TWI734946B - Red curable resin composition, color filter and display device - Google Patents

Abstract

[Subject] The color filters and display devices formed from the previously known red curable resin composition may not sufficiently satisfy the thinning in the dark (high chroma) region. [Solution] The present invention provides a red curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant includes a porphyrazine compound and a red pigment.

Description

Red curable resin composition, color filter and display device

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

In liquid crystal display devices, electroluminescence display devices, plasma displays and other display devices or CCD (Charge-Coupled Device) or CMOS (Complementary Metal-Oxide-Semiconductor, complementary metal oxide semiconductor) sensors and other solid-state imaging The color filter used in the element is made of a colored curable resin composition. As such a colored curable resin composition, a composition containing C.I. Pigment Red 177 as a coloring agent is known (Patent Document 1). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2004-341245

[The problem to be solved by the invention]

In recent years, research on expanding the color gamut has been conducted in display devices and the like, and the color filters used in these are further required to be dark (high chroma). If the film thickness of the color filter is increased, the color filter becomes dark (high chroma), but for color filters, it is required to be thinner (high chroma) at the same time as the color filter is required. However, the color filter formed by the previously known colored curable resin composition is not one that can satisfy the thin film in the dark (high chroma) area. [Means to solve the problem]

[1] A red curable resin composition comprising: a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein The coloring agent contains a tetraazaporphyrin compound and a red pigment.

[2] A color filter formed of the red curable resin composition as described in [1].

[3] A display device including the color filter as described in [2]. [Effects of Invention]

According to the red curable resin composition of the present invention, a dark color (high chroma) and thin film color filter can be formed.

The red curable resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as colorant (A)), resin (hereinafter, sometimes referred to as resin (B)), and a polymerizable compound (hereinafter, It may be called a polymerizable compound (C)) and a polymerization initiator (hereinafter, it may be called a polymerization initiator (D)).

The red curable resin composition of the present invention preferably further contains a solvent (hereinafter, it may be referred to as a solvent (E)).

The red curable resin composition of the present invention may further include a leveling agent.

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

＜Colorant (A)＞

The coloring agent (A) contains a porphyrazine compound and a red pigment. The porphyrazine compound is a compound having a porphyrazine skeleton in the molecule. In addition, when the porphyrazine compound is a salt, it may form a salt with any cation or anion.

（於式（1）中，R^1a 至R^1d 及R^2a 至R^{2 d} 分別獨立地表示可具有取代基之飽和烴基或可具有取代基之芳基； x表示1或2； 當x為1時，M1表示二價金屬原子、取代金屬原子或氧化金屬原子； 當x為2時，M1表示氫原子或一價金屬原子）The porphyrazine compound is preferably a compound represented by formula (1) (hereinafter, it may be referred to as compound (1)). [化1]

(In formula (1), R ^1a to R ^1d and R ^2a to R ^{2 d} each independently represent a saturated hydrocarbon group that may have a substituent or an aryl group that may have a substituent; x represents 1 or 2; when x is 1 When, M1 represents a divalent metal atom, a substituted metal atom or an oxidized metal atom; when x is 2, M1 represents a hydrogen atom or a monovalent metal atom)

In the formula (1), R ^1a to R ^1d and R ^2a to R ^{2 d} are groups bonded to the porphyrazine skeleton.

R ^1a to R ^1d may be the same or different, and are preferably the same; in addition, R ^2a to R ^{2 d} may be the same or different, and are preferably the same. More preferably, R ^1a to R ^{1d are the} same, and R ^2a to R ^{2 d are the} same.

Examples of saturated hydrocarbon groups representing R ^1a to R ^1d and R ^2a to R ^{2 d} include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, N-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and other linear alkyl groups; isopropyl, isobutyl, 2-butyl Base, tertiary butyl, 2-methylbutyl, 1-methylbutyl, neopentyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 4-methylpentyl Base, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethyl Butyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, 3-ethylbutyl, 2-ethylbutyl, 1-ethyl Butyl, 1,1,2-trimethylpropyl, 1-ethyl-2-methylpropyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methyl Hexyl, 1-ethylpentyl, 2,4-dimethylpentyl, 2-ethylhexyl, 2,5-dimethylhexyl, 2,5,5-trimethylpentyl, 2,4- Dimethylhexyl, 2,2,4-trimethylpentyl, 1,1-dimethylhexyl, 3,5,5-trimethylhexyl, 4-ethyloctyl, 4-ethyl-4 ,5-Dimethylhexyl, 1,3,5,7-tetramethyloctyl, 4-butyloctyl, 6,6-diethyloctyl, 6-methyl-4-butyloctyl , 3,5-dimethyl heptadecyl, 2,6-dimethyl heptadecyl, 2,4-dimethyl heptadecyl, 2,2,5,5-tetramethylhexyl and other branched chains Alkyl; Cycloalkyl groups such as cyclopentyl, cyclohexyl, 1-cyclopentyl-2,2-dimethylpropyl, 1-cyclohexyl-2,2-dimethylpropyl, etc.

The carbon number of the saturated hydrocarbon group is preferably from 1 to 20, more preferably from 1 to 15, further preferably from 1 to 10, and still more preferably from 1 to 5.

Among them, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

As the substituent which this saturated hydrocarbon group may have, a halogen atom is preferable. Examples of saturated hydrocarbon groups having halogen atoms include: chloromethyl, dichloromethyl, fluoromethyl, trifluoromethyl, pentafluoroethyl, nonafluorobutyl, perfluorocyclobutyl, perfluorocyclopentyl Wait.

Examples of the aryl group representing R ^1a to R ^1d and R ^2a to R ^2d include phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, naphthyl, methylnaphthyl, and the like.

Examples of substituents that the aryl group may have include nitro groups, cyano groups, halogen atoms (preferably fluorine atoms, chlorine atoms, and bromine atoms), hydroxyl groups, carboxyl groups, alkoxy groups having 1 to 8 carbon atoms, and Amino groups substituted by alkyl groups having 1 to 8 carbon atoms, etc.

Examples of the substituted aryl group include: fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, tetrafluorophenyl Chlorophenyl, pentachlorophenyl, bromophenyl, dibromophenyl, tribromophenyl, tetrabromophenyl, pentabromophenyl, trifluoromethylphenyl, bis-trifluoromethylphenyl, ginseng -Trifluoromethylphenyl, 4-trifluoromethylphenyl, fluoromethylphenyl, fluoronaphthyl, chloronaphthyl, bromonaphthyl, trifluoromethylnaphthyl and other aromatics substituted by halogen atoms Group; nitrophenyl, nitronaphthyl; cyanophenyl, cyanonaphthyl; hydroxyphenyl, hydroxynaphthyl; carboxyphenyl; methoxyphenyl, ethoxyphenyl; N,N- Dimethylaminophenyl and so on.

The carbon number of the aryl group is, for example, 6-20, preferably 6-18, more preferably 6-15, and still more preferably 6-10.

As the aryl group which may have a substituent, an unsubstituted aryl group or an aryl group substituted with a halogen atom is preferable.

Preferably, R ^1a to R ^1d are each independently a saturated hydrocarbon group of 1 to 10 carbons which may have a substituent, and more preferably each independently are a linear alkyl group of 1 to 10 carbons which may have a substituent or The branched chain alkyl group is more preferably each independently a linear alkyl group having 1 to 5 carbon atoms or a branched chain alkyl group which may have a substituent. R ^1a to R ^{1d are} particularly preferably tertiary butyl groups.

Preferably, R ^2a to R ^2d are each independently an aryl group having 6 to 20 carbon atoms that may have a substituent, more preferably each independently an aryl group having 6 to 20 carbon atoms that may have a substituent, and more preferably each independently Each independently is an aryl group having 6 to 20 carbons substituted by a halogen atom, and more preferably is an aryl group having 6 to 20 carbon atoms substituted by a fluorine atom. R ^2a to R ^{2d are} particularly preferably 2-fluorophenyl.

When x is 2, it represents an M1 monovalent metal atom, and examples include alkali metal atoms such as Na, K, and Li. In this case, >N—, —N< in formula (1) does not bridge but is bonded to each monovalent metal atom.

As the divalent metal atom that represents M1 when x is 1, examples include: Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg , Pb and Sn etc.

Examples of the substituted metal atom include: Al-Cl, Ga-Br, Ga-I, In-Cl, Al-C ₆ H ₅ , In-C ₆ H ₅ , Mn(OH), Mn[OSi(CH ₃ ) ₃ ] and Fe-Cl and so on.

Examples of oxidized metal atoms include V (=O), Mn (=O), Ti (=O), and the like.

M1 is preferably a divalent metal atom or an oxide metal atom, more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, V(=O) or Ti(=O), and further preferably Cu, Zn , Ni, Pd or V(=O), particularly preferably Cu, Pd or V(=O).

Preferably, in compound (1), x is 1 and M1 is a compound in which a divalent metal atom or an oxidized metal atom is used.

[化3]

[化4]

[化5]

[化6]

As specific examples of the compound (1), compounds represented by formula (2-1) to formula (2-38) and the like can be cited. [化2]

[化3]

[化4]

[化5]

[化6]

[化8]

[化9]

[化10]

As other specific examples, compounds represented by formula (2-39) to formula (2-45) and the like can be cited. [化7]

[化8]

[化9]

[化10]

Among them, particularly preferred are compounds represented by formula (2-29), formula (2-38), formula (2-39) to formula (2-45).

Compound (1) is usually a compound that absorbs orange light near 590 nm, and its absorption maximum wavelength (λmax) is preferably 570 nm or more and 620 nm or less, more preferably 575 nm or more and 615 nm Below meters.

The coloring agent (A) contains a red pigment. Examples of red pigments include red pigments and red dyes.

As red pigments, conventional pigments can be used, for example, the pigments classified as pigments in the Colour Index (published by The Society of Dyers and Colourists), are classified as red By. Two or more types can also be combined. However, the compound (1) is excluded.

Specifically, include: CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, etc.

Among the red pigments, anthraquinone pigments, azo pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments are preferred; CI Pigment Red 177, 179, 202, 208, 242, 254 are preferred , 269, brominated diketopyrrolopyrrole pigment; more preferably CI Pigment Red 177, 254, brominated diketopyrrolopyrrole pigment.

Examples of red dyes include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes or sulfonamide derivatives of acid dyes. Published by the Society of Colorists) are classified as dyes, that is, compounds other than pigments; or the conventional dyes recorded in the dyeing notes (color dyeing company). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes can be cited And acridine dyes and so on. Among them, organic solvent-soluble dyes are preferred. Two or more of these dyes may be used in combination.

Specifically, examples include: CI Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; C.I. Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289, etc.

The red curable resin composition of the present invention may contain the compound (1) and the red pigment, and a coloring agent other than the compound (1) (hereinafter, it may be referred to as a coloring agent (A1)) as the coloring agent (A).

The colorant (A1) may be a dye or a pigment. Examples of dyes include conventional dyes (except for red dyes) described in the Dye Index (published by the British Society of Dyestuffs and Colorists) and Dyeing Notes (Color Dyeing Company). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azo Methylene dyes, square acid cyanine (squarylium) dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes and phthalocyanine dyes, etc. Among them, organic solvent-soluble dyes are preferred. Two or more of these dyes may be used in combination.

Specifically, the dyes with the following dye index (C.I.) numbers can be listed. C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Reactive Yellow 2, 76, 116; CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102 , 108, 109, 129, 132, 136, 138, 141; C.I. Disperse Yellow 51, 54, 76; C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; C.I. Reactive Orange 16; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Acid Violet 34, 102; C.I. Disperse Violet 26, 27; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111 , 112, 122, 128, 132, 136, 139; C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112; C.I. Direct Blue 40; C.I. Disperse Blue 1, 14, 56, 60; C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33; C.I. Acid Green 3, 5, 9, 25, 27, 28, 41; C.I. Basic Green 1; C.I. Vat Green 1 etc.

As the pigment, conventional pigments can be used, for example, pigments classified as pigments in the Dyestuff Index (published by the British Society of Dyestuffs and Colorists). Two or more types can also be combined.

Specifically, include: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. Purple pigments such as pigment violet 1, 19, 23, 29, 32, 36, 38; C.I. Pigment Green 7, 36, 58, 59 and other green pigments.

Among them, the coloring agent (A1) is preferably one or both of a yellow pigment and an orange pigment, and more preferably a yellow pigment. That is, the coloring agent (A) further preferably contains a yellow pigment in addition to the porphyrazine compound and the red pigment.

The pigment as the colorant (A1) is preferably a yellow pigment and/or an orange pigment, and more preferably a yellow pigment.

Red pigments and pigments as colorants (A1) (sometimes referred to as pigments) may be treated with rosin, surface treatments such as coloring agent derivatives with acidic or basic groups introduced, and polymer Grafting treatment of the surface of pigments with compounds, etc., micronization treatment using sulfuric acid micronization method, cleaning treatment using organic solvent or water to remove impurities, ion exchange method using ionic impurities, etc. removal treatment, etc. The particle diameters of the pigments and the like are preferably each substantially uniform. The pigment can be uniformly dispersed in the dispersion liquid by containing a dispersant and performing a dispersion treatment.

As a dispersing agent, surfactant etc. are mentioned, and it may be any of a cationic, anionic, nonionic, and amphoteric surfactant. Specifically, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants, etc., can be cited. As other dispersants, the resin (B) described later can also be used. These dispersants can be used alone or in combination of two or more kinds. As a dispersant, if it is expressed by a trade name, it can include: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zelikon Co., Ltd.) ), EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Precision Technology Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK Chemie), BYK (registered trademark) ) (Manufactured by BYK Chemical Company) and so on.

In the case of using a dispersant, relative to 100 parts by mass of the pigment, the amount of the dispersant used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less. If the amount of dispersant used is in the aforementioned range, there is a tendency to obtain a pigment dispersion in a more uniform dispersion state.

Relative to the total solid content, the content of the compound (1) is preferably 0.2% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and still more preferably 1% by mass or more and 12% by mass %the following.

In 100% by mass of the coloring agent, the content of the red pigment is preferably from 45% by mass to 80% by mass, more preferably from 47% by mass to 75% by mass, and still more preferably from 50% by mass to 70% by mass.

Relative to the total solid content, the content of the red pigment is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, and still more preferably 10% by mass or more and 40% by mass or less .

With respect to 100 parts by mass of the red pigment, the content of the compound (1) is preferably 0.1 part by mass or more and 200 parts by mass or less, more preferably 1 part by mass or more and 100 parts by mass or less, and still more preferably 1 part by mass or more and 70 parts by mass The following.

Relative to the total solid content, the content of the colorant (A1) (preferably yellow pigment) is usually 0% by mass or more and 50% by mass or less, preferably 0% by mass or more and 40% by mass or less, more preferably 0% by mass or more and 30% by mass or less.

When a yellow pigment is included, the total content of the red pigment and the yellow pigment in the colorant is preferably 65% by mass or more and 97% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and more preferably It is 75% by mass or more and 93% by mass or less.

Relative to the total solid content, the content of the colorant (A) is preferably 5% by mass or more and 60% by mass or less, more preferably 8% by mass or more and 55% by mass or less, and still more preferably 10% by mass or more and 50% by mass. Less than mass%.

Here, the "total solid content" in this specification refers to the amount obtained by subtracting the solvent content from the total amount of the red curable resin composition. The total solid content and the content of each component relative to it can be measured, for example, by conventional analytical 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 monomer (a) derived from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter There is a resin with a structural unit called "(a)"). The resin (B) further preferably has at least one structural unit selected from the group consisting of the following structural units: a monomer derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond ( b) (Hereinafter, there are cases called "(b)") structural units derived from monomers (c) that can be copolymerized with (a) (but, different from (a) and (b)) (below There are structural units called "(c)") and structural units having ethylenically unsaturated bonds in the side chain.

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and succinic acid mono[2-(meth)propylene Acrylic oxyethyl] ester and the like are preferably acrylic acid, methacrylic acid, and maleic anhydride.

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

(B) Preferably, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxygen ring, and a tetrahydrofuran ring) and (methyl) The monomer of acryloxy group.

Examples of (b) include glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, 3-Ethyl-3-(meth)acryloyloxymethyloxy, tetrahydrofurfuryl (meth)acrylate, etc.; preferably glycidyl (meth)acrylate, (meth)acrylic acid -3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl ester, 3-ethyl-3-(meth)acryloyloxymethyloxy group.

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

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

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

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

In terms of solid content, the acid value of resin (B) is preferably 50 mg-KOH/g (mg-KOH/gram) to 170 mg-KOH/g, more preferably 60 mg-KOH/g to 150 mg- KOH/g is more preferably 70 mg-KOH/g to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 gram of the resin (B), and it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 10% by mass to 70% by mass relative to the total solid content, more preferably 15% by mass to 65% by mass, and still more preferably 20% by mass to 60% by mass.

＜Polymerizable compound (C)＞

The polymerizable compound (C) is a compound that can be polymerized by living radicals and/or acid generated from the polymerization initiator (D). For example, a polymerizable compound having an ethylenically unsaturated bond can be cited. It is preferably a (meth)acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dixin Pentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, etc.

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

The content of the polymerizable compound (C) relative to the total solid content is preferably 3% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, and still more preferably 11% by mass to 40% by mass.

＜Polymerization initiator (D)＞

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and conventional polymerization initiators can be used. As a polymerization initiator that generates living radicals, for example, N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N -Benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylhydro) Thiophenyl)-3-cyclopentylpropane-1-one-2-imine, 2-methyl-2-morpholinyl-1-(4-methylhydrosulfanylphenyl)propane-1 -Ketone, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4-bis( Trichloromethyl)-6-sunflower-1,3,5-triazine, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,2'-bis(2-chloro Phenyl) -4,4',5,5'-tetraphenylbiimidazole and the like.

The polymerization initiator preferably includes polymerization of at least one selected from the group consisting of a triazine compound, an phosphine oxide compound, a phenalkyl ketone compound, an O-acyl oxime compound, and a biimidazole compound. The initiator is more preferably a polymerization initiator containing an O-acetoxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and polymerizable compound (C) . If the content of the polymerization initiator (D) is within the aforementioned range, the sensitivity tends to be increased and the exposure time is shortened, so the productivity of the color filter is improved.

With respect to the total amount of the polymerization initiator (D), the content of the O-acetoxime compound is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95 Above mass%. If the content of the O-acetoxime compound is within the aforementioned range, there is a tendency to produce a high-brightness color filter even when the sensitivity or developability at the time of forming a colored pattern and the content of the coloring agent are high. .

The red curable resin composition of the present invention may also contain a polymerization initiation assistant.

＜Polymerization initiator (D1)＞

The polymerization initiator (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound that starts polymerization by a polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

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

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

The red curable resin composition of the present invention preferably contains a solvent.

＜Solvent (E)＞

The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. Examples include: ester solvents (solvents containing -COO- and not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (containing-in the molecule) COO- and -O- solvents), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (containing OH in the molecule and not containing -O-, -CO- and -COO- Solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc.

As the solvent, one can cite: Ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetylacetate, cyclohexanol acetate and Ester solvents such as γ-butyrolactone; Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and other ether solvents; Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethyl Ether ester solvents such as glycol monoethyl ether acetate; Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone and cyclohexanone; Alcohol solvents such as butanol, cyclohexanol and propylene glycol; Aromatic hydrocarbon solvents such as toluene and xylene; Amine solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

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

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

＜Other ingredients＞

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

＜Manufacturing method of red curable resin composition＞

The red curable resin composition of the present invention can be prepared by mixing colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E) and other components as needed And preparation.

＜Manufacturing method of color filter＞

As a method of producing a colored pattern from the red curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. can be cited. Among them, photolithography is preferred. In the photolithography method, a colored coating film that is a hardened product of the colored resin composition layer can be formed by not using a photomask during exposure and/or not performing development. The colored pattern or colored coating film thus formed is the color filter of the present invention.

According to the red curable resin composition of the present invention, a dark color (high chroma) and thin film color filter can be produced. The color filter can be useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL (electroluminescence, electroluminescence) devices, electronic paper, etc.) and solid-state imaging devices.

[Example]

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

[Synthesis Example 1]

(Synthesis of dicyanoethylene derivatives)

The compound represented by the formula (x) and the compound represented by the formula (y) were respectively obtained by the synthesis method described in Japanese Patent No. 3961078. [化11]

(Synthesis of diimino isopyrrole derivatives)

It is performed in the same manner as the synthesis method described in Japanese Patent Application Laid-Open No. 02-000665, and the compound represented by the formula (z) is obtained from the compound represented by the formula (x). [化12]

(Synthesis of porphyrazine compounds)

The compound represented by the formula (a-1) is obtained from the compound represented by the formula (x) by the synthesis method described in Japanese Patent No. 3961078. [化13]

Furthermore, the compound represented by the formula (a-1) means the compound represented by the formula (a-1-1) to the formula (a-1-4), and the products obtained by the above-mentioned synthesis method are these A mixture of structural isomers. [化14]

[Synthesis Example 2]

Put the compound represented by formula (x) (4.6 g), pentanol (20 ml), and diazabicycloundecene (4.6 g) into a reactor equipped with a cooling tube, a thermometer, and a stirrer. Add zinc chloride (0.82 g) at 120°C. After stirring for 4 hours, it was discharged into a methanol-water mixed liquid and the precipitated solid was separated by filtration to obtain 1.1 g of the compound represented by the formula (a-2). [化15]

[Synthesis Example 3]

Except for changing the zinc chloride in the synthesis of the compound represented by the formula (a-2) (Synthesis Example 2) to nickel chloride, the same procedure was performed to obtain 0.7 g of the compound represented by the formula (a-3) . [化16]

[Synthesis Example 4]

Except that the zinc chloride in the synthesis of the compound represented by the formula (a-2) (Synthesis Example 2) was changed to palladium chloride, the same procedure was performed to obtain 0.6 g of the compound represented by the formula (a-4) . [化17]

[Synthesis Example 5] Except that the compound represented by the formula (x) in the synthesis of the compound represented by the formula (a-2) (synthesis example 2) was changed to the compound represented by the formula (y), and the chlorine Except for changing the zinc chloride to vanadium (III) chloride, the same procedure was performed to obtain 1.5 g of the compound represented by the formula (a-5). [化18]

[Synthesis Example 6]

The compound represented by formula (S-1) is obtained by the synthesis method described in Japanese Patent Application Laid-Open No. 2016-27075. [化19]

[Synthesis Example 7]

A suitable amount of nitrogen was circulated in a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere. 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85°C while stirring. Then, the following mixed solution was added dropwise over 5 hours: 38 parts of acrylic acid, acrylic acid-3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] dec-8-yl ester and acrylic acid-3,4-epoxy tricyclo [5.2.1.0 2,6] 25 parts of cyclo[5.2.1.0 ^2,6 ]dec-9-yl ester mixture (content ratio 1:1), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, propylene glycol 338 parts of monomethyl ether acetate. On the other hand, a mixed solution obtained by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropping, keep it at this temperature for 4 hours, then cool to room temperature, and obtain a type B viscosity (23°C) of 23 mPa. Second (mPa·s), 25.6% solid content copolymer (resin (B-1)) solution. The resulting copolymer has a weight average molecular weight Mw of 8000, a solid acid value of 111 mg-KOH/g, and a dispersion degree of 2.1. The resin (B-1) has the following structural unit. [化20]

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin in terms of polystyrene is carried out under the following conditions using GPC (Gel Permeation Chromatography). Device: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: THF (tetrahydrofuran, tetrahydrofuran) Flow rate: 1.0 ml/min (mL/min) Detected liquid solid content concentration: 0.001% to 0.01% by mass Injection volume: 50 microliters (μL) Detector: RI Standard materials for calibration: TSK STANDARD POLYSTYRENE (standard polystyrene) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

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

＜Production of colored resin composition＞

〔Production of Dispersion 1〕

13 parts of CI Pigment Red 177 (pigment), 3.3 parts of acrylic pigment dispersant (in terms of solid content), resin as resin (B-1) (in terms of solid content) 5.2 parts, and 76 parts of propylene glycol monomethyl ether acetate , 3.0 parts of ethyl lactate were mixed, and the pigment was sufficiently dispersed using a bead mill to prepare a dispersion liquid 1.

〔Production of Dispersion 2〕

14 parts of CI Pigment Red 254 (pigment), 4.9 parts of acrylic pigment dispersant (in terms of solid content), resin as resin (B-1) (in terms of solid content) 4.2 parts, and 74 parts of propylene glycol monomethyl ether acetate , 2.5 parts of ethyl lactate are mixed, and the pigment is fully dispersed using a bead mill to prepare a dispersion liquid 2.

〔Production of Dispersion 3〕

12 parts of CI Pigment Yellow 139 (pigment), 4.2 parts of acrylic pigment dispersant (in terms of solid content), 4.2 parts of resin as resin (B-1) (in terms of solid content), and 77 parts of propylene glycol monomethyl ether acetate , 2.4 parts of ethyl lactate were mixed, and the pigment was sufficiently dispersed using a bead mill to prepare a dispersion liquid 3.

〔Production of Dispersion 4〕

5 parts of CI Pigment Yellow 185 (pigment), 3.5 parts of acrylic pigment dispersant (in terms of solid content), 3.5 parts of resin (B-1) (in terms of solid content), and 86 parts of propylene glycol monomethyl ether acetate , 2.0 parts of ethyl lactate were mixed, and the pigment was sufficiently dispersed using a bead mill to prepare dispersion 4.

＜Production of red curable resin composition＞

[Example 1]

The red curable resin composition is obtained by mixing the following components. Porphyrazine: 17 parts of compound represented by formula (a-1) Red pigment: 1,435 parts of dispersion Yellow pigment: 3 309 parts of dispersion Resin (B): Resin (B-1) (calculated as solid content) 29 parts Polymerizable compound (C): 35 parts of dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Manufactured by the company; O-acetoxime compound) 7.0 parts Solvent (E): 510 parts of propylene glycol monomethyl ether acetate 17 parts of ethyl lactate Leveling agent: polyether modified silicone oil (conversion of solid content) (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.10 parts

[Example 2]

Except having used the compound represented by formula (a-2) instead of the compound represented by formula (a-1), it carried out similarly to Example 1, and obtained the red curable resin composition.

[Example 3]

Except having used the compound represented by formula (a-3) instead of the compound represented by formula (a-1), it carried out similarly to Example 1, and obtained the red curable resin composition.

[Example 4]

Except having used the compound represented by formula (a-4) instead of the compound represented by formula (a-1), it carried out similarly to Example 1, and obtained the red curable resin composition.

[Example 5]

Except having used the compound represented by formula (a-5) instead of the compound represented by formula (a-1), it carried out similarly to Example 1, and obtained the red curable resin composition.

[Example 6]

The red curable resin composition is obtained by mixing the following components. Porphyrazine: 11 parts of compound represented by formula (a-1) Red dye: 16 parts of compound represented by formula (S-1) Red pigment: 1,293 parts of dispersion Yellow pigment: 3,357 parts of dispersion Resin (B): Resin (B-1) (in terms of solid content) 35 parts Polymerizable compound (C): 35 parts of dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Manufactured by the company; O-acetoxime compound) 7.0 parts Solvent (E): 251 parts of propylene glycol monomethyl ether acetate Diacetone alcohol 308 parts 20 parts of ethyl lactate Leveling agent: polyether modified silicone oil (conversion of solid content) (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.10 parts

[Example 7]

The red curable resin composition is obtained by mixing the following components. Porphyrazine: 17 parts of compound represented by formula (a-1) Red pigment: 1,354 parts of dispersion Red pigment: 2 80 parts of dispersion Yellow pigment: 3 312 parts of dispersion Resin (B): Resin (B-1) (calculated as solid content) 30 parts Polymerizable compound (C): 35 parts of dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Manufactured by the company; O-acetoxime compound) 7.0 parts Solvent (E): 521 parts of propylene glycol monomethyl ether acetate 25 parts of ethyl lactate Leveling agent: polyether modified silicone oil (conversion of solid content) (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.10 parts

[Example 8]

The red curable resin composition is obtained by mixing the following components. Porphyrazine: 19 parts of compound represented by formula (a-1) Red pigment: 1,496 parts of dispersion Yellow pigment: 4,854 parts of dispersion Resin (B): Resin (B-1) (calculated as solid content) 9 parts Polymerizable compound (C): 35 parts of dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Manufactured by the company; O-acetoxime compound) 7.0 parts Solvent (E): 124 parts of propylene glycol monomethyl ether acetate 5 parts of ethyl lactate Leveling agent: polyether modified silicone oil (conversion of solid content) (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.10 parts

[Comparative Example 1]

The red curable resin composition is obtained by mixing the following components. Red pigment: 1,859 parts of dispersion Resin (B): Resin (B-1) (calculated as solid content) 20 parts Polymerizable compound (C): 35 parts of dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Manufactured by the company; O-acetoxime compound) 7.0 parts Solvent (E): 435 parts of propylene glycol monomethyl ether acetate 12 parts of ethyl lactate Leveling agent: polyether modified silicone oil (conversion of solid content) (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.10 parts

＜Production of color filter＞

On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated), the red curable resin composition was applied by spin coating, and then pre-baked at 100°C for 3 minutes to form a colored resin composition layer. After being left to cool, use an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) to irradiate light with an exposure amount of ^{60 millijoules/cm² (mJ/cm 2) (365nm standard) in an atmospheric atmosphere.} Thereafter, in an oven, post-baking was performed at 230°C for 20 minutes to obtain a color filter.

＜Measurement of film thickness＞

Regarding the obtained color filter, a film thickness measuring device (DEKTAK 3; manufactured by Nippon Vacuum Technology Co., Ltd.) was used to measure the film thickness. The results are shown in Table 1.

＜Chromaticity evaluation＞

Regarding the obtained color filter, a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) was used to measure the spectroscopy, and the characteristic function of the C light source was measured in CIE (International Commission on Illumination, International Commission on Illumination). Illumination Committee) xy chromaticity coordinates (x, y) in the 1931 color system. The results are shown in Table 1. When comparing with the same x, the thinner the film thickness, the more it can be said to be a dark color (high chroma) and thin film color filter.

[Table 1]

When x becomes 0.688, it is a dark (high chroma) red area. The color filter formed from the red curable resin composition of the present invention has a film thickness of 3 microns or less, which can be said to be a dark color (high chroma) and thin film color filter. On the other hand, although the color filter formed of the red curable resin composition of the comparative example can reproduce dark (high chroma) red, it cannot achieve thinning.

none

none

none.

Claims (3)

A red curable resin composition comprising: based on the total solid content of the red curable resin composition, 5 to 60% by mass of coloring agent (A), and 10 to 70% by mass of alkali-soluble resin (B), and 3% to 60% by mass of the polymerizable compound (C); and polymerization initiator (D), wherein the total amount of the alkali-soluble resin (B) and the polymerizable compound (C) is 100 mass The content of the polymerization initiator (D) is 0.1 to 30 parts by mass, wherein the colorant contains a tetraazaporphyrin (tetraazaporphyrin) compound and a red pigment, and when it is formed from the red curable resin composition When the color filter is measured by the characteristic function of C light source in CIE 1931, x=0.688, 0.298

y

0.310, and the film thickness of the color filter is 3 microns or less. A color filter which is formed of the red curable resin composition as described in claim 1. A display device comprising the color filter according to claim 2.