[1] A colored curable resin composition containing a colorant (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D), the colorant (A) is composed of a pigment The coloring agent of the compound (Aa) composed of the cation of the skeleton and the anion of the compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen, as the polymerizable compound (C), includes two The first polymerizable compound (C1) having the above ethylenically unsaturated bonds and the second polymerizable compound (C2) having more ethylenically unsaturated bonds than the first polymerizable compound (C1).

[2] The colored curable resin composition according to [1], wherein the number of ethylenically unsaturated bonds possessed by the first polymerizable compound (C1) is 2 to 4, and the second polymerizable The number of ethylenically unsaturated bonds that the compound (C2) has is 5 or more and 8 or less.

[3] The colored curable resin composition according to [1] or [2], wherein the ratio of the first polymerizable compound (C1) is relative to the first polymerizable compound (C1) and the second polymerizable compound (C1) The total of the sexual compounds (C2) is 5% by mass or more and 50% by mass or less.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the compound (Aa) is a compound represented by formula (A-I).

[式(A-I)中，R⁴¹~R⁴⁴各自獨立地表示氫原子、碳數1~20的飽和烴基、可具有取代基的碳數6~20的芳香族烴基或可具有取代基的碳數7~30的芳烷基，該碳數1~20的飽和烴基中，該飽和烴基中所含的氫原子可被取代或未取代的胺基或鹵素原子取代，該飽和烴基的碳數為2~20的情況下，該飽和烴基中所含的亞甲基可替換為氧原子或-CO-。R⁴¹與R⁴²可結合而與它們結合的氮原子一起形成環，R⁴³與R⁴⁴可結合而與它們結合的氮原子一起形成環。

[In formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons, or a substituted carbon number An aralkyl group of 7 to 30. In the saturated hydrocarbon group with 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amine group or halogen atom. The saturated hydrocarbon group has 2 carbon atoms In the case of ~20, the methylene group contained in the saturated hydrocarbon group can be replaced with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may be combined to form a ring with the nitrogen atom to which they are combined, and R ⁴³ and R ⁴⁴ may be combined to form a ring with the nitrogen atom to which they are combined.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms. When the alkyl group has 2 to 8 carbon atoms, the The methyl group can be replaced with an oxygen atom or -CO-. R ⁴⁸ and R ⁵² may combine with each other to form -NH-, -O-, -S- or -SO ₂ -.

Ring T ¹ represents an optionally substituted aromatic heterocyclic ring having 3 to 10 carbon atoms.

[Y] ^m- represents an arbitrary m-valent anion containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements.

m represents any natural number. ]

[5] A color filter formed of the colored curable resin composition according to any one of [1] to [4].

[6] A display device including the color filter described in [5].

The coloring curable resin composition of the present invention can produce a color filter having a fast development speed, high brightness, and a pattern with good linearity when a colored pattern is formed.

Detailed ways

The colored curable resin composition of the present invention contains a colorant (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D).

It should be noted that in this specification, when a plurality of constituent elements are exemplified in parallel, unless otherwise specified, it means that each element can be used alone or a plurality of types can be used in combination.

Colorant (A)

The coloring agent (A) contains a compound (Aa) composed of a cation having a pigment skeleton and an anion of a compound containing at least one element selected from tungsten, molybdenum, silicon and phosphorus and oxygen (hereinafter sometimes referred to as compound ( Aa).). The colorant (A) may further include a dye (Ab).

Compound (Aa)

The pigment skeleton in the present invention refers to a partial structure of a compound that selectively absorbs visible light (wavelength; 400 to 750 nm) and has a unique color, and this partial structure includes a structure for expressing the characteristic of having a unique color.

色素骨架、吖嗪色素骨架、菁色素骨架、吖啶色素骨架、蒽醌色素骨架、方酸菁色素骨架等中具有鎓結構的色素骨架；三芳基甲烷色素骨架；使三芳基甲烷骨架的芳香族烴環的1個以上為芳香族雜環的色素骨架等。其中，優選為使三芳基甲烷色素骨架的芳香族烴環的1個以上為芳香族雜環的色素骨架。 Examples of the dye skeleton of the cation constituting the compound (Aa) include an azo dye skeleton,

Pigment skeletons, azine pigment skeletons, cyanine pigment skeletons, acridine pigment skeletons, anthraquinone pigment skeletons, squaraine pigment skeletons, etc. have onium structure pigment skeletons; triarylmethane pigment skeletons; aromatics that make triarylmethane skeletons One or more of the hydrocarbon rings is a dye skeleton of an aromatic heterocyclic ring. Among them, a dye skeleton in which one or more of the aromatic hydrocarbon rings of the triarylmethane dye skeleton is an aromatic heterocyclic ring is preferable.

Examples of anions derived from compounds containing at least one element selected from tungsten, molybdenum, silicon and phosphorus and oxygen include heteropolyanions containing tungsten and homopolyanions containing tungsten, more preferably, examples include Phosphotungstic acid anion, silicotungstate anion and tungsten series homopolyacid anion.

Examples of the heteropoly acid anion containing tungsten and the homopoly acid anion containing tungsten include Keggin type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- and Dawson type phosphotungstic acid ion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type tungstosilicic acid ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ-[ SiW ₁₂ O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and their mixtures.

The compound (Aa) is preferably a compound represented by formula (A-I) (hereinafter also referred to as compound (A-I)).

[式(A-I)中，R⁴¹~R⁴⁴各自獨立地表示氫原子、碳數1~20的飽和烴基、可具有取代基的碳數6~20的芳香族烴基或可具有取代基的碳數7~30的芳烷基，該碳數1~20的飽和烴基中，該飽和烴基中所含的氫原子可以被取代或未取代的胺基或鹵素原子取代，該飽和烴基的碳數為2~20的情況 下，該飽和烴基中所含的亞甲基可以替換為氧原子或-CO-。R⁴¹與R⁴²可結合而與它們結合的氮原子一起形成環，R⁴³與R⁴⁴可結合而與它們結合的氮原子一起形成環。

[In formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons, or a substituted carbon number An aralkyl group of 7 to 30. In the saturated hydrocarbon group with 1 to 20 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted by substituted or unsubstituted amine groups or halogen atoms. The saturated hydrocarbon group has 2 carbon atoms In the case of ~20, the methylene group contained in the saturated hydrocarbon group can be replaced with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may be combined to form a ring with the nitrogen atom to which they are combined, and R ⁴³ and R ⁴⁴ may be combined to form a ring with the nitrogen atom to which they are combined.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms. When the alkyl group has 2 to 8 carbon atoms, the The methyl group can be replaced with an oxygen atom or -CO-. R ⁴⁸ and R ⁵² may combine with each other to form -NH-, -O-, -S- or -SO ₂ -.

Ring T ¹ represents an optionally substituted aromatic heterocyclic ring having 3 to 10 carbon atoms.

[Y] ^m- represents any m-valent anion containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen.

m represents any natural number.

In addition, when a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

[式中，環T¹、R⁴¹~R⁴⁴和R⁴⁷~R⁵⁴分別與上述同義。]]

[In the formula, ring T ¹ , R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ have the same meanings as above. ]]

The aromatic heterocyclic ring of ring T ¹ may be a monocyclic ring or a condensed ring. T by the ring carbon atoms of the aromatic heterocyclic ring ^represented 3 to 10, preferably 3 to 8.

Examples of substituents that the aromatic heterocyclic ring of ring T ¹ may have include halogen atoms, cyano groups, and optionally substituted saturated hydrocarbon groups having 1 to 20 carbons (preferably alkyl groups having 1 to 20 carbons), An optionally substituted aromatic hydrocarbon group having 6 to 20 carbons or an optionally substituted amino group, etc., preferably, a saturated hydrocarbon group having 1 to 20 carbons (preferably an alkyl group having 1 to 20 carbons) , Amino groups that may have substituents, or aromatic hydrocarbon groups with 6 to 20 carbons that may have substituents.

Among them, the aromatic heterocyclic ring of ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a 5-membered aromatic heterocyclic ring containing a nitrogen atom. The ring T ¹ preferably has an amino group which may have a substituent such as an alkyl group having 1 to 10 carbon atoms.

Wherein the aromatic heterocyclic ring T ¹ is preferably an aromatic heterocyclic containing a nitrogen atom, more preferably a 5-membered nitrogen containing aromatic heterocyclic ring.

Furthermore, the ring T ^{1 is} particularly preferably a ring represented by the formula (Ab2-y1).

[式(Ab2-y1)中，R⁵⁶表示氫原子、碳數1~20的飽和烴基、或可具有取代基的碳數6~20的芳香族烴基。

[In the formula (Ab2-y1), R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons.

X2 represents an oxygen atom, -NR ⁵⁷ -or a sulfur atom.

R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons which may have a substituent, an aromatic hydrocarbon group with 6 to 20 carbons which may have a substituent, or a carbon 7 to 20 which may have a substituent In an aralkyl group of 30, when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-. R ⁴⁵ and R ⁴⁶ may be combined to form a ring together with the nitrogen atom to which they are bonded.

* Indicates the bonding end to the carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ and R ⁵⁶ may be any of linear, branched and cyclic. Examples of linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and hexadecyl. Straight-chain alkyl groups such as isopropyl and eicosyl groups; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

The cyclic saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ and R ⁵⁶ may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and the like. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

Specific examples of saturated hydrocarbon groups represented by R ⁴¹ to R ⁴⁶ and R ⁵⁶ include groups represented by the following formulas. In the following formula, * represents a bonding end.

The saturated hydrocarbon groups of R ⁴¹ to R ⁴⁶ and R ⁵⁶ may be substituted with substituted or unsubstituted amine groups or halogen atoms. Examples of substituted amino groups include alkylamino groups such as dimethylamino and diethylamino. In addition, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. In addition, when the halogen atom is a fluorine atom, it is preferably a perfluoroalkyl group such as a trifluoromethyl unit, a pentafluoroethyl unit, and a heptafluoropropyl unit.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include groups having 1 to 8 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by R ⁴¹ .

In addition, examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ include groups having 1 to 10 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by R ⁴¹ .

When the saturated hydrocarbon group (preferably an alkyl group) represented by R ⁴¹ to R ⁵⁴ has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-, preferably Is replaced by an oxygen atom. In addition, an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group), and a linear saturated hydrocarbon group (that is, a linear alkyl group) is more preferable. . The preferable carbon number of the saturated hydrocarbon group in which a methylene group can be substituted with an oxygen atom or -CO- is 2-10, More preferably, it is 2-8. The saturated hydrocarbon group (preferably an alkyl group) preferably has 2-10 carbon atoms, more preferably 2-8 carbon atoms. In addition, when the methylene group is replaced with an oxygen atom or -CO-, the number of carbons between the terminal and the oxygen atom or -CO-, or between the oxygen atom or -CO- and the oxygen atom or -CO- is, for example, 1~ 5, preferably 2 to 3, more preferably 2.

In addition, the optionally substituted aromatic hydrocarbon group represented by R ⁴¹ to R ⁴⁶ and R ⁵⁶ preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, biphenyl, terphenyl, etc., preferably phenyl, naphthyl, tolyl, The xylyl group is particularly preferably a phenyl group. In addition, the aromatic hydrocarbon group may have 1 or 2 or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; and carbon atoms such as chloromethyl and trifluoromethyl. Haloalkyl with 1 to 6; Alkoxy with 1 to 6 carbons such as methoxy and ethoxy; Hydroxyl; Sulfamylsulfonyl; Alkylsulfonyl with 1 to 6 carbons such as methylsulfonyl ; C1-C6 alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl.

Examples of the optionally substituted aralkyl group represented by R ⁴¹ to R ⁴⁶ include alkylene groups having 1 to 5 carbon atoms such as methylene, ethylene, and propylene, and the aromatic hydrocarbon groups described above. Groups formed by combining groups, etc.

As a ring formed by combining R ⁴¹ and R ⁴² with the nitrogen atom to which they are bound, a ring formed by combining R ⁴³ and R ⁴⁴ with the nitrogen atom to which they are bound, and a nitrogen bound to them by R ⁴⁵ and R ^{46 being} bound The ring formed by the atoms includes a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperazine ring and other nitrogen-containing non-aromatic 4-7 membered rings. Preferably, a pyrrolidine ring, a piperidine ring, etc. The heteroatom has only one nitrogen atom in a 4- to 7-membered ring.

Among them, as R ⁴¹ to R ⁴⁴ and R ⁵⁶ , a saturated hydrocarbon group having 1 to 20 carbons or an aromatic hydrocarbon group that may have a substituent is preferable, and it is more preferable that each independently is a saturated hydrocarbon group having 1 to 8 carbons or is represented by the following formula Represents the group. In the following formula, * represents a bonding terminal to a nitrogen atom.

Preferably, R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbons, a group in which an oxygen atom is inserted between the carbon atoms of an alkyl group having 2 to 20 carbons, or an aromatic hydrocarbon group that may have a substituent, Alternatively, R ⁴⁵ and R ⁴⁶ are bonded to form a ring together with the nitrogen atom to which they are bonded. A more preferable aspect is the following aspect: R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbons, an alkoxyalkyl group, or a group represented by the following formula, or R ⁴⁵ and R ^{46 are} combined A 4- to 7-membered ring with only one nitrogen atom as a heteroatom is formed. In the following formula, * represents a bonding terminal to a nitrogen atom.

From the viewpoint of ease of synthesis, R ⁴⁷ to R ^{54 are} preferably each independently a hydrogen atom, a halogen atom, or a C 1-8 alkyl group, and more preferably each independently are a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

As the cation part of the formula (A-I), as shown in the following Table 1, cation 1 to cation 16 represented by the formula (A-I-1) and the like can be cited.

In Table 1, Ph1 to Ph9 mean groups represented by the following formulas. In the formula, * represents the bonding end.

In addition, in Table 1, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bu represents an n-butyl group, and EOE represents an ethoxyethyl group.

Among them, as the cationic portion of the formula (A-I), cation 1 to cation 6, cation 11 to cation 16 are preferred, cation 1, cation 2, or cation 12 to cation 16 are particularly preferred, and cations 12, 15, and 16 are most preferred.

As a compound (Aa), the compound represented by the following formula is mentioned.

【Table 2】

The content of the compound (Aa) in the colored curable resin composition, relative to the total solid content, is usually 1% by mass to 70% by mass, preferably 5% by mass to 60% by mass, and more preferably 10 Mass% or more and 60 mass% or less, and particularly preferably 15 mass% or more and 50 mass% or less. In addition, the content of the compound (Aa) relative to the total amount of the colorant (A) is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 60% by mass or more, and particularly preferably 80% by mass Above, it is preferably 100% by mass or less. If the content of the compound (Aa) is within the above-mentioned range, it is easier to obtain the desired spectral and color density. In addition, the "total amount of solid content" in this specification refers to the total amount of the components from the colored curable resin composition of this invention except a solvent. The total amount of solid content and the content (content rate) of each component relative to it can be measured, for example, by known analytical means such as liquid chromatography and gas chromatography.

Compound (A-I) can be produced in accordance with the method described in JP 2015-28121 A.

Dye (Ab)

As the dye, for example, compounds classified as substances having a hue in addition to pigments in the Excellent Index (published by The Society of Dyers and Colourists), and well-known dyes described in the Dyeing Notes (Sei Dyers Company) can be cited. In addition, the dye is different from the compound (Aa). Xanthene dyes are particularly preferred.

The xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule, and the xanthene dye is more preferably a compound represented by the following formula (a1-1) (hereinafter also referred to as compound (a1-1)). Compound (a1-1) may be its tautomer.

[式(a1-1)中，R¹~R⁴相互獨立地表示氫原子、可具有取代基的碳數1~20的1價的飽和烴基、或者、可具有取代基的碳數6~10的1價的芳香族烴基，該飽和烴基中所含的亞甲基(-CH₂-)可被-O-、-CO-或-NR¹¹-替換。R¹和R²可一起形成包含氮原子的環，R³和R⁴可一起形成包含氮原子的環。

[In the formula (a1-1), R ¹ to R ⁴ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbons which may have a substituent, or a carbon 6 to 10 which may have a substituent The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR ¹¹ -. R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.

R ⁵ represents _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ .

R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ⁵ may be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ¹¹ may be the same or different.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ⁹ and R ¹⁰ independently represent a hydrogen atom or an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbon atoms. The -CH ₂ -contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR ⁸ -replacement, R ⁹ and R ¹⁰ can be combined with each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ]

As the xanthene dye, a compound represented by the following formula (a1-2) (hereinafter also referred to as a compound (a1-2)) is also more preferable. Compound (a1-2) may be its tautomer.

[In formula (a1-2), R ²¹ and R ²² independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon groups of R ²¹ and R ²² may be replaced by 6 carbon atoms. ~10 aromatic hydrocarbon group or halogen atom substitution, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a C 1 to 3 alkoxy group, the above-mentioned R ²¹ , R ²² saturated hydrocarbon group contains -CH ₂ -Can be replaced by -O-, -CO- or -NR ¹¹ -.

R ²³ and R ²⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

R ²¹ and R ²³ may form a ring containing a nitrogen atom together, and R ²² and R ²⁴ may form a ring containing a nitrogen atom together.

p and q represent an integer from 0 to 5 independently of each other. When p is 2 or more, the plurality of R ³³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different.

R ¹¹ has the same meaning as above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbons in R ²¹ and R ²² include groups having 1 to 10 carbons among the groups in R ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that can be possessed as a substituent include the same groups as those in R ¹ .

Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

R ²¹ and R ^{22 are} preferably monovalent saturated hydrocarbon groups having 1 to 3 carbon atoms (for example, methyl, ethyl, propyl, isopropyl) independently of each other.

Examples of the alkyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, and tert-butyl.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, and isopropylsulfanyl. Alkyl and so on.

Examples of the alkylsulfonyl groups having 1 to 4 carbon atoms in R ²³ and R ²⁴ include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropylsulfonyl. Li Ji et al.

R ²³ and R ^{24 are} preferably alkyl groups having 1 to 4 carbon atoms, more preferably methyl and ethyl groups, and still more preferably methyl groups.

p and q are preferably an integer of 0-2, preferably 1 or 2.

Among these, the xanthene dye is preferably a sulfonamide of C.I. Acid Red 289, a quaternary ammonium salt of C.I. Acid Red 289, a sulfonamide of C.I. Acid Violet 102, or a quaternary ammonium salt of C.I. Acid Violet 102.

As xanthene dyes, for example, C.I. Acid Red 51 (with The description of C.I. Acid Red is omitted below, and only the serial number is used. The same goes for others. ), 52, 87, 92, 94, 388, CI Acid Violet 9, 30, CI Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, CI Basic Red 10 (Rhodamine B) , 11, CI Basic Violet 10, 11, 25, CI Solvent Red 218, CI Mordant Red 27, CI Reactive Red 36 (Rose Red B), Sulorhodamine G, described in JP 2010-32999 Xanthene dyes and xanthene dyes described in Patent No. 4492760.

The colorant (A) may further include a pigment (Ac).

As the pigment (Ac), a known pigment can be used without particular limitation. For example, pigments classified as pigments in the Excellence Index (published by The Society of Dyers and Colourists) can be cited, and these can be used alone or in combination of two or more.

Coloring mixture

When manufacturing the colored curable resin composition of the present invention, the compound (Aa) is preferably dissolved or dispersed and mixed in a solvent to prepare a colored mixed liquid. The colored curable resin composition is prepared by mixing the colored mixed solution, the binder resin (B), the polymerizable compound (C), the polymerization initiator (D), etc., and the formation of the colored curable resin composition can be further improved. The heat resistance of the color filter.

As the solvent, any solvent can be used as long as it can be used as the solvent (E) of the colored curable resin composition. Examples of the solvent include ether ester solvents. Preferably, a solvent obtained by etherifying one hydroxyl group of alkylene glycol or polyalkylene glycol and esterifying the remaining hydroxyl group, for example, propylene glycol monomethyl Base ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, etc. These may be used alone or in plural.

In the coloring mixture, the content of the solvent is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 10 parts by mass relative to 1 part by mass of the compound (Aa).

(共榮社化學(株)製造)、

(

(株)製造)、EFKA(BASF公司製造)、

(味之素

(株)製造)、Disperbyk(

社製造)等。 When the compound (Aa) is dispersed in a solvent to prepare a colored mixed liquid, it is preferable to use a dispersant. As the dispersant, for example, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, etc. can be used. These pigment dispersants may be used alone or in combination of two or more kinds. As a pigment dispersant, it is represented by a trade name, and includes KP (manufactured by Shin-Etsu Chemical Co., Ltd.),

(Manufactured by Kyoeisha Chemical Co., Ltd.),

(

(Manufactured by Co., Ltd.), EFKA (manufactured by BASF Corporation),

(Ajinomoto

(Manufactured by Co., Ltd.), Disperbyk (

Manufactured by the company) and so on.

In the coloring mixture, the content of the dispersant relative to 100 parts by mass of the compound (Aa) is, for example, 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 50 parts by mass, and still more preferably 10 ~30 parts by mass.

When the dye (Ab) is contained in the colorant (A), the color mixture may contain a part or all, preferably a part of the dye (Ab) in advance. When the dye (Ab) is contained in the color mixture, the amount of the dye (Ab) is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably, relative to 100 parts by mass of the compound (Aa) 1~5 parts by mass.

When the compound (Aa) is dispersed in a solvent to prepare a colored mixed liquid, the colored mixed liquid may contain a part or all, preferably a part of, the binder resin (B) contained in the colored curable resin composition in advance. By containing the binder resin (B) in advance, it is possible to further improve the dispersion stability when it is made into a colored curable resin composition. The content of the binder resin (B) in the colored mixed liquid is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 70 parts by mass relative to 100 parts by mass of the compound (Aa).

In the colored curable resin composition, the content of the colorant (A) relative to the total solid content is usually 1% by mass to 80% by mass, preferably 5% by mass to 70% by mass, and more preferably 10% by mass or more and 70% by mass or less, more preferably 15% by mass or more and 65% by mass or less. If the content of the colorant (A) is within the above range, it is easier to obtain the desired spectral and color density. In addition, in this specification, the "total amount of solid content" refers to the total amount of the components from the colored curable resin composition of the present invention from which the solvent is removed. The total amount of solid content and the content of each component relative to it can be measured by known analysis means such as liquid chromatography and gas chromatography.

When the colorant (A) contains the dye (Ab), the ratio (Aa/Ab) of the compound (Aa) to the dye (Ab) is on a mass basis, and is preferably 2 or more, more preferably 5 or more, and still more preferably 10 Above, it is particularly preferably 12 or more, preferably 400 or less, more preferably 100 or less, still more preferably 30 or less, particularly preferably 20 or less, and most preferably 18 or less.

When the colorant (A) contains the dye (Ab), it can be prepared in advance The above-mentioned colored mixed liquid containing a dye (Ab), or a mixed liquid containing a dye (Ab) and a solvent.

Binder resin (B)

The binder resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one monomer (b1) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (below Sometimes called "(b1)") a polymer of structural units.

The binder resin (B) is preferably a structural unit derived from a monomer (b2) (hereinafter sometimes referred to as "(b2)") having a cyclic ether structure with a carbon number of 2 to 4 and an ethylenically unsaturated bond, and Copolymers of other structural units.

Examples of other structural units include monomers (b3) that are copolymerizable with monomer (b1) (however, they are different from monomer (b1) and monomer (b2). Hereinafter, it may be referred to as "(b3)" ) Structural units, structural units having ethylenically unsaturated bonds, etc.

Examples of (b1) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinyl benzoic acid; maleic acid, fumaric acid, citraconic acid, medium Conic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydro Unsaturated dicarboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5 -Carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxymethylbicyclo[2.2.1]hept-2-ene, 5 -Carboxyethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid Acid anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride Unsaturated dicarboxylic anhydrides such as phthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

Examples include succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl] ester, etc. Unsaturated mono[(meth)acryloxyalkyl] esters; unsaturated acrylates such as α-(hydroxymeth)acrylic acid that contain a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

(b2) refers to the polymerization of a cyclic ether structure with a carbon number of 2 to 4 (for example, at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Sexual compounds. (b2) It is preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and a (meth)acryloxy group.

Examples of (b2) include monomers (b2-1) having oxirane groups and ethylenically unsaturated bonds (hereinafter sometimes referred to as "(b2-1)"), oxetanyl groups and ethylenic groups. The monomer (b2-2) having an unsaturated bond (hereinafter sometimes referred to as "(b2-2)") and the monomer having a tetrahydrofuran group and an ethylenically unsaturated bond (b2-3) (hereinafter sometimes referred to as " (b2-3)”).

Examples of (b2-1) include monomers (b2-1-1) having a structure in which linear or branched aliphatic unsaturated hydrocarbons are epoxidized (hereinafter sometimes referred to as "(b2-1- 1)") and a monomer (b2-1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b2-1-2)").

(B2-1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. Specific examples of (b2-1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl (meth)acrylate. Glyceryl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl Glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl) Styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene , 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl) Yl)styrene, 3,4,5-tris(glycidoxymethyl)styrene and 2,4,6-tris(glycidoxymethyl)styrene.

(註冊商標)2000；(株)大賽璐製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如，

(註冊商標)A400；(株)大賽璐製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如，

(註冊商標)M100；(株)大賽璐製造)、由式(1)表示的化合物和由式(2)表示的化合物。 Examples of (b2-1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example,

(Registered trademark) 2000; (manufactured by Daicel), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example,

(Registered trademark) A400; (manufactured by Daicel), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example,

(Registered trademark) M100; (manufactured by Daicel Co., Ltd.), the compound represented by formula (1), and the compound represented by formula (2).

[In the formula, R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. X ^a and X ^b each independently represents a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-. R ^c represents an alkylene group having 1 to 6 carbon atoms. * Indicates the bonding end with O. ]

The compound represented by formula (1) and the compound represented by formula (2) may each be used alone, or the compound represented by formula (1) and the compound represented by formula (2) may be used in combination. When they are used in combination, the ratio of the compound represented by formula (1) and the compound represented by formula (2) (compound represented by formula (1): compound represented by formula (2)) is expressed on a molar basis, It is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and still more preferably 20:80 to 80:20.

As (b2-2), a monomer having an oxetanyl group and a (meth)acryloxy group is more preferable. As (b2-3), a monomer having a tetrahydrofuran group and a (meth)acryloxy group is more preferable.

(B2) is preferably (b2-1) in terms of being able to further improve the reliability of the resulting color filter such as heat resistance and chemical resistance. In terms of excellent storage stability of the colored curable resin composition, (b2-1) is preferably (b2-1-2).

As said (b3), the monomer (b3-2) of the (meth)acrylate monomer (b3-1) containing a hydroxyl group and a dicarbonyl imine derivative is mentioned.

Examples of the hydroxyl-containing (meth)acrylate monomer (b3-1) include 2-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxy (meth)acrylate Propyl ester, 4-hydroxybutyl (meth)acrylate, 1,3-butanediol (meth)acrylate, 1,4-butanediol (meth)acrylate, 1,6- Hydroxyl group-containing alkyl (meth)acrylates such as hexanediol (meth)acrylate and 3-methylpentanediol (meth)acrylate.

The above-mentioned hydroxyl-containing (meth)acrylate monomer is preferably a hydroxyalkyl (meth)acrylate having an alkyl group having 1 to 10 carbons, more preferably having 1 to 8 carbons, and even more preferably 1 ~6. Particularly preferred is a hydroxyl group-containing (meth)acrylate of an alkyl group having 1 to 4 carbon atoms.

(b3-1) is preferably hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and more Preferably, it is 2-hydroxyethyl (meth)acrylate.

The monomer (b3-2) of the dicarbonylimine derivative includes dicarbonylimine having aromatic hydrocarbon groups such as N-phenylmaleimide and N-tolylmaleimide, and N- Dicarbonylimine with alicyclic hydrocarbon groups such as cyclohexylmaleimide, N-cycloheptylmaleimide, N-benzylmaleimide, N-phenethylmaleimide Dicarbonyl imines with aralkyl groups.

The monomer (b3-2) of the dicarbonylimine derivative is preferably an N-substituted maleimidimide having a hydrocarbon group with 4 to 20 carbons, and more preferably an alicyclic hydrocarbon group with 4 to 20 carbons. N-substituted maleimines of 6-20 aromatic hydrocarbon groups, 7-20 aralkyl groups, or succinimidyl groups. The substituent that the N-substituted maleimines has is more preferably an alicyclic hydrocarbon group having 4 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 16 carbon atoms, and an aralkyl group having 7 to 16 carbon atoms.

The hydrogen atom contained in the hydrocarbon group may be substituted with an amino group, an alkoxy group having 1 to 5 carbon atoms, a phenylamino group, a halogen atom, a hydroxyl group, and the like.

Among them, the monomer of the dicarbonylimine derivative is preferably an N-substituted maleimide having an alicyclic hydrocarbon group with 4 to 20 carbon atoms, and more preferably N-cyclohexylmaleimide N-cycloheptylmaleimide, N-cyclooctylmaleimide, N-cyclododecylmaleimide, more preferably N-cyclohexylmaleimide amine.

As (b3), examples of monomers (b3-3) other than (b3-1) and (b3-2) include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth) N-Butyl acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, (meth) Lauryl acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, three (meth)acrylate Cyclo[5.2.1.0 ^2,6 ]decane-8-yl ester (in this technical field, it is called "dicyclopentyl (meth)acrylate" as a common name. In addition, it is sometimes called "(methyl) Tricyclodecyl acrylate".), tricyclo[5.2.1.0 ^2,6 ]decene-8-yl (meth)acrylate (in this technical field, as a common name, it is called "(meth)acrylate bicyclo Pentenyl ester".), biscyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, (meth) (Meth)acrylates such as propargyl acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; diethyl maleate, diethyl fumarate, Dicarboxylic acid diesters such as diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1 ]Hept-2-ene and other bicyclic unsaturated compounds; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, etc. contain ethylene Aromatic compounds containing vinyl groups; vinyl-containing nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl-containing amides such as acrylamide and methacrylamide; vinyl acetate And other esters; 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene diene, etc.

Among these, as (b3-3), from the viewpoint of copolymerization reactivity and heat resistance, aromatic compounds and bicyclic unsaturated compounds containing vinyl groups are preferred. Specifically, styrene, vinyl toluene, benzyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, and bicyclo[2.2.1]heptan are preferred. -2-ene.

The polymer having the structural unit derived from (b1) can be produced, for example, by polymerizing the monomer introduced into the structural unit of the polymer in a solvent in the presence of a polymerization initiator. As a solvent, what is necessary is just to dissolve each monomer, and the solvent etc. mentioned later as a solvent (E) of the coloring curable resin composition of this invention are mentioned.

If necessary, a reaction catalyst of a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (for example, hydroquinone, etc.), etc. can be used.

As a carboxylic anhydride, the acid anhydride etc. which were mentioned in (b1) are mentioned.

The resin may be used alone or in combination of two or more kinds.

The weight average molecular weight in terms of polystyrene of the binder resin (B) is usually 3,000 to 100,000, preferably 4,000 to 50,000, more preferably 5,000 to 35,000, still more preferably 5,000 to 30,000, and particularly preferably 5,500 to 30,000. If the molecular weight is within the above-mentioned range, the hardness of the coating film increases, the residual film rate is also high, the solubility of the unexposed portion to the developer is good, and the resolution of the colored pattern tends to increase. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the binder resin (B) is preferably 1.1-6, more preferably It is selected from 1.2 to 4, and more preferably from 1.3 to 3.

The acid value (in terms of solid content) of the binder resin (B) is preferably 1 to 170 mg-KOH/g, more preferably 15 to 150 mg-KOH/g, and still more preferably 80 mg-KOH/g to 135 mg-KOH/g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the binder resin (B), and it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

Among them, the binder resin (B) preferably contains at least a structural unit derived from (b1) and a structural unit derived from (b2).

In addition, the binder resin (B) of the present invention preferably further contains a structural unit derived from (b3), and more preferably contains a structural unit derived from a hydroxyl group-containing (meth)acrylate monomer (b3-1) and a structural unit derived from a dicarbonyl subunit. At least one (preferably both) of the structural units of the monomer (b3-2) of the amine derivative.

In this case, the binder resin (B) preferably contains a copolymer of (b1), (b2), (b3-1) and (b3-2). The content of the copolymer in the binder resin (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 100% by mass or less.

The total of (b3-1) and (b3-2), in all monomers constituting the binder resin (B), is preferably 25% by mass or more and 90% by mass or less, more preferably 35% by mass or more, and still more preferably 40% by mass or more, particularly preferably 45% by mass or more, more preferably 90% by mass or less, and still more preferably 80% by mass or less.

The total content of the binder resin (B) relative to the total solid content is preferably 7-65% by mass, more preferably 10-60% by mass, still more preferably 13-60% by mass, and particularly preferably 17 ~55 mass%. If the content of the binder resin (B) is within the above range, the colored pattern The process is easy, and the resolution of the colored pattern and the residual film rate tend to increase.

Polymeric compound (C)

As the polymerizable compound (C), a polymerizable compound having two or more ethylenic unsaturated bonds is used. Among them, in the present invention, as the polymerizable compound (C), 2 different in the number of ethylenic unsaturated bonds are used. More than one compound. That is, the polymerizable compound (C) includes a first polymerizable compound (C1) having two or more ethylenically unsaturated bonds, and a second polymerizable compound (C1) having more ethylenically unsaturated bonds than the first polymerizable compound (C1). Polymerizable compound (C2).

The difference between the number of ethylenically unsaturated bonds of the first polymerizable compound (C1) and the number of ethylenically unsaturated bonds of the second polymerizable compound (C2) is preferably 2 or more, and preferably 4 or less. In addition, the number of ethylenically unsaturated bonds possessed by the first polymerizable compound (C1) is preferably 2 or more and 4 or less. The number of ethylenically unsaturated bonds that the second polymerizable compound (C2) has is preferably 5 or more, and preferably 8 or less.

In addition, when the first polymerizable compound (C1) or the second polymerizable compound (C2) contains two or more types of polymerizable compounds, the number of the above-mentioned ethylenically unsaturated bonds is set to be relative to the first polymerizable compound (C1) or the value obtained by the weighted average of the second polymerizable compound (C2). Specifically, the product of the mass ratio and the number of ethylenically unsaturated bonds is calculated for each of the contained polymerizable compounds, and the value obtained is a value obtained by adding up the obtained values.

The first polymerizable compound (C1) and the second polymerizable compound (C2) are preferably compounds having a (meth)acrylate structure, and more preferably compounds having an acrylate structure. In addition, the polymerizable compounds (C1) and (C2) are more preferably (meth)acrylates of polyol compounds (preferably acrylic acid ester).

Examples of polyol compounds include diols such as alkanediol and benzenediol; triols such as trimethylolpropane, tris(hydroxyethyl)isocyanurate, and tris(hydroxymethyl)ethylsuccinic acid ; Pentaerythritol and other four alcohols; dipentaerythritol and other six alcohols; tripentaerythritol and other eight alcohols; four seasons pentaerythritol and other ten alcohols.

Examples of polymerizable compounds having two or more ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. (Meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. have 2 A polymerizable compound with an ethylenically unsaturated bond; trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-(meth)acryloxyethyl) isocyanide Polymeric compounds with 3 ethylenically unsaturated bonds such as urate, 2,2,2-tris(meth)acryloyloxymethylethyl succinic acid; pentaerythritol tetra(meth)acrylate, ethylene diacrylate Alcohol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and other polymerizable compounds with 4 ethylenically unsaturated bonds ; Dipentaerythritol penta(meth)acrylate and other polymerizable compounds with 5 ethylenically unsaturated bonds; dipentaerythritol hexa(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol Polymeric compounds with 6 ethylenically unsaturated bonds such as modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc.; tripentaerythritol hepta(meth)acrylate, etc. Polymerizable compounds with 7 ethylenically unsaturated bonds; polymerizable compounds with 8 ethylenically unsaturated bonds such as tripentaerythritol octa(meth)acrylate; pentaerythritol nine (meth) Yl) polymerizable compounds having 9 ethylenically unsaturated bonds such as acrylate; polymerizable compounds having 10 ethylenically unsaturated bonds such as pentaerythritol deca(meth)acrylate, etc.

The molecular weight of the polymerizable compound (C) is preferably 150 or more, 2,900 or less, and more preferably 250 or more and 1,500 or less. In addition, the molecular weight of the first polymerizable compound (C1) is preferably 150 or more and less than 500, and more preferably 200 or more and 450 or less. The molecular weight of the second polymerizable compound (C2) is preferably 500 or more, 2,900 or less, and more preferably 550 or more and 1,500 or less.

The ratio of the first polymerizable compound (C1) relative to the total of the first polymerizable compound (C1) and the second polymerizable compound (C2) is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass The above 35 mass% or less, more preferably 15 mass% or more and 30 mass% or less.

The total ratio of the first polymerizable compound (C1) and the second polymerizable compound (C2) contained in the polymerizable compound (C) is preferably 80 in 100% by mass of the total amount of the polymerizable compound (C) % By mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably 98% by mass or more, and particularly preferably 100% by mass or less.

The polymerizable compound (C) may further include another polymerizable compound (C3). Examples of other polymerizable compounds (C3) include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and 2-hydroxy acrylate Ethyl ester, N-vinylpyrrolidone, polymerizable compounds having one ethylenically unsaturated bond such as (a), (b) and (c) mentioned above.

When the polymerizable compound (C) contains other polymerizable compounds (C3) Below, the content of the polymerizable compound (C) is 100% by mass, preferably 2% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 10% by mass or less.

The content of the polymerizable compound (C) in the colored curable resin composition of the present invention is preferably 1% by mass or more and 60% by mass or less, and more preferably 5% by mass and 50% by mass relative to the total solid content. Hereinafter, it is more preferably 10% by mass or more and 40% by mass or less, and particularly preferably 12% by mass or more and 37% by mass or less. The content ratio of the binder resin (B) to the polymerizable compound (C) (binder resin (B): polymerizable compound (C)) on a mass basis, preferably 20:80 to 80:20, more preferably 35 : 65~80:20. If the content of the polymerizable compound (C) is within the above-mentioned range, the residual film rate during the formation of the colored pattern and the chemical resistance of the color filter tend to increase.

Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. by the action of light and heat, and a known polymerization initiator can be used. The polymerization initiator (D) is preferably a photopolymerization initiator that can initiate polymerization by the action of light.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, an phosphine oxide compound, an O-oxime compound, and a biimidazole compound, and is more preferably A polymerization initiator containing an O-oxime compound.

Examples of O-acetoxime compounds include: N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy -1-(4-Phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2 -Methylbenzyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4 -(3,3-Dimethyl-2,4-dioxolylmethoxy)benzyl}-9H-carbazol-3-yl)ethane-1-imine, N-ethyl Oxyoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine and N-benzene Methoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-ylidene amine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (the above are made by BASF), N-1919, and NCI-930 (made by ADEKA) can also be used. Among them, it is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzyloxy-1-(4 -Phenylsulfanylphenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane- At least one of 1-keto-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine.

Examples of alkyl phenyl ketone compounds include: 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1 -(4-morpholinophenyl)-2-benzylbutane-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ 4-(4-morpholinyl)phenyl]butan-1-one. Commercial products such as Irgacure 369, 907, and 379 (the above are made by BASF Corporation) can be used.

The alkyl phenyl ketone compound can be 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)benzene Base) propane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl) propan-1-one oligomer, α, α -Diethoxy acetophenone and benzyl dimethyl ketal.

Examples of triazine compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl) (Methyl)-6-piperonyl-1,3,5-triazine.

As an acylphosphine oxide compound, 2,4,6-trimethylbenzyldiphenylphosphine oxide can be mentioned. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can be used.

Specific examples of the biimidazole compound include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and Japanese Patent Application Laid-Open No. 6-75372 , Japanese Patent Application Publication No. 6-75373, Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, Japanese Patent Application Publication No. 07-010913, and the compounds represented by the following formulas .

As other polymerization initiators, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzoin, o- Benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butyl) Peroxycarbonyl) benzophenone compounds such as benzophenone and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-Butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These polymerization initiators are preferably combined with the polymerization initiation aids described later (especially Amine-based polymerization initiator) used in combination.

In addition, as the polymerization initiator (D), it is preferable to combine an O-acyl oxime compound with at least one selected from alkyl phenyl ketone compounds, triazine compounds, acyl phosphine oxide compounds, and biimidazole compounds (more preferably Alkyl phenyl ketone compound) combination.

In the polymerization initiator (D), the content of the O-acetoxime compound is preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 100% by mass or less.

The content of the polymerization initiator (D), relative to 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C), is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass, and more preferably 1 to 30 parts by mass, particularly preferably 1 to 20 parts by mass.

Polymerization initiator

The polymerization initiation auxiliary agent is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator (D). When the colored curable resin composition of the present invention contains a polymerization initiator, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aids include amine-based polymerization initiation aids, alkoxyanthracene-based polymerization initiation aids, thioxanthone-based polymerization initiation aids, and carboxylic acid-based polymerization initiation aids.

Examples of amine-based polymerization initiators include: alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; N,N-dimethyl-p-toluidine, 4,4'-bis(di Methylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-bis(ethylmethylamino)benzophenone A The ketone preferably includes alkylamino benzophenone such as 4,4'-bis(diethylamino)benzophenone, more preferably alkylamino benzophenone, and further Preferably, 4,4'-bis(diethylamino)benzophenone is mentioned. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of alkoxyanthracene-based polymerization initiation aids include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone-based polymerization initiation aid include: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Xanthone and 1-chloro-4-propoxythioxanthone.

Examples of the carboxylic acid-based polymerization initiation aid include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, and N-phenylglycine.

When a polymerization initiation assistant is used, its content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C). If the content of the polymerization initiation assistant is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to increase.

Solvent (E)

The solvent (E) is not limited, and a solvent generally used in this field may be used alone or in combination of two or more kinds. Specifically, examples include: 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 (molecular Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- and no -COO- in the molecule) Solvents), alcohol solvents (solvents that contain OH in the molecule and do not contain -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amine solvents and dimethyl sulfide.

Examples of the ester solvent include: methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, and isoamyl acetate , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclic Hexanol acetate and γ-butyrolactone.

Examples of ether solvents include: ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether Ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, two Glycol methyl ethyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, and methyl anisole.

Examples of ether ester solvents include: butyl methoxyacetate, methyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-methoxypropionic acid Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3 -Methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene two Alcohol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate, propylene glycol diacetate.

Examples of ketone solvents include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 -Pentanone, Cyclopentanone, cyclohexanone and isophorone.

Examples of alcohol solvents include butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

As the amide solvent, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone can be mentioned.

These solvents can combine two or more types.

Among the above-mentioned solvents, organic solvents having a boiling point of 120°C or more and 210°C or less at 1 atm are preferred from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether are preferred. Alcohol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, Cyclohexanone, N,N-dimethylformamide and N-methylpyrrolidone, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl Ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, cyclohexanone, ethyl 3-ethoxypropionate, N,N-di Methylformamide and N-methylpyrrolidone.

The content of the solvent (E) is usually 70 to 95% by mass, preferably 75 to 92% by mass, and more preferably 75 to 90% by mass relative to the total amount of the colored curable resin composition. If the content of the solvent (E) is in the above-mentioned range, the flatness at the time of coating becomes good, and since the color density is not insufficient when the color filter is formed, the display characteristics tend to become good.

Leveling agent

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

Examples of the organosilicon-based surfactant include surfactants having siloxane bonds in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Contract Company).

Examples of fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554 , Megafac R30, Megafac RS-718-K (manufactured by DIC Co., Ltd.), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381 , Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute).

Examples of the organosilicon surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Co., Ltd.) can be cited.

The content of the leveling agent relative to the total amount of the colored curable resin composition is usually 0.0005 mass% to 0.6 mass%, preferably 0.001 mass% to 0.5 mass%, and more preferably 0.001 mass% to 0.2 mass% Hereinafter, it is more preferably 0.002% by mass or more and 0.1% by mass or less, and particularly preferably 0.005% by mass or more and 0.07% by mass or less. If the content of the leveling agent is within the above-mentioned range, the flatness of the color filter can be improved.

Other ingredients

The colored curable 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.

Method for producing colored curable resin composition

The colored curable resin composition of the present invention, for example, can be obtained by combining the compound (Aa) as the colorant (A), the binder resin (B), the polymerizable compound (C), the polymerization initiator (D), and It is prepared by mixing dyes, solvents, leveling agents, polymerization initiation aids and other ingredients added as needed. As the colorant (A), in addition to the compound (Aa), a colorant such as a pigment can be further mixed. The pigment is preferably mixed with a part or all of the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes 0.2 μm or less The state of the pigment dispersion is used. In this case, part or all of the above-mentioned pigment dispersant and binder resin (B) can be blended as needed.

It is preferable to filter the mixed colored curable resin composition using a filter with a pore diameter of about 0.01 to 10 μm.

Manufacturing method of color filter

As a method of manufacturing a coloring pattern as a pixel from the coloring curable resin composition of this invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, photolithography is preferred. The photolithography method is a method of applying a colored curable resin composition to a substrate, drying it to form a colored composition layer, and exposing the colored composition layer through a photomask to develop and obtain a colored pattern. In the photolithography method, by not using a photomask and/or not developing during exposure, it is possible to form a colored coating film as a cured product of the colored composition layer. The colored pattern and colored coating film formed in this way can be used as the color filter of the present invention.

The film thickness of the produced color filter can be appropriately adjusted according to the purpose, application, etc., and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate, a resin plate, silicon, or a substrate on which aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed can be used. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The formation of the pixels of each color by photolithography can be performed by well-known or customary equipment and conditions. For example, it can be produced as follows.

First, the colored curable resin composition is coated on a substrate, and then heated and dried (pre-baked) and/or dried under reduced pressure to remove solvents and other volatiles. Dry the ingredients to obtain a smooth coloring composition layer. As the coating method, a spin coating method, a slit coating method, and a slit and spin coating method can be cited.

Next, the coloring composition layer is exposed to light through a photomask for forming the target coloring pattern. In order to be able to irradiate the entire exposure surface with parallel light uniformly or to enable accurate alignment of the photomask and the substrate on which the coloring composition layer is formed, it is preferable to use an exposure device such as a mask aligner and a stepper. The coloring composition layer after exposure is brought into contact with a developing solution for development to form a coloring pattern on the substrate. By development, the unexposed part of the colored composition layer is dissolved in the developer and removed. As the developing solution, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The development method may be any of the rotary immersion method, dipping method, and spray method. Furthermore, during development, the substrate can be tilted at any angle. After development, it is preferable to perform water washing.

Preferably, the obtained colored pattern is further post-baked. The color filter having the colored pattern and colored coating film obtained in this way can be further subjected to surface coating treatment in order to impart various characteristics.

The color filter formed from the colored curable resin composition of the present invention 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

The following examples are given to illustrate the present invention more specifically. Of course, the present invention is not limited by the following examples. It is of course possible to appropriately change and implement them within the scope of the aforementioned and the following points. These are all included in the present invention. Within the technical scope of the invention. Furthermore, in the following, as long as there is no special mention Clearly, "parts" means "parts by mass" and "%" means "mass%".

Synthesis example 1

The following reactions were carried out in a nitrogen atmosphere. After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide into a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, the mixture was stirred for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little, and stirred at room temperature for 24 hours. After adding the reaction liquid to 200 parts of ice water little by little, it was left standing at room temperature for 15 hours, and the water was removed by decantation to obtain a viscous solid as a residue. After adding 60 parts of methanol to this viscous solid, it was stirred at room temperature for 15 hours. After the precipitated solid was separated by filtration, it was purified by column chromatography. The purified light yellow solid was dried at 60°C under reduced pressure to obtain 9.8 parts of the compound represented by formula (C-I-18).

The following reactions were carried out in a nitrogen atmosphere. Put 8.2 parts of the compound represented by formula (BI-7), 10 parts of the compound represented by formula (CI-18), and 20 parts of toluene into a flask equipped with a cooling tube and a stirring device, and then add phosphorus oxychloride 12.2 parts, stir at 95~100°C for 3 hours. Next, after the reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropanol. Next, after pouring the diluted reaction solution into 300 parts of saturated brine, add toluene 100 parts, stirring for 30 minutes. Next, the stirring was stopped, and the mixture was allowed to stand for 30 minutes to separate into an organic layer and an aqueous layer. After the water layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, and after stirring for 30 minutes, a filtered and dried organic layer was obtained. The solvent was distilled off from the obtained organic layer with an evaporator to obtain a blue-purple solid. Furthermore, the blue-violet solid was dried at 60°C under reduced pressure to obtain 18.4 parts of the compound represented by the formula (A-II-18).

The following reactions were carried out in a nitrogen atmosphere. After putting 8 parts of the compound represented by formula (A-II-18) and 396 parts of methanol into a flask equipped with a cooling tube and a stirring device, it stirred at room temperature for 30 minutes, and prepared the cyan solution. Next, after adding 396 parts of water to the cyan solution, it was further stirred at room temperature for 30 minutes to obtain a reaction solution.

53 parts of water were put into the beaker, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water, and they were mixed in an air atmosphere at room temperature to prepare a phosphotungstic acid solution.

The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. After further stirring for 30 minutes at room temperature, it was filtered to obtain a cyan solid. The obtained cyan solid was poured into 200 parts of methanol, dispersed for 1 hour, and then filtered, and this operation was repeated twice. Will be obtained by this operation The colored solid was put into 200 parts of water, dispersed for 1 hour, and filtered, and this operation was repeated twice. The cyan solid obtained by this operation was dried at 60° C. under reduced pressure to obtain 17.1 parts of the compound represented by formula (A-I-18).

Synthesis Example 2

The following reactions were carried out in a nitrogen atmosphere. Put 0.5 part of tris(dibenzylideneacetone)dipalladium (manufactured by Aldrich), 1.1 part of XPhos (manufactured by Aldrich), and sodium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) into a flask equipped with a cooling tube and a stirring device. ) 34 parts, 40 parts of 4,4'-dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 43 parts of N-isopropylaniline (manufactured by Wako Pure Chemical Industries, Ltd.), toluene 531 parts of solution. The temperature was raised to 80°C, and after stirring for 2 hours, it was cooled to room temperature. After filtering the reaction liquid, the filtrate was separated and purified with 200 parts of 1 equivalent hydrochloric acid. The obtained organic layer was purified by liquid separation with 200 parts of 5% sodium carbonate aqueous solution. The obtained organic layer was dried with 120 parts of magnesium sulfate, and the solid content was separated by filtration. After distilling the obtained organic layer, it was dried at 60°C under reduced pressure to obtain 47 parts of a compound represented by formula (C-I-19).

The following reactions were carried out in a nitrogen atmosphere. After putting 1.9 parts of the compound represented by formula (BI-7), 3.1 parts of the compound represented by formula (CI-19), and 20 parts of toluene into a flask equipped with a cooling tube and a stirring device, 9.0 parts of phosphorus oxychloride was added, Stir at 95~100°C for 3 hours. After the reaction mixture was cooled to room temperature, it was diluted with 46.6 parts of isopropanol. After the diluted reaction solution was poured into 149.1 parts of saturated saline, 124.2 parts of isopropanol was added and stirred for 30 minutes. The stirring was stopped, and the mixture was allowed to stand for 30 minutes. As a result, the organic layer and the aqueous layer were separated. After the water layer was discarded by a liquid separation operation, the organic layer was washed twice with 91.6 parts of saturated brine. An appropriate amount of magnesium sulfate was added to the organic layer, and after stirring for 30 minutes, a filtered and dried organic layer was obtained. The solvent was distilled off from the obtained organic layer with an evaporator to obtain a blue-purple solid. Furthermore, the blue-violet solid was dried at 60°C under reduced pressure to obtain 4.0 parts of the compound represented by the formula (A-II-19).

The following reactions were carried out in a nitrogen atmosphere. Put 8 parts of the compound represented by formula (A-II-19) and methanol in a flask equipped with a cooling tube and a stirring device After 396 parts, it was stirred at room temperature for 30 minutes to prepare a cyan solution. Next, after adding 396 parts of water to the cyan solution, it was further stirred at room temperature for 30 minutes to obtain a reaction solution.

Put into the beaker 53 parts of water, and further put 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol into the water, and mix them in an air atmosphere at room temperature to prepare a phosphotungstic acid solution.

The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. After further stirring for 30 minutes at room temperature, it was filtered to obtain a cyan solid. The obtained cyan solid was poured into 200 parts of methanol, dispersed for 1 hour, and then filtered, and this operation was repeated twice. The cyan solid obtained by this operation was put into 200 parts of water, dispersed for 1 hour, and then filtered, and this operation was repeated twice. The cyan solid obtained by this operation was dried at 60° C. under reduced pressure to obtain 17.1 parts of the compound represented by formula (A-I-19).

Synthesis Example 3

The following reactions were carried out in a nitrogen atmosphere. Put 2.7 parts of tris(dibenzylideneacetone)dipalladium (manufactured by Aldrich), 5.7 parts of XPhos (manufactured by Aldrich), and sodium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) into a flask equipped with a cooling tube and a stirring device. ) 25.3 parts, 4,4'-dichlorobenzophenone (Tokyo Chemical Industry After 30 parts, a solution of 29 parts of 2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) and 154.6 parts of toluene was dropped. After raising the temperature to 80°C and stirring for 2 hours, it was cooled to room temperature. After the reaction liquid was diluted with 900 parts of ethyl acetate, it was separated and purified with 900 parts of ion-exchanged water. The obtained organic layer was purified by liquid separation with 900 parts of 1 equivalent hydrochloric acid, and then purified by liquid separation with 900 parts of 5% sodium carbonate aqueous solution. The obtained organic layer was dried with 90 parts of magnesium sulfate, and the solid content was separated by filtration. After distilling the obtained organic layer with a rotary evaporator, the obtained solid was washed with 560 parts of toluene. After the obtained solid was washed again with 186.9 parts of toluene, it was dried at 60° C. under reduced pressure to obtain 42.2 parts of the compound represented by formula (C-I-20-1).

The following reactions were carried out in a nitrogen atmosphere. Put 10.0 parts of the compound represented by formula (CI-20-1) and 75.2 parts of DMF into a flask equipped with a cooling tube and a stirring device. After stirring for 30 minutes, put potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.0 copies. After stirring for 30 minutes, 11.1 parts of ethane iodide was dropped, and the mixture was stirred at 35°C for 3 hours. After the reaction solution was cooled to room temperature, it was dropped into 300 parts of ion-exchange water and stirred for 30 minutes. The obtained suspension was filtered, and the filtered solid was washed with 300 parts of ion exchange water. The obtained solid was washed with 74.8 parts of methanol, washed with 41.0 parts of methanol, and dried at 60° C. under reduced pressure to obtain 1.6 parts of a compound represented by formula (C-I-20-2).

[化22]

The compound represented by formula (A-I-20) was obtained in the same manner as in Synthesis Example 1, except that the compound represented by formula (C-I-18) was changed to the compound represented by formula (C-I-20-2).

Synthesis Example 4

A compound represented by formula (C-I-21) was obtained in the same manner as in Synthesis Example 3 except that ethane iodide was changed to butane iodide.

The compound represented by formula (A-I-21) was obtained in the same manner as in Synthesis Example 1, except that the compound represented by formula (C-I-18) was changed to the compound represented by formula (C-I-21).

[化25]

Synthesis Example 5

20 parts of the compound represented by formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under shading conditions, and the resulting solution was heated at 110°C Stir for 6 hours. After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 800 parts of water and 50 parts of 35% by weight hydrochloric acid, and stirred at room temperature for 1 hour. As a result, crystals precipitated. The precipitated crystal was obtained as a residue of suction filtration and then dried to obtain a compound represented by formula (1-32).

Synthesis Example 6

Into a flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was introduced at 0.02L/min to form a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 3-methoxybutyl acetate were charged. 105 parts, heated to 70°C while stirring. Next, 60 parts of methacrylic acid, 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by formula (1-1) and a compound represented by formula (2-1)) A mixture with a molar ratio of 50:50.) 240 parts were dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and the solution was dropped into a flask kept at 70° C. using a dropping funnel over 4 hours. On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate over 4 hours using another dropping funnel. The solution in the flask dripped into the flask. After dropping the polymerization initiator solution, the solution was kept at 70°C for 4 hours and then cooled to room temperature to obtain a resin B-1b solution with a solid content of 32.6% and an acid value of 110 mg-KOH/g (in terms of solid content) . The weight average molecular weight Mw of the obtained resin B-1b was 13,400, and the molecular weight distribution was 2.50.

Preparation of dispersion

社製造))2份、樹脂B-1b(固體成分換算)4份、丙二醇單甲基醚乙酸酯84份和0.2mm的氧化鋯珠粒300份混合，使用塗料調理器(Red Devil社製造)振盪6小時，製備分散液(1)。 10 parts of the compound represented by formula (AI-18), dispersant (BYK (registered trademark) -LPN6919 (

Co., Ltd.)) 2 parts, 4 parts of resin B-1b (in terms of solid content), 84 parts of propylene glycol monomethyl ether acetate and 300 parts of 0.2mm zirconia beads were mixed, and a paint conditioner (manufactured by Red Devil) ) Shake for 6 hours to prepare dispersion (1).

Synthesis Example 7

Pour an appropriate amount of nitrogen into a 1L flask equipped with a reflux cooler, dropping funnel and stirrer, replace it with a nitrogen atmosphere, charge 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate, and heat while stirring To 85°C. Next, 38 parts of acrylic acid, 25 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]dec-8 or/and 9-yl ester of acrylic acid, and cyclohexyl maleic acid were dropped over 5 hours. A mixed solution of 137 parts of amine, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution in which 5 parts of 2,2-azobisisobutyronitrile was dissolved in 88 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After the dropwise addition, the copolymer was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer with a type B viscosity (23°C) of 22 mPas, a solid content of 25.5%, and a solution acid value of 28 mg-KOH/g. The weight average molecular weight Mw of the resulting copolymer was 7,700, and the molecular weight distribution was 2.1.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the above-mentioned binder polymer was carried out under the following conditions using the GPC method.

Device; K2479 (manufactured by Shimadzu Corporation)

Column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40℃

Solvent; THF (tetrahydrofuran)

Concentration of tested solution; 25mg/mL (solvent; THF)

Flow rate; 1.0mL/min

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

Examples 1-7 and Comparative Example 1

Each component was mixed so that it might become a composition shown in Table 4, and the colored curable resin composition was obtained.

【Table 4】

A1-1 ¹⁾ is prepared by mixing the dispersant, B- ¹⁵⁾ , and propylene glycol monomethyl ether acetate in the amount described in the column E- ¹⁶⁾ and pre-dispersing them.

A1-2 ⁷⁾ as a dispersing agent, B-1 ^5), and E-1 ⁶⁾ as the fields described in propylene glycol monomethyl ether acetate were mixed in advance dispersed therein.

A1-3 ⁸⁾ as a dispersing agent, B-1 ^5), and E-1 ⁶⁾ as the fields described in propylene glycol monomethyl ether acetate were mixed in advance dispersed therein.

A1-4 ⁹⁾ as the dispersant, propylene glycol monomethyl ether acetate, a mixed amount of a B-1 ^5), and E-1 ⁶⁾ described in the column, previously dispersed.

A1-5 ²⁾ is an acrylic pigment dispersant, B-1 ^5), and E-1 ⁶⁾ as the fields described in propylene glycol monomethyl ether acetate were mixed in advance dispersed therein.

B-1 ³⁾ shows the total content of resin B-1.

E-1 ⁴⁾ represents the total content of propylene glycol monomethyl ether acetate.

In addition, in Table 4, each component represents the following substances. another In addition, the binder resin (B) represents parts by mass in terms of solid content.

Coloring agent (A); 1-1; compound represented by formula (1-32)

Coloring agent (A); A1-1; compound represented by formula (A-I-18)

Coloring agent (A); A1-2; compound represented by formula (A-I-19)

Coloring agent (A); A1-3; compound represented by formula (A-I-20)

Coloring agent (A); A1-4; compound represented by formula (A-I-21)

Coloring agent (A); A1-5; C.I. Pigment Blue 15:6

社製造)) Dispersant; (BYK(registered trademark)-LPN6919(

Company made))

Binder resin (B); (B-1); resin (B-1)

Polymeric compound (C); (C1-1); Trimethylolpropane triacrylate (KAYARAD TMPTA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerizable compound (C); (C1-2); pentaerythritol triacrylate (A-TMM-3L; manufactured by Shinnakamura Chemical Co., Ltd.)

Polymerizable compound (C); (C1-3); 2,2,2-tripropylene oxymethyl ethyl succinic acid (CBX-0; manufactured by Shinnakamura Chemical Co., Ltd.)

Polymerizable compound (C); (C1-4); ethoxylated isocyanuric acid triacrylate (A-9300; manufactured by Shinnakamura Chemical Co., Ltd.)

Polymerizable compound (C); (C2-1); Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D); (D-1); N-benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure OXE 01; (Product made in BASF company)

Solvent (E); (E-1); Propylene glycol monomethyl ether acetate

Solvent (E); (E-2); Propylene glycol monomethyl ether

Leveling agent (F); (F-1); Polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

Pattern making

(株)製造)，在大氣氣氛下、以35mJ/cm2的曝光量(365nm基準)進行光照射。作為光掩模，使用了形成了50μm線和間隙圖案的光掩模。光照射後，將上述塗膜在顯影液(以質量分率計，分別包含氫氧化鉀0.05%和丁基萘磺酸鈉0.2%的水溶液)中在25℃下浸漬顯影60秒，水洗後，在烘箱中、230℃下進行30分鐘後烘焙，得到了著色圖案。 After applying the colored curable resin composition to a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by a spin coating method, it was pre-baked at 100°C for 3 minutes. After leaving to cool, the space between the substrate coated with the colored curable resin composition and the photomask made of quartz glass was set to 80 μm, and an exposure machine (TME-150RSK;

(Manufactured by Co., Ltd.), light was irradiated at an exposure amount of 35 mJ/cm2 (365 nm standard) in an air atmosphere. As the photomask, a photomask formed with a pattern of 50 μm lines and gaps was used. After light irradiation, the above-mentioned coating film was immersed and developed in a developing solution (in terms of mass fraction, each containing 0.05% potassium hydroxide and 0.2% sodium butyl naphthalene sulfonate) at 25°C for 60 seconds. After washing, Post-baking was performed in an oven at 230°C for 30 minutes to obtain a colored pattern.

Solubility evaluation

A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was washed sequentially with a neutral lotion, water, and ethanol, and then dried. The colored curable resin composition was spin-coated on the glass substrate, and then prebaked in a clean oven at 100°C for 3 minutes to form a colored composition layer.

Next, the substrate on which the coloring composition layer is formed is immersed and developed in a developing solution (in terms of mass fraction, each containing 0.05% potassium hydroxide and 0.2% sodium butyl naphthalene sulfonate) in a liquid temperature of 25°C. The time when the partial dissolution of 10 mm from the center of the substrate was completed was regarded as the dissolution time. If the dissolution time is 25 seconds or less, the solubility is good. For such colored curable resin The composition can produce a colored pattern in which development defects such as residues are suppressed even if the development time is short, so it can be said that the productivity is high. The results are shown in Table 5.

Film thickness measurement

With respect to the obtained colored pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 5.

Chromaticity evaluation

For the obtained coloring pattern, the spectroscopy was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the characteristic function of the C light source was used to measure the xy chromaticity coordinates in the XYZ color system of CIE ( x, y) and lightness Y. The results are shown in Table 5.

Linear observation

製造)觀察形成的圖案的直線性。將形成的圖案的偏差寬度為1.0μm以下的情形記為○，將形成的圖案的偏差寬度超過1.0μm、直線性存在問題的情形記為×，示於表5中。 For the substrate washed with water after development, use a scanning electron microscope (S-4000; Hitachi Co., Ltd.)

Manufacturing) Observe the linearity of the formed pattern. The case where the deviation width of the formed pattern was 1.0 μm or less was marked as ○, and the case where the deviation width of the formed pattern exceeded 1.0 μm and the linearity was problematic was marked as ×, and is shown in Table 5.

Industrial availability

According to the colored curable resin composition of the present invention, it is possible to form a color filter that has a fast development speed, high brightness, and good linearity when a colored pattern is formed.

Claims (5)

A colored curable resin composition containing a colorant (A), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D), the colorant (A) is composed of a pigment skeleton A coloring agent of a compound (Aa) composed of a cation, and an anion of a compound containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen. The polymerizable compound (C) contains an ethylenically unsaturated bond The first polymerizable compound (C1) having a number of 2 or more and 4 or less and the second polymerizable compound (C2) having an ethylenically unsaturated bond of 5 or more and 8 or less. The colored curable resin composition of claim 1, wherein the ratio of the first polymerizable compound (C1) to the total of the first polymerizable compound (C1) and the second polymerizable compound (C2) is 5 Mass% or more and 50 mass% or less. The coloring curable resin composition of claim 1, wherein the compound (Aa) is a compound represented by formula (AI):

In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons, or a substituted carbon number 7 ~30 aralkyl group. In the saturated hydrocarbon group with 1 to 20 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted by substituted or unsubstituted amine groups or halogen atoms, and the saturated hydrocarbon group has 2~ In the case of 20, the methylene group contained in the saturated hydrocarbon group can be replaced by an oxygen atom or -CO-, R ⁴¹ and R ⁴² can be combined to form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ can be combined And together with the nitrogen atom to which they are bonded to form a ring, R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and the carbon number of the alkyl group is 2 to In the case of 8, the methylene group constituting the alkyl group can be replaced with an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² can be combined to form -NH-, -O-, -S- or -SO _2- , Ring T ¹ represents an aromatic heterocyclic ring with a carbon number of 3-10 that may have a substituent, [Y] ^m- represents containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus, and oxygen as essential elements Any m-valent anion of, m represents an arbitrary natural number. A color filter formed of the coloring curable resin composition according to any one of claims 1 to 3. A display device including the color filter as claimed in claim 4.