TW201910441A - Colored curable resin composition, color filter and display device - Google Patents

Abstract

The present invention provides a colored curable resin composition capable of forming a color filter and a display device which are excellent in contrast. A colored curable resin composition according to the present invention is characterized by comprising: a coloring agent, a resin, a polymerizable compound, and a polymerization initiator, wherein the coloring agent comprises a compound represented by formula (I): in formula (I), R 1 and R 2 each independently represents a hydrocarbon group having from 1 to 8 carbon atoms, a halogen atom or an -OR 3 group, wherein R 3 represents a hydrocarbon group having 1 to 8 carbon atoms and capable of having substituent groups, and M k+ represents a k-valent cation, k represents an integer of 1 or more and 5 or less, m represents an integer of 0 or more and 4 or less, when m is 2 or more, theses R 1s can be the same or different, n represents an integer of 1 or more and 5 or less, and when n is 2 or more, these R2s can be the same or different.

Description

   Colored curable resin composition, color filter and display device   

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

Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCDs and CMOS sensors are manufactured from colored curable resin compositions. As such a colored curable resin composition, a composition containing C.I. Pigment Red 269 as a colorant is known (Patent Document 1).

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2016-170324

However, a color filter formed by the above-mentioned colored curable resin composition cannot satisfy the contrast sufficiently. Therefore, the present invention provides a colored curable resin composition capable of forming a color filter with excellent contrast.

The present disclosure includes the following inventions.

[1] A colored curable resin composition including a colorant, a resin, a polymerizable compound, and a polymerization initiator, and the colorant includes a compound represented by formula (I).

[In the formula (I), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 8 carbon atoms, which may have a substituent, a halogen atom, or a —OR ³ group.

R ³ represents a hydrocarbon group having 1 to 8 carbons which may have a substituent.

M ^{k +} represents a k-valent cation.

k represents an integer of 1 or more and 5 or less.

m represents an integer of 0 or more and 4 or less. When m is 2 or more, the R ¹ may be the same or different.

n represents an integer of 1 or more and 5 or less. When n is 2 or more, these R ² may be the same or different. ]

[2] A color filter formed of the colored curable resin composition according to [1].

[3] A display device including the color filter according to [2].

According to the present invention, a colored curable resin composition capable of forming a color filter with excellent contrast is provided.

<Colored curable resin composition>

The colored curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and includes a compound represented by the formula (I).

The colored curable resin composition of the present invention may further include a polymerization initiation aid (D1), a solvent (E), and a leveling agent (F).

In the present specification, the compounds exemplified as each component can be used alone or in combination of a plurality of types unless otherwise specified.

<Colorant (A)>

The colored curable resin composition of the present invention contains a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)) as a colorant (A).

[In formula (I), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 8 carbon atoms, which may have a substituent, a halogen atom, or a —OR ³ group.

R ³ represents a hydrocarbon group having 1 to 8 carbons which may have a substituent.

M ^{k +} represents a k-valent cation.

k represents an integer of 1 or more and 5 or less.

m represents an integer of 0 or more and 4 or less. When m is 2 or more, the R ¹ may be the same or different.

n represents an integer of 1 or more and 5 or less. When n is 2 or more, these R ² may be the same or different. ]

The hydrocarbon group having 1 to 8 carbon atoms which may have a substituent represented by R ¹ , R ² and R ³ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent or 6 carbon atoms which may have a substituent. The aromatic hydrocarbon group of 8 to 8 is more preferably an aliphatic hydrocarbon group of 1 to 8 carbons which may have a substituent.

The aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ¹ , R ² and R ³ may be a linear, branched or cyclic aliphatic hydrocarbon group.

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

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

Examples of the aromatic hydrocarbon group having 6 to 8 carbon atoms in R ¹ , R ² and R ³ include a phenyl group, a tolyl group, a xylyl group, a phenethyl group, an α-methylbenzyl group, and the like. The carbon number of the aromatic hydrocarbon group is preferably 6.

The hydrocarbon group having 1 to 8 carbon atoms represented by R ¹ , R ² and R ³ may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, a bromine atom, and the like; a nitro group ; Cyano; amine; hydroxy; alkoxy having 1 to 6 carbons, such as methoxy, ethoxy, etc .; hydrogenthio; alkylhydrothio having 1 to 6 carbons, such as methylhydrosulfide Alkyl, ethylhydrothio, etc .; carboxyl; carbamoyl; alkoxycarbonyl having 1 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc .; sulfonic acid group; aminesulfonyl; carbon number 1 to 6 alkoxysulfonyl groups, such as methoxysulfonyl, ethoxysulfonyl and the like; and others.

R ¹ , R ² and R ³ are each preferably independently methyl, ethyl, propyl, trifluoromethyl or phenyl, and more preferably methyl or ethyl. Moreover, R ¹ , R ² and R ³ may be the same or different.

Examples of the halogen atom represented by R ¹ or R ² include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom. A chlorine atom is preferred.

The -OR ³ group represented by R ¹ or R ² is particularly preferably a methoxy group or an ethoxy group.

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

Examples of k-valent metal ions represented by M ^{k +} include alkali metal ions, such as lithium ions, sodium ions, and potassium ions; alkaline earth metal ions such as magnesium ions, calcium ions, strontium ions, and barium ions; transitions; Metal ions, such as titanium ions, zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, etc .; main group metal ions, such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, Lead ions, bismuth ions, etc .; and others.

Examples of the substituted or unsubstituted ammonium ion represented by M ^{k +} include a quaternary ammonium ion such as a tetraalkylammonium ion.

M ^{k + is} preferably a hydrogen ion or a k-valent metal ion, more preferably a hydrogen ion, an alkali metal ion or an alkaline earth metal ion, and even more preferably an alkaline earth metal ion. As M ^{k +} , a hydrogen ion, a sodium ion, a potassium ion, a magnesium ion, a strontium ion, a barium ion, a zirconium ion, a manganese ion, or a zinc ion is preferable, and a hydrogen ion or a barium ion is more preferable.

k is preferably 4 or less, more preferably 3 or less, and even more preferably 1 or 2.

m is preferably 3 or less, more preferably 2 or less, particularly preferably 1 or less, and particularly preferably 0. When m is 2 or more, these R ¹ may be the same or different.

n is preferably 2 or more, more preferably 5 or less, more preferably 4 or less, particularly preferably 3 or less, and particularly preferably 3. When n is 2 or more, these R ² may be the same or different.

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

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

[In the formula (II), R ²¹ to R ²⁵ are each independently a hydrogen atom, a halogen atom, or an -OR ³ group, and at least one of R ²¹ to R ²⁵ is a halogen atom or an -OR ³ group.

R ¹ , m, R ³ , M ^{k +} and k are the same as described above. ]

Examples of the halogen atom in the formula (II) include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom. A chlorine atom is preferred.

Of the above R ²¹ to R ²⁵ , more than two (preferably four or less) are preferably halogen atoms and / or -OR ³ groups, and more preferably three of R ²¹ to R ²⁵ are halogen atoms and / or -OR. ³ bases.

In formula (II), either R ²¹ or R ²³ or both R ²¹ and R ²³ is preferred, and R ²¹ and R ²³ are more preferably a -OR ³ group.

In formula (II), either R ²⁴ or R ²⁵ or both R ²⁴ and R ^{25 is} preferred, and R ²⁴ is more preferably a halogen atom.

The compound (II) is preferably at least one selected from the group consisting of a compound represented by formula (II-a), a compound represented by formula (II-b), and a compound represented by formula (II-c). Among them, in order to have good contrast, a compound represented by the formula (II-b) or a compound represented by the formula (II-c) is preferable, and a compound represented by the formula (II-b) is more preferable.

[In the formula (II-a), the formula (II-b), and the formula (II-c), R ²¹ to R ²⁵ , M ^{k +} and k are the same as described above. ]

Examples of the compound (I) include the compounds shown in Tables 1 to 3 and the like represented by the formula (I-1) to the formula (I-216).

The compound (I) is preferably a compound represented by the formula (I-13) to (I-20), a compound represented by the formula (I-85) to (I-92), and a compound represented by the formula (I-157) To a compound represented by formula (I-164); more preferably a compound represented by formula (I-13) to formula (I-16), a compound represented by formula (I-85) to formula (I-88), Compounds represented by formula (I-157) to formula (I-160); still more preferred are compounds represented by formula (I-85) to formula (I-88), and formula (I-157) to formula ( I-160).

In Tables 1 to 3, OMe represents a methoxy group, and OEt represents an ethoxy group.

In addition, in Tables 1 to 3, "PH" in the formula (I) represents a phenyl group in which SO ₃ ^- and (R ¹ ) _{m are} bonded (* represents a bonding end with a nitrogen atom), and specifically, it means by the formula (Ph1) to a group represented by formula (Ph3).

The compound represented by the formula (I) (where M ^{k +} = H ⁺ ) can cause a nitrite (such as sodium nitrite) to act on the compound represented by the formula (pt1) in an acidic aqueous solution to generate a diazonium salt. It is produced by reacting the generated diazonium salt with a compound represented by the formula (pt2). In this reaction, the amount of the compound represented by the formula (pt1) is preferably 0.5 to 1.5 moles relative to the compound 1 mole represented by the formula (pt2).

In addition, the compound represented by the formula (I) (where M ^{k +} ≠ H ⁺ ) can be obtained by combining the compound represented by the formula (I) (where M ^{k +} = H ⁺ ) and a k-valent cation M ^{k +} (where , M ^{k +} ≠ H ⁺ ), produced by the reaction of a halide (preferably chloride), acetate, phosphate, sulfate, silicate or cyanide.

[In formulae (pt1), (pt2), and (I), R ¹ , R ² , m, n, M ^{k +,} and k are the same as described above. ]

The content of the compound (I) is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 30 mass% or more, and even more preferably 50 mass% in the total amount of the colorant (A). Above 80% by mass, particularly preferably above 90% by mass.

The colored curable resin composition of the present invention may contain, as the colorant (A), in addition to the compound (I), a dye (A1) and a pigment (A2).

The dye (A1) is not particularly limited, and conventional dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye include compounds classified as having a hue in pigments other than pigments in the Outstanding Index (published by The Society of Dyers and Colourists), or a practice described in a dyeing note (color dyeing society). Known dyes. In addition, according to the chemical structure, azo dyes (but not including compound (I)), cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dye, Naphthoquinone dyes, quinone imine dyes, methine dyes, methine azo dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes Wait. Among these, a dye having an organic solvent solubility is preferred.

The pigment (A2) is not particularly limited, and conventional pigments can be used, and examples thereof include pigments classified as pigments in the Outstanding Index (published by the British Dye and Colorists Association).

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

The content of the colorant (A) is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and still more preferably 1 to 50% by mass with respect to the total amount of the solid content.

Here, the "total amount of solid content" in the present specification means an amount after removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid component and the content of each component relative to the solid component can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one (a) derived from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as "(a) ""). The resin (B) is more preferably a structural unit having at least one selected from the group consisting of a monomer (b) derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as ("(B)"), a structural unit derived from a monomer (c) copolymerizable with (a) (but different from (a) and (b).) (Hereinafter sometimes referred to as "(c)") A structural unit and a structural unit having an ethylenically unsaturated bond in a side chain.

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

(b) A cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth) acryloxy group Monomer.

In addition, in this specification, "(meth) acrylic acid" means at least 1 sort (s) chosen from acrylic acid and methacrylic acid. The expressions "(meth) acrylfluorenyl" and "(meth) acrylate" have the same meaning.

Examples of (b) include glycidyl (meth) acrylate, vinyl benzyl glycidyl ether, and (meth) acrylic-3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane Ester, 3-ethyl-3- (meth) acryloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate, and the like, preferably glycidyl (meth) acrylate, (formaldehyde) (Meth) acrylic acid 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ester, 3-ethyl-3- (meth) propenyloxymethyloxetane.

Examples of (c) include methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and (formyl) (Triyl) acrylic acid tricyclic [5.2.1.0 ^2,6 ] decane-8-yl ester, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene, etc., preferably, styrene, vinyltoluene, (meth) acrylic acid-2- Hydroxyethyl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and the like.

The resin system having a structural unit having an ethylenically unsaturated bond in the side chain can be added to (b) and (c) to the copolymer of (a) and (c) or (a) to (b) and (c). ) Copolymer. The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c), and further reacting a carboxylic anhydride.

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

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

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

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

<Polymerizable Compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by using living radicals and / or acids generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. (Meth) acrylate compounds.

Among these, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dioxin Pentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, and the like.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) with respect to the total amount of the solid content is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that generates living radicals, acids, and the like by the action of light and heat and can initiate polymerization, and a conventional polymerization initiator can be used. Examples of the polymerization initiator that generates living radicals include N-benzyloxy-1- (4-phenylhydrothiophenyl) butane-1-one-2-imine, and N-benzene Methyloxy-1- (4-phenylhydrothiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylhydrothiophenyl) ) -3-cyclopentylpropane-1-one-2-imine, 2-methyl-2-morpholinyl-1- (4-methylhydrothiophenyl) propane-1-one, 2 -Dimethylamino-1- (4-morpholinylphenyl) -2-benzylbutane-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4-bis (trichloromethyl) ) -6-Sunfloweryl-1,3,5-triazine, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 2,2'-bis (2-chlorophenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole and the like.

The content of the polymerization initiator (D) 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 resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above-mentioned range, the sensitivity tends to increase and the exposure time tends to decrease, so the productivity of the color filter is improved.

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

<Polymerization Initiation Auxiliary (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound that has been polymerized by a polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include 4,4'-bis (dimethylamino) benzophenone (commonly known as Michelin), 4,4'-bis (diethylamino) Benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine and the like.

When using these polymerization initiation aids (D1), the content is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 100 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter tends to be improved.

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

<Solvent (E)>

The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. Examples include an ester solvent (a solvent containing -COO- and no -O- in the molecule), an ether solvent (a solvent containing -O- and no -COO- in the molecule), and an ether ester solvent (in a molecule Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH and no -O-, -CO in the molecule) -And -COO- solvents), aromatic hydrocarbon solvents, amidine solvents, dimethylsulfinium, and the like.

Examples of the solvent include ester solvents (solvents containing -COO- and no -O- in the molecule), such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, Ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone, etc .; ether solvents (containing -O- and -COO in the molecule -Solvents), such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, Ethylene glycol methyl ethyl ether, etc .; ether ester solvents (solvents containing -COO- and -O- in the molecule), such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, etc .; ketone solvents (in the molecule Solvents containing -CO- and -COO-), such as 4-hydroxy-4-methyl-2-pentanone, heptone, 4-methyl-2-pentanone, cyclohexanone, etc .; alcohol solvents ( Solvents that contain OH in the molecule and do not contain -O-, -CO- and -COO-), such as butanol, cyclohexanol, propylene glycol, etc .; amine solvents, such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; etc .; and others.

As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and 4-hydroxy-4-methyl-2-pentanone are more preferable.

When the solvent (E) is contained, the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, with respect to the total amount of the colored curable resin composition of the present invention. In other words, the total amount of solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above-mentioned range, the flatness at the time of coating becomes good, and when the color filter is formed, the color density is not insufficient, so that the display characteristics tend to be good.

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

<Leveling agent (F)>

Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have polymerizable groups in a side chain.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specific examples include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Advanced Materials Japan Co., Ltd.).

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

Examples of the organosilicon surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include MEGAFAC (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

In the case where the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, and more preferably 0.002 to 0.1% by mass, with respect to the total amount of the colored curable resin composition. The content of the pigment dispersant is not included in the content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be made good.

<Other ingredients>

The colored curable resin composition of the present invention may contain additives known in this technical field, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as necessary.

<Manufacturing method of colored curable resin composition>

The colored curable resin composition of the present invention can be obtained by combining a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a polymerization initiation aid (D1) as required. , Solvent (E), leveling agent (F) and other ingredients.

<Manufacturing Method of Color Filter>

Examples of a method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, photolithography is preferred.

By containing the compound (I) as a colorant, the colored curable resin composition can produce a color filter having particularly excellent contrast. This color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Examples

Hereinafter, the colored curable resin composition of the present invention will be described in more detail through examples. Unless otherwise specified, "%" and "part" in the examples are mass% and mass part.

[Synthesis example 1]

After 100 parts of water was added to 17.3 parts of o-aminobenzenesulfonic acid, 4.0 parts of sodium hydroxide was added to dissolve. 21.7 parts of a 35% sodium nitrite aqueous solution was added to an ice bath, and then 11.5 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

37.6 parts of 5'-chloro-3-hydroxy-2 ', 4'-dimethoxy-2-naphthylafenanilide was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The above-mentioned suspension containing the diazonium salt was added dropwise thereto over 15 minutes. After completion of the dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. After the suspension was stirred for 1 hour, it was further stirred for 1 hour. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 53.2 parts of a compound represented by formula (I-1).

5.4 parts of the compound represented by the formula (I-1) was added to 100 parts of water to prepare a liquid (aqueous solution 1) in which the compound represented by the formula (I-1) was dissolved. In addition, a liquid (aqueous solution 2) in which 4.9 parts of barium chloride dihydrate was dissolved in 80 parts of water was prepared. The aqueous solution 2 was dropped into the aqueous solution 1 at 40 ° C. over 2 hours, and then stirred for 4 hours. After cooling, it was filtered, washed twice with 100 parts of ion-exchanged water, and the crystals were dried under reduced pressure at 100 ° C to obtain 6.8 parts of a compound represented by formula (I-13).

[Synthesis example 2]

In Synthesis Example 1, the compounds represented by Formula (I-73) and Formula (I-85) were obtained in the same manner as in Synthesis Example 1, except that m-aminobenzenesulfonic acid was used instead of o-aminobenzenesulfonic acid.

[Synthesis example 3]

In Synthesis Example 1, the compounds represented by Formula (I-145) and Formula (I-157) were obtained in the same manner as in Synthesis Example 1, except that p-aminobenzenesulfonic acid was used instead of o-aminobenzenesulfonic acid.

[Resin Synthesis Example 1]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was caused to flow into a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was charged and heated to 80 ° C. while stirring. Next, the following solution was dripped into this flask using a drip pump over about 5 hours: 38 parts of acrylic acid, and acrylic-3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8- A mixture of butyl ester and acrylic acid-3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-yl ester (content 1: 1) 289 parts dissolved in propylene glycol monomethyl ether acetate 125 Portions of the solution. On the other hand, the following solution was dropped into the flask using another dropping pump over about 6 hours: 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in propylene glycol mono A solution in 235 parts of methyl ether acetate. After the dropwise addition was completed, the solution was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a 35.1% copolymer (resin (B-1)) solution having a solid content. The weight average molecular weight Mw of the produced copolymer was 9,200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. The resin (B-1) has the following structural units.

[Resin Synthesis Example 2]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was allowed to flow into a nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was charged and heated to 85 ° C. while stirring. Next, the following solution was added dropwise over 4 hours: 54 parts of acrylic acid, acrylic acid-3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester, and acrylic acid-3,4-epoxytricyclic A mixture of cyclo [5.2.1.0 ^2,6 ] decane-9-yl ester (content 1: 1) 225 parts, vinyl toluene (isomer mixture) 81 parts, and propylene glycol monomethyl ether acetate 80 Parts of the mixed solution. On the other hand, the following solution was added dropwise over 5 hours: 30 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 160 parts of propylene glycol monomethyl ether acetate Solution. After the addition of the initiator solution was completed, the solution was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a type B viscosity (23 ° C) of 246 mPa. A copolymer (resin (B-2)) solution with a solid content of 37.5%. The weight average molecular weight Mw of the resulting copolymer was 10600, the degree of dispersion was 2.01, and the acid value in terms of solid content was 112 mg-KOH / g. The resin (B-2) has the following structural units.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by gel permeation chromatography (GPC method) under the following conditions.

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

Column: TSK-GELG2000HXL

Column temperature: 40 ℃

Solvent: THF

Flow rate: 1.0 ml / min

Solid content concentration of test liquid: 0.001 to 0.01% by mass

Injection volume: 50 microliters (μL)

Detector: RI

Calibration reference materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

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

(Preparation of colored curable resin composition)

[Preparation of dispersion (P-1)]

10 parts of a compound represented by formula (I-13), 13.3 parts of a dispersant BYK-LPN21116 (manufactured by BYK; 60% propylene glycol monomethyl ether acetate solution), and resin (B-2) (solid content conversion) 8 Parts, 20 parts of 4-hydroxy-4-methyl-2-pentanone and 149 parts of propylene glycol monomethyl ether acetate, 600 parts of 0.2 micron zirconia beads were added, and a paint conditioner (manufactured by LAU) was used. After shaking for 6 hours, the zirconia beads were removed by filtration to obtain a dispersion (P-1).

[Preparation of dispersion (P-2)]

10 parts of a compound represented by formula (I-85), 16.7 parts of a dispersant BYK-LPN21116 (manufactured by BYK; 60% propylene glycol monomethyl ether acetate solution), and resin (B-2) (solid content conversion) 8 Parts, 20 parts of 4-hydroxy-4-methyl-2-pentanone and 145 parts of propylene glycol monomethyl ether acetate, 600 parts of 0.2 micron zirconia beads were added, and a paint conditioner (manufactured by LAU) was used. Shake for 3 hours. Then, the zirconia beads were removed by filtration to obtain a dispersion (P-2).

[Preparation of dispersion (P-3)]

A dispersion liquid (P-3) was prepared in the same manner as the dispersion liquid (P-2), except that the compound represented by the formula (I-85) was replaced with a compound represented by the formula (I-157).

[Preparation of dispersion (P-4)]

A dispersion liquid (P-4) was produced in the same manner as in the dispersion liquid (P-2), except that the compound represented by the formula (I-85) was replaced with C.I. Pigment Red 269.

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

In Table 4, each component shows the following compounds.

(B-1): Resin (B-1) (solid content conversion)

(C-1): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark)

(DPHA; manufactured by Nippon Kayaku Co., Ltd.)

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

(E-1): Propylene glycol monomethyl ether acetate

(E-2): 4-hydroxy-4-methyl-2-pentanone

(F-1): Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Corporation)

<Creation of color filters>

A colored curable resin composition was applied on a 5 cm 2 glass substrate (Eagle 2000; manufactured by Corning) by a spin coating method, and then pre-baked at 100 ° C. for 3 minutes to obtain a colored composition layer. After leaving to cool, it was post-baked at 230 ° C. for 20 minutes in an oven to obtain a color filter.

<Contrast evaluation>

For the obtained color filters, a contrast meter (CT-1, manufactured by Husaka Electric Co., Ltd .; a chromatic aberration meter BM-5A, manufactured by Topcon Corporation; light source, F-10; polarizing film, Husaka (Manufactured by Denki Co., Ltd.), the blank value was set to 30,000, and the contrast was measured. The results are shown in Table 5.

[table 5]

Industrial availability

According to the colored curable resin composition of the present invention, a color filter having excellent contrast can be produced.

Claims (3)

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, the colorant comprising a compound represented by formula (I), In formula (I), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 8 carbon atoms, a halogen atom, or an -OR ³ group which may have a substituent, and R ³ represents a carbon group having 1 to 8 carbon atoms which may have a substituent. For a hydrocarbon group, M ^{k +} represents a k-valent cation, k represents an integer of 1 or more and 5 or less, m represents an integer of 0 or more and 4 or less, and when m is 2 or more, these R ¹ may be the same or different, and n represents 1 or more and When the integer is 5 or less, and n is 2 or more, the R ² may be the same or different.     A color filter formed from the colored curable resin composition according to claim 1.         A display device includes the color filter according to claim 2.