KR20210114872A - Colored curable resin composition - Google Patents

Abstract

The objective of the present invention is to provide a colored curable resin composition which is capable of suppressing a decrease of maximum absorption in a visible light region even in a film deposition process such as an exposure step and a post exposure bake step. To this end, the present invention provides a colored curable resin composition comprising: a colorant; a resin; a polymerizable compound; a polymerization initiator; and an antioxidant, wherein the colorant includes a squarylium dye having maximum absorption in the visible light region, and the antioxidant includes a phenolic antioxidant.

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

The color filter used for display apparatuses, such as a liquid crystal display device, an electroluminescent display device, and a plasma display, and solid-state imaging elements, such as a CCD and CMOS sensor, is manufactured from a colored curable resin composition. As a coloring agent used for such colored curable resin composition, squarylium dye is known (patent documents 1, 2 etc.).

Japanese Patent Laid-Open No. 2015-86379 Japanese Patent Laid-Open No. 2015-86380

However, in the said colored curable resin composition containing squarylium dye, when post-baking was performed after exposure, the maximum absorption in a visible region may fall. Then, this invention makes it a subject to provide the colored curable resin composition which can suppress the fall of the maximum absorption in a visible region also in film-forming processes, such as an exposure process and a post-baking process.

The gist of the present invention is as follows.

[1] a colorant, a resin, a polymerizable compound, a polymerization initiator, and an antioxidant,

The colorant includes a squarylium dye having a maximum absorption in the visible region,

The colored curable resin composition in which the said antioxidant contains a phenolic antioxidant.

[2] The colored curable resin composition according to [1], wherein the phenolic antioxidant is a compound having no vinyl group and no ethene-1,1-diyl group.

[3] The phenolic antioxidant is a compound in which a tertiary alkyl group is bonded to one carbon atom among two ortho positions of the phenolic hydroxyl group and a hydrogen atom or an alkyl group is bonded to the other carbon atom [1] or The colored curable resin composition according to [2].

[4] In the phenolic antioxidant, a tertiary alkyl group is bonded to one carbon atom among two ortho positions of the phenolic hydroxyl group, and a hydrogen atom, a methyl group, or a primary alkyl group is bonded to the other carbon atom The colored curable resin composition according to any one of [1] to [3], which is a compound.

[5] The colored curable resin composition according to any one of [1] to [4], wherein the mass ratio of the antioxidant and the squarylium dye (antioxidant/squarylium dye) is 0.8 or more.

[6] The colored curable resin composition according to any one of [1] to [5], wherein the squarylium dye is a compound represented by formula (AI).

[Formula 1]

[In Formula (AI),

R ¹ to ^{R 4} each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.

R ⁵ to ^{R 8} each independently represent a hydrogen atom or a hydroxyl group.

Ar ¹ and Ar ² each independently represent a group represented by formula (i).

[Formula 2]

[In formula (i),

R ¹² represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxy group, or a carboxy group, and m is an integer of 0 to 5 indicates The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, some R ¹² may be the same or different, respectively. * indicates a bond with a nitrogen atom.]

R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by formula (i). The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.]

[7] The colored curable resin composition according to any one of [1] to [6], wherein the squarylium dye is a compound represented by formula (AII).

[Formula 3]

[In formula (AII),

R ¹ to ^{R 4} each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.

R ⁵ to ^{R 8} each independently represent a hydrogen atom or a hydroxyl group.

Ar ¹ and Ar ² each independently represent a group represented by formula (i).

[Formula 4]

[In formula (i),

R ¹² represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxy group, or a carboxy group, and m is an integer of 0 to 5 indicates The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, some R ¹² may be the same or different, respectively. * indicates a bond with a nitrogen atom.]

R ¹³ and R ¹⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group or a carboxy group, and the methylene group constituting the monovalent saturated hydrocarbon group is substituted with -O- or -S- There may be.]

[8] A color filter formed from the colored curable resin composition according to any one of [1] to [7].

[9] A display device comprising the color filter according to [8].

ADVANTAGE OF THE INVENTION According to this invention, also in a film-forming process, the fall of the maximum absorption in a visible region can be provided the colored curable resin composition which can suppress.

<Colored Curable Resin Composition>

The colored curable resin composition of the present invention includes a coloring agent (hereinafter, sometimes referred to as a coloring agent (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, a polymerizable compound (C)). ), a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)), and an antioxidant (hereinafter sometimes referred to as an antioxidant (E)), including the colorant (A ) contains a squarylium dye having a maximum absorption in the visible region, and the antioxidant (E) contains a phenolic antioxidant. In addition, in this specification, the compound illustrated as each component can be used individually or in combination of multiple types, unless otherwise indicated.

<Colorant (A)>

The colorant (A) contains a squarylium dye having a maximum absorption in the visible region. In addition, the visible region here refers to the wavelength region of 380 nm or more and 780 nm or less. The squarylium dye is preferably a compound having a maximum absorption at 390 nm or more (preferably 400 nm or more) and less than 700 nm (preferably 650 nm or less).

As said squarylium dye, if it is a compound which has maximum absorption in a visible region, it will not specifically limit, A well-known squarylium dye can be used, It is preferable that it is a compound represented by Formula (AI).

[Formula 5]

[In Formula (AI),

R ¹ to ^{R 4} each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.

R ⁵ to ^{R 8} each independently represent a hydrogen atom or a hydroxyl group.

Ar ¹ and Ar ² each independently represent a group represented by formula (i).

[Formula 6]

[In formula (i),

R ¹² represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxy group, or a carboxy group, and m is an integer of 0 to 5 indicates The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, some R ¹² may be the same or different, respectively. * indicates a bond with a nitrogen atom.]

R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by formula (i). The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.]

Examples of the halogen atom represented by R ^{1 to R 4} include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to ^{R 4} , R ⁹ , R ¹⁰ , and R ¹² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a linear alkyl group having 1 to 20 carbon atoms, such as a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group and an icosyl group; branched alkyl groups having 3 to 20 carbon atoms, such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group and an adamantyl group.

As a substituent of such a saturated hydrocarbon group, Halogen atoms, such as a fluorine atom, a chlorine atom, and an iodine atom; hydroxyl group; carboxyl group; -NR ^a R ^b (R ^a and R ^b are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); nitro group; an alkoxycarbonyl group having 1 to 10 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group; etc. are mentioned, As a C1-C20 monovalent|monohydric saturated hydrocarbon group which has a substituent, the group represented by a following formula is mentioned, for example. In the following formula, * represents a bond.

[Formula 7]

As a group in which the methylene group which comprises such a saturated hydrocarbon group is substituted by -O- or -S-, the group represented by the following formula is mentioned, for example. In the following formula, * represents a bond.

[Formula 8]

Examples of the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms for R ¹² include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group. can

As a substituent of the said unsaturated hydrocarbon group, Halogen atoms, such as a fluorine atom, a chlorine atom, and an iodine atom; hydroxyl group; carboxyl group; -NR ^c R ^d (R ^c and R ^d are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); nitro group; C1-C10 alkoxy groups, such as a methoxy group and an ethoxy group; an alkoxycarbonyl group having 1 to 10 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group; and the like.

As R ¹ to ^{R 4} , a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms is preferable, a hydrogen atom, a hydroxyl group or a methyl group is more preferable, and a hydrogen atom is still more preferable.

Examples of R ⁵ ~R ^8, of at least one dog and a hydroxy group is preferable and, R ⁵ and R ⁶ is a hydroxy group of at least one, and more preferably R ⁷ and R ⁸ is a hydroxy group of at least one, R ⁵ and R ⁶ which it is either a hydroxy group, that the R ⁷ and R ⁸ either is a hydroxy group of more preferred.

R ⁹ and R ¹⁰ are preferably a linear alkyl group having 1 to 20 carbon atoms which may have a substituent or a branched chain alkyl group having 3 to 20 carbon atoms which may have a substituent, and a straight chain alkyl group having 1 to 10 carbon atoms which may have a substituent. A chain alkyl group or a branched alkyl group having 3 to 10 carbon atoms which may have a substituent is more preferable, a linear alkyl group having 1 to 5 carbon atoms having a hydroxy group at the terminal, and a straight chain alkyl group having 1 to 5 carbon atoms having a carboxy group at the terminal , or a branched-chain alkyl group having 3 to 10 carbon atoms is more preferable.

As R ¹² , a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is preferable, and a linear alkyl group having 1 to 5 carbon atoms which may have a substituent is more preferable.

m becomes like this. Preferably it is 1-5, More preferably, it is 1-3.

Ar ¹ and Ar ² are preferably groups represented by formula (ii).

[Formula 9]

[In formula (ii),

R ¹⁵ represents a hydroxyl group, a carboxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group or a carboxy group, and p represents an integer of 0 to 5; The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When p is 2 or more, some R<^15> may be same or different, respectively.

R ¹⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, and q represents an integer of 0 to 5; However, p+q represents the integer of 0-5. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When q is 2 or more, a plurality of R ¹⁶ may be the same or different, respectively.

* indicates a bond with a nitrogen atom.]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁵ include those exemplified as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms described above. Especially, a C1-C20 linear alkyl group is preferable, a C1-C10 linear alkyl group is more preferable, A C1-C5 linear alkyl group is still more preferable.

The hydroxyl group or carboxy group included in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably bonded to the molecular chain terminal of the saturated hydrocarbon group.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxy group or a carboxy group include a group represented by the following formula. In the following formula, * represents a bond.

[Formula 10]

R ¹⁵ is preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group. Further, it is preferable that at least one of the methylene groups constituting the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by ^{R 15 is substituted with -O-.} Examples of the group in which at least one of the methylene groups constituting the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{15 are substituted with -O- include groups represented by the following formula.} In the following formula, * represents a bond.

[Formula 11]

As the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent represented by ^{R 16 , the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent described above is} Examples of the monovalent saturated hydrocarbon group of 20 and the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent may be mentioned. Especially, a C1-C20 monovalent saturated hydrocarbon group which may have a substituent is preferable, a C1-C5 linear alkyl group which may have a substituent is more preferable, A C1-C3 linear alkyl group is still more preferable. and a methyl group is particularly preferred.

It is preferable that p is an integer of 0-3, More preferably, it is an integer of 0-1, Especially preferably, it is 1.

It is preferable that q is an integer of 1-3, More preferably, it is an integer of 1-2.

Among the compounds represented by the formula (AI), the compound represented by the formula (AII) is more preferable. When the said squarylium dye is a compound represented by Formula (AII), the fall of the maximum absorption in a film-forming process can be suppressed more, Furthermore, the color change in a film-forming process can also be suppressed more.

[Formula 12]

[In formula (AII),

R ¹ to ^{R 8} , Ar ¹ and Ar ² are the same as described above.

R ¹³ and R ¹⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group or a carboxy group, and the methylene group constituting the monovalent saturated hydrocarbon group is substituted with -O- or -S- There may be.]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹³ and R ¹⁴ include those exemplified as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms described above. Especially, a C1-C20 linear alkyl group is preferable, a C1-C10 linear alkyl group is more preferable, A C1-C5 linear alkyl group is still more preferable.

The hydroxyl group or carboxy group included in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably bonded to the molecular chain terminal of the saturated hydrocarbon group.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxy group or a carboxy group include a group represented by the following formula. In the following formula, * represents a bond.

[Formula 13]

^{Preferred embodiments of R 1} to ^{R 8} , Ar ¹ and Ar ^{2 in} the formula (AII) are the same as described above.

As the compound represented by the formula (AI), for example, the compounds represented by the formulas (AI-1) to (AI-60) shown in Tables 1-2 can be exemplified, and among them, the availability of raw materials From the viewpoint, compounds represented by formulas (AI-1) to (AI-20) are preferable.

As a compound represented by a formula (AI), it is more preferable that it is a compound represented by a formula (AI-1) - a formula (AI-5), a formula (AI-11) - a formula (AI-20),

It is more preferable that it is a compound represented by a formula (AI-11) - a formula (AI-20),

It is more preferable that it is a compound represented by a formula (AI-11) - a formula (AI-15).

In Tables 1-2, x-1 to x-4 represent a group represented by the following formula (* means a bond).

[Formula 14]

In Tables 1-2, y-1 to y-5 represent a group represented by the following formula (* means a bond).

[Formula 15]

The compound represented by the formula (AI) can be produced by, for example, reacting the compound represented by the formula (pt1), the compound represented by the formula (pt2), and the compound represented by the formula (pt3) . In this reaction, the total amount of the compound represented by the formula (pt1) and the compound represented by the formula (pt2) is preferably 1.5 to 2.5 mol with respect to 1 mol of the compound represented by the formula (pt3).

[Formula 16]

In the formula, R ¹ to ^{R 10} , Ar ¹ and Ar ² each have the same meanings as described above.

30 degreeC - 180 degreeC are preferable and, as for reaction temperature, 80 degreeC - 140 degreeC are more preferable. 1 hour - 12 hours are preferable and, as for reaction time, 3 hours - 8 hours are more preferable.

It is preferable to perform reaction in an organic solvent from the point of a yield. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitro hydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone; etc. are mentioned, You may mix and use these. Among them, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 30 parts by mass to 1 part by mass in total of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). It is more than part and 150 mass parts or less.

The method for extracting the compound represented by Formula (AI) which is the target compound from the reaction mixture is not specifically limited, A well-known various method can be used. For example, a method in which a solvent is distilled off from a reaction solution to obtain a target product, or a method in which a crystal is cooled after completion of the reaction and the precipitated crystals are obtained by filtration. The crystals obtained by filtration are preferably washed with water or the like and then dried. Moreover, you may further refine|purify by well-known methods, such as column chromatography and recrystallization, as needed.

The content rate of the said squarylium dye in a coloring agent (A) becomes like this. Preferably it is 50 mass % or more, More preferably, it is 70 mass % or more, More preferably, it is 80 mass % or more, Especially preferably, it is 90 mass % or more. and 95 mass % or more may be sufficient, and 100 mass % may be sufficient.

The coloring agent (A) may contain the coloring agent different from the said squarylium dye other than the said squarylium dye, When the coloring agent different from the said squarylium dye is dye (henceforth dye (A1)) may be any of) and a pigment (hereinafter sometimes referred to as a pigment (A2)). The coloring agent different from the said squarylium dye may contain one or both of these dyes (A1) and a pigment (A2).

As long as the said squarylium dye is not included, a dye (A1) is not specifically limited, A well-known dye can be used, A solvent dye, an acid dye, a direct dye, a mordant dye, etc. are mentioned. As the dye, for example, a compound classified as having a color other than a pigment in the color index (published by The Society of Dyers and Colorists) and a known dye described in a dyeing note (Skisensha) can be mentioned. . In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, acridine dyes, and styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferable.

Specifically, C.I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162 , 163, 167, 189;

C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;

C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. C.I. solvent dyes,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C.I. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, CIs of 104, 105, 106, 109, etc. acid dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C.I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. direct dye,

C.I. Disperse Yellow 51, 54, 76;

C.I. Disperse Violet 26, 27;

C.I. Disperse Blue 1, 14, 56, 60, etc. C.I. dispers dye,

C.I. Basic Red 1, 10;

C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;

C.I. Basic Violet 2;

C.I. Basic Red 9;

C.I. Basic Green 1, etc. C.I. basic dye,

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. Reactive Red 36 and other C.I. reactive dyes,

C.I. modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

C.I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;

C.I. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc. C.I. modern dye,

C.I. Bat Green 1, etc. C.I. Vat dye etc. are mentioned.

What is necessary is just to select such a dye suitably according to the spectral spectrum of a desired color filter.

It does not specifically limit as a pigment (A2), A well-known pigment can be used, For example, the pigment classified into the pigment by the color index (The Society of Dyers and Colorists publication) is mentioned.

As the pigment, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194, 214 yellow pigments;

C.I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 red pigment ;

C.I. Blue pigments, such as pigment blue 15:6 and 60;

C.I. Violet pigments, such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments, such as Pigment Green 7, 36, and 58;

C.I. Brown pigments, such as Pigment Brown 23 and 25;

C.I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

If necessary, the pigment may be subjected to rosin treatment, surface treatment using a pigment derivative introduced with acidic or basic groups, etc., graft treatment to the pigment surface with a high molecular compound, etc., atomization treatment by sulfuric acid atomization method, etc., or to remove impurities For example, a washing treatment with an organic solvent, water, or the like, a removal treatment with an ion exchange method for ionic impurities, or the like may be performed.

It is preferable that a pigment has a uniform particle size. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was uniformly disperse|distributed in the solution can be obtained.

As said pigment dispersant, surfactant, such as a cationic type, an anionic type, a nonionic type, amphoteric type, a polyester type, a polyamine type, an acrylic type, is mentioned, for example. These pigment dispersants may be used individually or in combination of 2 or more type. As the pigment dispersant, as a trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Lubrizol), EFKA (manufactured by CIBA), Azispa (Ajinomoto Fine) Techno Co., Ltd. product), Disperbyk (made by Big Chemie), etc. are mentioned.

When using a pigment dispersant, the usage-amount becomes like this with respect to the total amount of a pigment (A2). Preferably they are 1 mass % or more and 100 mass % or less, More preferably, they are 5 mass % or more and 50 mass % or less. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

With respect to the total amount of solid content, the content rate of the coloring agent (A) in colored curable resin composition becomes like this. Preferably it is 0.1 mass % or more and 70 mass % or less, More preferably, they are 0.5 mass % or more and 60 mass % or less, More preferably Preferably, it is 1 mass % or more and 50 mass % or less. When the content rate of the coloring agent (A) is within the above range, the color density when a color filter is used is sufficient, and the resin (B) and the polymerizable compound (C) can be contained in the required amount in the composition, so that the mechanical strength is sufficient. pattern can be formed.

Here, the "total amount of solid content" in this specification means the quantity which removed content of the solvent from the total amount of colored curable resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

<Resin (B)>

Although resin (B) is not specifically limited, It is preferable that it is alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

resin [K1]; A structural unit derived from at least one (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and a cyclic having 2 to 4 carbon atoms a copolymer having a structural unit derived from a monomer (b) having an ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);

resin [K2]; A structural unit derived from (a), a structural unit derived from (b), and a monomer copolymerizable with (a) (c) (however, different from (a) and (b)) (hereinafter “(c)” copolymers having a structural unit derived from );

resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c);

resin [K4]; a copolymer having a structural unit derived from (c) and a structural unit obtained by adding (b) to the structural unit derived from (a);

resin [K5]; a copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to the structural unit derived from (b);

resin [K6]; A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to the structural unit derived from (b) and further adding carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic 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-Carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxy group, such as [2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

Unsaturated mono[(meth)acryloyloxyalkyl] of polyhydric carboxylic acids with divalence or higher, such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] esters;

unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid; and the like.

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

(b) has, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond polymerizable compound. As for (b), the monomer which has a C2-C4 cyclic ether and a (meth)acryloyloxy group is preferable.

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”).

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)"), alicyclic unsaturated and monomers (b1-2) having a structure in which hydrocarbons are epoxidized (hereinafter sometimes referred to as “(b1-2)”).

As (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl 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-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxy) methyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc. are mentioned. can

As (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Seroxide 2000; Daicel Co., Ltd. product), 3,4-epoxycyclohexylmethyl (meta) ) acrylate (eg, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cyclomer M100; manufactured by Daicel Corporation), formula ( The compound represented by I), the compound represented by Formula (II), etc. are mentioned.

[Formula 17]

[In formulas (I) and (II),

R ^a and R ^b 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 with a hydroxy group.

X ^a and X ^b represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S-, or *-R ^c -NH-.

R ^c represents a C1-C6 alkanediyl group.

* indicates a bond with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, and 1-hydroxy group. and a hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.

R ^a and R ^b preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1 group. ,6-diyl group, etc. are mentioned.

As X ^a and X ^b , Preferably, a single bond, a methylene group, an ethylene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O- are mentioned, More preferably, a single bond, *- CH ₂ CH ₂ -O- (* indicates a bond with O).

As a compound represented by Formula (I), the compound etc. which are represented by any one of Formula (I-1) - Formula (I-15) are mentioned. Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) ) is preferable, and the compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferable.

[Formula 18]

[Formula 19]

As a compound represented by Formula (II), the compound etc. which are represented by any one of Formula (II-1) - Formula (II-15) are mentioned. Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) ) is preferable, and the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15) is more preferable.

[Formula 20]

[Formula 21]

The compound represented by Formula (I) and the compound represented by Formula (II) may be used individually, respectively, or may use 2 or more types together. When the compound represented by the formula (I) and the compound represented by the formula (II) are used together, their content ratio [the compound represented by the formula (I): the compound represented by the formula (II)] is on a molar basis, Preferably it is 5:95-95:5, More preferably, it is 20:80-80:20.

As (b2), the monomer which has an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. are mentioned.

As (b3), the monomer which has a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), it is preferable that it is (b1) from the point which can improve reliability, such as heat resistance of the color filter obtained, chemical-resistance, etc. more. Moreover, (b1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

As (c), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclo Hexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the technical field, it is called "dicyclofentanyl (meth) acrylate" as a common name. , "tricyclodecyl (meth) acrylate" in some cases), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the technical field, as a common name, "dicyclophene" tenyl (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propar (meth)acrylic acid esters, such as gil (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexylox bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutylate, N-succinimidyl dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Of these, from the viewpoint of copolymerization reactivity and heat resistance, 2-hydroxyethyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo[2.2] .1]hept-2-ene and the like are preferred.

In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1],

a structural unit derived from (a); 2-60 mol%

a structural unit derived from (b); It is preferable that it is 40-98 mol%,

a structural unit derived from (a); 10-50 mol%

a structural unit derived from (b); It is more preferable that it is 50-90 mol%.

When the ratio of the structural unit of resin [K1] exists in the said range, there exists a tendency excellent in the storage stability of a colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance of the color filter obtained.

Resin [K1] is, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing House, Chemical Dongin, 1st Edition, 1st Edition, March 1, 1972) and citations described in the document It can be prepared by referring to the literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are put in a reaction vessel, for example, by replacing oxygen with nitrogen, a deoxidized atmosphere is created, and heating and keeping warm while stirring how to do it In addition, the polymerization initiator, a solvent, etc. used here are not specifically limited, What is normally used in the said field|area can be used. For example, as the polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) ) is mentioned, what is necessary is just to melt|dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (F) of the colored curable resin composition of this invention are mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as solid (powder) by methods, such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention, so the colored curable resin of the present invention The manufacturing process of the composition can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the total structural units constituting the resin [K2],

a structural unit derived from (a); 2-45 mol%

a structural unit derived from (b); 2-95 mol%

a structural unit derived from (c); It is preferable that it is 1-65 mol%,

a structural unit derived from (a); 5-40 mol%

a structural unit derived from (b); 5-80 mol%

a structural unit derived from (c); It is more preferable that it is 5-60 mol%.

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter are excellent. tends to

The resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

In the resin [K3], the ratio of the structural units derived from each of the total structural units constituting the resin [K3],

a structural unit derived from (a); 2-60 mol%

a structural unit derived from (c); It is preferable that it is 40-98 mol%,

a structural unit derived from (a); 10-50 mol%

a structural unit derived from (c); It is more preferable that it is 50-90 mol%.

The resin [K3] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

Resin [K4] can be prepared by obtaining the copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid and/or carboxylic acid anhydride of (a). can

First, the copolymer of (a) and (c) is produced in the same manner as described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as that given in the resin [K3].

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the said copolymer.

Continuing with the preparation of the copolymer of (a) and (c), the atmosphere in the flask is substituted from nitrogen to air, and (b), a reaction catalyst between carboxylic acid or carboxylic acid anhydride and a cyclic ether (e.g., tris ( dimethylaminomethyl)phenol) and a polymerization inhibitor (such as hydroquinone) are placed in a flask and reacted at, for example, 60 to 130°C for 1 to 10 hours, whereby the resin [K4] can be produced. .

As for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of the storage stability of colored curable resin composition, developability at the time of forming a pattern, and solvent resistance, heat resistance, mechanical strength, and sensitivity of the pattern obtained to become favorable. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable and (b1-1) is more preferable as (b) used for resin [K4].

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c).

Reaction conditions, such as the preparation method, reaction temperature, and time, can be suitably adjusted in consideration of manufacturing equipment, the amount of heat generated by polymerization, and the like. In addition, similarly to polymerization conditions, the preparation method and reaction temperature can be adjusted suitably in consideration of manufacturing equipment, the calorific value by polymerization, etc.

The resin [K5] is the first step, in the same manner as in the above-described method for producing the resin [K1], to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer may use the solution after reaction as it is, may use a concentrated or diluted solution, or may use what was taken out as a solid (powder) by methods, such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer,

a structural unit derived from (b); 5-95 mol%

a structural unit derived from (c); It is preferable that it is 5-95 mol%,

a structural unit derived from (b); 10-90 mol%

a structural unit derived from (c); It is more preferable that it is 10-90 mol%.

Moreover, under the same conditions as the manufacturing method of resin [K4], the carboxylic acid or carboxylic acid anhydride of (a) is reacted with the cyclic ether derived from (b) which the copolymer of (b) and (c) has. By doing so, resin [K5] can be obtained.

As for the usage-amount of (a) made to react with said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, as (b) used for the resin [K5], (b1) is preferable, and (b1-1) is more preferable.

Resin [K6] is resin in which resin [K5] was further made to react with carboxylic acid anhydride. A hydroxy group generated by reaction of a cyclic ether with carboxylic acid or carboxylic acid anhydride is reacted with carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. are mentioned. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amounts of (a).

Specifically as the resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decylacrylate/( resin [K1] such as meth)acrylic acid copolymer; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2,6 ]decylacrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decylacrylate/(meth)acrylic acid/N- Resin [K2], such as a cyclohexylmaleimide/2-hydroxyethyl (meth)acrylate copolymer and 3-methyl-3- (meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer; resins [K3] such as benzyl (meth)acrylate/(meth)acrylic acid copolymer and styrene/(meth)acrylic acid copolymer; Resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) to tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer ) Resin to which acrylate was added, resin [K4], such as a resin which added glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer; Tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate copolymer with (meth)acrylic acid, tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate resin [K5] such as a resin obtained by reacting (meth)acrylic acid with a copolymer; and resin [K6] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting with tetrahydrophthalic anhydride. have.

Especially, as resin (B), resin [K1] and resin [K2] are preferable, and resin [K1] is especially preferable.

The weight average molecular weight of resin (B) in terms of polystyrene becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility in the developing solution of the unexposed portion is good, and the resolution of the colored pattern tends to be improved.

The degree of dispersion [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.

The acid value of resin (B) is preferably 30-170 mg-KOH/g in conversion of solid content, More preferably, it is 40-150 mg-KOH/g, More preferably, it is 50-135 mg-KOH/g. Here, an acid value is a value measured as the quantity (mg) of potassium hydroxide required in order to neutralize 1 g of resin (B), For example, it can obtain|require by titrating using potassium hydroxide aqueous solution.

To [ the content rate of resin (B) ] with respect to the total amount of solid content, Preferably it is 7-65 mass %, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %. When the content rate of resin (B) exists in said range, a coloring pattern can be formed and there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, preferably is a (meth)acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Pentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth) ) acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

Especially, dipentaerythritol penta (meth)acrylate and dipentaerythritol hexa (meth)acrylate are preferable.

It is preferable that the content rate of a polymeric compound (C) is 1-65 mass % with respect to the total amount of solid content, More preferably, it is 5-60 mass %, More preferably, it is 10-55 mass %. When the content rate of a polymeric compound (C) exists in said range, there exists a tendency for the residual-film rate at the time of coloring pattern formation and the chemical-resistance of a color filter to improve.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating an active radical, an acid, etc. under the action of light or heat, and a known polymerization initiator can be used. As a polymerization initiator which generate|occur|produces an active radical, an O-acyl oxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound are mentioned, for example.

Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanyl). Phenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-( O-acyl oxime compounds having a diphenyl sulfide skeleton such as 4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine; N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6- {2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2) O-acyloxime compounds having a carbazole skeleton such as -methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine; O-acyloxime compounds having a fluorene skeleton such as 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime; and the like. Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA), DFI-091 (manufactured by Daitokemix Co., Ltd.), PBG-327 (manufactured by Sangju Strong Electronic Materials Co., Ltd.) You may use commercial items, such as these. Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl) -3-Cyclohexylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclo) Fentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl] At least one selected from the group consisting of ethanone O-acetyloxime is preferable. If it is such an O-acyl oxime compound, there exists a tendency for the color filter of high brightness to be obtained.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl). )-2-Benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2 -Hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxy and oxycyclohexylphenyl ketone, an oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal. . You may use commercial items, such as Irgacure (trademark) 369, 907, 379 (above, BASF Corporation make).

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 -bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-) 2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro and romethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use commercial items, such as Irgacure (trademark) 819 (made by BASF).

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3). -dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'-bis (2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl ) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Application Publication Nos. 48-38403 and 62-174204), 4,4',5 and a biimidazole compound in which the phenyl group at the 5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.

Examples of the acid-generating polymerization initiator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p -Toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- Onium salts, such as toluenesulfonate and diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

Moreover, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoylbenzoate methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone , benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned.

The polymerization initiator (D) is preferably an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a polymerization initiator containing at least one selected from the group consisting of a biimidazole compound, O - The polymerization initiator containing an acyl oxime compound is more preferable.

To [ content of a polymerization initiator (D) / 100 mass parts of total amounts of resin (B) and a polymeric compound (C)), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. When content of a polymerization initiator (D) exists in said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, productivity of a color filter improves.

<Antioxidant (E)>

Antioxidant (E) contains a phenolic antioxidant. When the colored curable resin composition of this invention contains a phenolic antioxidant, the fall of the maximum absorption in a film-forming process can be suppressed.

As the phenolic antioxidant, a known phenolic antioxidant can be used, for example, Irganox (registered trademark) 1010:pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate] (manufactured by BASF Corporation), Irganox (registered trademark) 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (BASF Corporation) ) agent), Irganox (registered trademark) 1330:3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2, 4,6-triyl)tri-p-cresol (manufactured by BASF Corporation), Irganox (registered trademark) 3114:1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) )-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Corporation), Irganox (registered trademark) 3790:1,3,5-tris (( 4-tert-Butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (BASF Corporation) ), Irganox (registered trademark) 1035: thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Co., Ltd.), Irganox (registered trademark) ) 1135: Benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy C7-C9 branched alkyl ester (manufactured by BASF Co., Ltd.), Irganox (registered trademark) 1520L: 4,6-bis (Octylthiomethyl)-o-cresol (manufactured by BASF Corporation), Irganox (trademark) 3125 (manufactured by BASF Corporation), Irganox (registered trademark) 565:2,4-bis(n-octylthio)- 6-(4-hydroxy 3',5'-di-tert-butylanilino)-1,3,5-triazine (manufactured by BASF Co., Ltd.), Irganox (registered trademark) 1726:1,3,5 -tris[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxy]ethyl]hexahydro-1,3,5-triazine-2,4,6- Trion (manufactured by BASF Corporation), adecastab (registered trademark) AO-80:3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyl oxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxa Spiro[5.5]undecane (manufactured by ADEKA Co., Ltd.), adekastave (registered trademark) AO-20: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trion (manufactured by ADEKA Corporation), ADEKA STAB (registered trademark) AO-30:4,4',4' '-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol) (manufactured by ADEKA Corporation), ADEKA STAB (registered trademark) AO-40:6,6'- Di-tert-butyl-4,4'-butylidene di-m-cresol (manufactured by ADEKA Co., Ltd.), adekastave (registered trademark) AO-50: octadecyl 3-(3,5-di-tert- Butyl-4-hydroxyphenyl) propionate (manufactured by ADEKA Corporation), adekastave (registered trademark) AO-60: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4- Hydroxyphenyl) propionate] (manufactured by ADEKA Corporation), ADEKA STAB (registered trademark) AO-330: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl) Methyl)-2,4,6-trimethylbenzene (manufactured by ADEKA Co., Ltd.), Sumilizer (registered trademark) BHT: 2,6-di-tert-butyl-p-cresol (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (manufactured by Sumitomo Chemical Co., Ltd.) Trademark) GA-80:3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4 ,8,10-tetraoxaspiro[5.5]undecane (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered trademark) GP:2-tert-butyl-6-methyl-4-{3-[(2,4, 8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl}phenol (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered trademark) ) GS:2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl = acrylate (manufactured by Sumitomo Chemical Co., Ltd.); Sumilizer (registered trademark) GM: 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl = acrylate (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 :1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5 -triazine-2,4,6(1H,3H,5H)-trion (manufactured by Cytech Corporation), and vitamin E (manufactured by Eisai Corporation), and the like.

It is preferable that it is a compound which does not have a vinyl group and an ethene-1, 1- diyl group as a phenolic antioxidant. By using a phenolic antioxidant, although the fall of the maximum absorption in a film-forming process can be suppressed, the color change ((DELTA)Eab*) may become large. However, by using a compound which does not have a vinyl group and an ethene-1,1-diyl group as a phenolic antioxidant, not only suppression of the fall of the maximum absorption in a film-forming process, but a color change can also be suppressed.

It is preferable that the number of phenolic hydroxyl groups which 1 molecule of phenolic antioxidant has is 1-5, More preferably, it is 1-4, More preferably, it is 2-4.

Among phenolic antioxidants, hindered phenolic antioxidants are preferable. It is preferable that it is a compound which a tertiary alkyl group couple|bonds with at least one carbon atom among two ortho positions of a phenolic hydroxyl group as a hindered phenol type antioxidant;

It is more preferable that it is a compound in which a tertiary alkyl group is bonded to one carbon atom among the two ortho positions of the phenolic hydroxyl group and a hydrogen atom or an alkyl group is bonded to the other carbon atom;

It is more preferable that it is a compound in which a tertiary alkyl group is bonded to one carbon atom among two ortho positions of the phenolic hydroxyl group and a hydrogen atom, a methyl group, or a primary alkyl group is bonded to the other carbon atom;

It is especially preferable that it is a compound which a tertiary alkyl group couple|bonds with one carbon atom among two ortho positions of a phenolic hydroxyl group, and a hydrogen atom or a methyl group couple|bonds with the other carbon atom.

Moreover, as a hindered phenol type antioxidant, it has two or more phenolic hydroxyl groups in a molecule|numerator, and a tertiary alkyl group couple|bonds with one carbon atom among two ortho positions of a phenolic hydroxyl group, and hydrogen is attached to the other carbon atom. It is preferable that it is a compound to which an atom, a methyl group, or a primary alkyl group couple|bonds.

Examples of the alkyl group include a methyl group, a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group.

As a primary alkyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group etc. are mentioned, An ethyl group and n-propyl group are preferable.

As a secondary alkyl group, an isopropyl group, an isobutyl group, etc. are mentioned.

Examples of the tertiary alkyl group include a tert-butyl group, a tert-pentyl group, a tert-hexyl group, and a texyl group. A tert-butyl group and a tert-pentyl group are preferable, and a tert-butyl group is more preferable.

Specific examples of the hindered phenolic antioxidant include Irganox (registered trademark) 1010, Irganox (registered trademark) 1076, Irganox (registered trademark) 1330, Irganox (registered trademark) 3114, Irganox (registered trademark) 3790, Irganox (registered trademark) ) 1035, Irganox (registered trademark) 1135, Irganox (registered trademark) 3125, Irganox (registered trademark) 565, adecastab (registered trademark) AO-80, adekastave (registered trademark) AO-20, adecastab ( Registered trademark) AO-30, ADEKASTAVE (registered trademark) AO-40, ADEKASTAVE (registered trademark) AO-50, ADEKASTAVE (registered trademark) AO-60, ADEKASTAVE (registered trademark) AO-330 , Sumilizer (registered trademark) BHT, Sumilizer (registered trademark) GA-80, Sumilizer (registered trademark) GP, Sumilizer (registered trademark) GM, Cyanox 1790, etc. to at least one carbon atom of two ortho positions of phenolic hydroxyl groups It is preferable that it is a compound to which a tert-butyl group is bonded,

Irganox (registered trademark) 1010, Irganox (registered trademark) 1076, Irganox (registered trademark) 1330, Irganox (registered trademark) 3114, Irganox (registered trademark) 3790, Irganox (registered trademark) 1035, Irganox (registered trademark) 1135, Irganox (trademark) 3125, Irganox (registered trademark) 565, adekastave (registered trademark) AO-80, adekastave (registered trademark) AO-20, adekastave (registered trademark) AO-30, adekastave (registered trademark) Registered trademark) AO-40, ADEKASTAVE (registered trademark) AO-50, ADEKASTAVE (registered trademark) AO-60, ADEKASTAVE (registered trademark) AO-330, Sumilizer (registered trademark) BHT, Sumilizer (registered trademark) Trademark) GA-80, Sumilizer (registered trademark) GP, Cyanox 1790, etc. of two ortho positions of phenolic hydroxyl groups, a tert-butyl group is bonded to one carbon atom, and a hydrogen atom, a methyl group, or tert is bonded to the other carbon atom. -It is more preferable that it is a compound to which a butyl group bonds,

Irganox (registered trademark) 3790, adekastave (registered trademark) AO-80, adekastave (registered trademark) AO-30, adekastave (registered trademark) AO-40, Sumilizer (registered trademark) GA-80, Sumilizer (registered trademark) GP, Cyanox 1790, etc. of the two ortho positions of the phenolic hydroxyl group, a tert-butyl group is bonded to one carbon atom, more preferably a compound in which a hydrogen atom or a methyl group is bonded to the other carbon atom,

Irganox (registered trademark) 3790, adekastave (registered trademark) AO-80, adekastave (registered trademark) AO-30, adekastave (registered trademark) AO-40, Sumilizer (registered trademark) GA-80, Cyanox It is particularly a compound having two or more phenolic hydroxyl groups, such as 1790, in which a tert-butyl group is bonded to one carbon atom among two ortho positions of the phenolic hydroxyl group and a hydrogen atom or a methyl group is bonded to the other carbon atom. desirable.

Antioxidant (E) may use other antioxidant together with a phenolic antioxidant. As other antioxidants, phosphorus antioxidants, sulfur antioxidants, hindered amine antioxidants, and the like can be used.

The content rate of the phenolic antioxidant in antioxidant (E) becomes like this. Preferably it is 50 mass % or more, More preferably, it is 70 mass % or more, More preferably, it is 80 mass % or more, Especially preferably, 90 mass % or more. and 95 mass % or more may be sufficient, and 100 mass % may be sufficient.

It is preferable that the mass ratio of antioxidant (E) and the said squarylium dye (antioxidant (E)/squarylium dye) is 0.8 or more, More preferably, it is 1.0 or more, More preferably, it is 1.5 or more, Especially preferably is 2.0 or more, preferably 13 or less, more preferably 10 or less, still more preferably 8 or less.

It is preferable that the content rate of antioxidant (E) is 0.5-20 mass % with respect to the total amount of solid content, More preferably, it is 1-17 mass %, More preferably, it is 1.5-15 mass %.

<Solvent (F)>

It is preferable that the colored curable resin composition of this invention contains the solvent (F) further. The solvent (F) is not specifically limited, The solvent normally used in this field|area can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether esters Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (containing OH in the molecule, - solvents not containing O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methylanisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and methyl 3-ethoxypropionate. , 3-ethoxypropionate ethyl, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionate propyl, 2-ethoxypropionate methyl, 2-ethoxypropionate ethyl, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono and propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone (hereinafter sometimes referred to as diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, and 4-heptane. one, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

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

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

Among the above solvents, from the viewpoint of coating properties and drying properties, organic solvents having a boiling point of 120°C or more and 180°C or less at 1 atm are preferable. Examples of the solvent include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diacetone alcohol and N,N-dimethylformamide is preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diacetone alcohol, ethyl lactate, and ethyl 3-ethoxypropionate are more preferable.

To [ the content rate of a solvent (F) ] the total amount of the colored curable resin composition of this invention, Preferably it is 70-95 mass %, More preferably, it is 75-92 mass %. In other words, the total content of solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When the content rate of a solvent (F) exists in said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

<Leveling agent (G)>

The colored curable resin composition of this invention may contain the leveling agent (G) further. As a leveling agent (G), silicone type surfactant, the silicone type surfactant etc. which have a silicone type surfactant, a fluorine type surfactant, and a fluorine atom are mentioned. These may have a polymeric group in a side chain.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray Silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper 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 Co., Ltd.) .

As said fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapac (registered trademark) F142D, east F171, east F172, east F173, east F177, east F183, east F554, east R30, RS-718-K (manufactured by DIC Co., Ltd.), EFTO (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electric Chemical Co., Ltd.), Sufflon (registered trademark) S381 , copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute), and the like.

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

With respect to the total amount of colored curable resin composition, the content rate of a leveling agent (G) becomes like this. Preferably they are 0.001 mass % or more and 0.2 mass % or less, More preferably, they are 0.002 mass % or more and 0.2 mass % or less, More preferably It is 0.005 mass % or more and 0.2 mass % or less. In addition, the content rate of the said dispersing agent is not included in this content rate. When the content rate of a leveling agent (G) exists in said range, the flatness of a color filter can be made favorable.

<Other ingredients>

The colored curable resin composition of the present invention may contain additives known in the art, such as polymerization initiation aids, fillers, other high molecular compounds, adhesion promoters, light stabilizers, chain transfer agents, and the like, if necessary.

<Method for producing colored curable resin composition>

The colored curable resin composition of the present invention includes, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), an antioxidant (E), and optionally a solvent (F). ), a leveling agent (G), and other components can be prepared by mixing.

<Method for manufacturing color filter>

As a method of manufacturing a colored pattern with the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable. The photolithographic method is a method of apply|coating the said colored curable resin composition to a board|substrate, drying it, forming a coloring composition layer, exposing the said coloring composition layer through a photomask, and developing. The photolithographic method WHEREIN: The colored coating film which is hardened|cured material of the said coloring composition layer can be formed by not using a photomask at the time of exposure, and/or not developing. The colored pattern and colored coating film formed in this way are the color filter of this invention.

The film thickness of the color filter to be produced is not specifically limited, It can adjust suitably according to the objective, a use, etc., For example, 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers. .

Examples of the substrate include a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass coated with silica, a resin plate such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and aluminum on the substrate. , silver, silver/copper/palladium alloy thin films, etc. are used. On such a board|substrate, another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed.

Formation of each color pixel by the photolithographic method can be performed with a well-known or customary apparatus and conditions. For example, it can be produced as follows.

First, a colored curable resin composition is apply|coated on a board|substrate, volatile components, such as a solvent, are removed and dried by heat-drying (pre-baking) and/or drying under reduced pressure, and a smooth coloring composition layer is obtained.

As a coating method, the spin coating method, the slit coating method, the slit-and-spin coating method, etc. are mentioned.

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable that they are 10 second - 60 minutes, and it is more preferable that they are 30 second - 30 minutes.

When drying under reduced pressure, it is preferable to carry out under a pressure of 50 to 150 Pa at a temperature range of 20 to 25°C.

The film thickness of the coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the color filter made into the objective.

Next, the coloring composition layer is exposed in order to form a colored coating film. In addition, when forming a coloring pattern, a coloring composition layer is exposed through a photomask. The pattern on the said photomask is not specifically limited, The pattern according to the intended use is used.

As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250-450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength region, or light around 436 nm, 408 nm, or 365 nm is selectively extracted using a bandpass filter that extracts these wavelength regions. You can do it. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, in order to irradiate a parallel light beam uniformly to the whole exposure surface, or to accurately position a photomask and the board|substrate with a coloring composition layer formed.

A coloring pattern is formed on a board|substrate by making a developing solution contact and developing the coloring composition layer after exposure. By image development, the unexposed part of a coloring composition layer melt|dissolves in a developing solution, and is removed. As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, is preferable, for example. The concentration in the aqueous solution of such an alkaline compound is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. Moreover, the developing solution may contain surfactant.

Any of a paddle method, a dipping method, a spray method, etc. may be sufficient as the image development method. Moreover, you may incline a board|substrate at an arbitrary angle at the time of image development.

After image development, it is preferable to wash with water.

Moreover, it is preferable to post-baking to the obtained colored coating film or a colored pattern. 150-250 degreeC is preferable and, as for post-baking temperature, 160-235 degreeC is more preferable. 1 to 120 minutes are preferable and, as for post-baking time, 10 to 60 minutes are more preferable.

ADVANTAGE OF THE INVENTION According to this invention, the colored curable resin composition with high aptitude in a film-forming process can be provided. The color filter produced from the said colored curable resin composition is useful as a color filter used for a display apparatus (For example, a liquid crystal display device, an organic electroluminescent display apparatus, electronic paper, etc.) and a solid-state image sensor.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the original examples, and it is of course also carried out with appropriate changes within the range that can be suitable for the purpose of the preceding and latter period. possible, and they are all included in the technical scope of the present invention. In the examples, % and parts indicating the content or the amount used are based on mass unless otherwise specified.

[Colorant Synthesis Example 1]

10.0 parts of 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 17.0 parts of 2-ethylhexane bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 44.0 parts of tetrabutylammonium bromide (manufactured by Wako Chemical Industry Co., Ltd.) mixed wealth. The obtained mixture was stirred at 90 degreeC for 8 hours. After completion of the reaction, 50 parts of 10% sodium bicarbonate water was added, and then 100 parts of ethyl acetate was added to discard the aqueous layer. After repeating the operation of washing with water and 10% hydrochloric acid twice, the solvent was distilled off. The obtained oil was dried under reduced pressure at 60°C for 24 hours to obtain 9.3 parts of a compound represented by the following formula (a-1).

[Formula 22]

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ) of the compound represented by formula (a-1)

δ 0.85 (m, 6H), 1.23-1.42 (br ,8H), 1.59 (br, 1H), 2.04 (s, 3H), 2.12 (s, 3H), 2.91 (d, 2H), 4.37 (br, 1H) ), 6.38 (d, 1H), 6.75 (s, 1H), 6.77 (d, 1H)

3.0 parts of the compound represented by the formula (a-1) obtained above, 2.2 parts of 3-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.015 parts of palladium acetate, and sodium tert-butoxy (Tokyo Chemical Industry Co., Ltd.) 3.2 parts), 0.055 parts of tritert-butylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 25.6 parts of toluene were mixed, followed by stirring at 100°C for 15 hours. To the obtained mixture, 30 parts of ethyl acetate and 100 parts of water were added, and the aqueous layer was discarded. After repeating the operation of washing with water twice, the solvent was distilled off. The residue was purified by silica gel chromatography (chloroform/hexane = 1/1), and the obtained oil was dried under reduced pressure at 60°C for 24 hours to obtain 1.9 parts of a compound represented by the compound represented by the following formula (a-2).

[Formula 23]

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ) of the compound represented by formula (a-2)

δ 0.85 (m, 6H), 1.23-1.42 (br, 8H), 1.55 (br, 1H), 1.94 (s, 3H), 2.27 (s, 3H), 2.90 (d, 2H), 6.37 (d, 1H) ), 6.75(s, 1H), 6.76(d, 1H), 6.92-7.14(m, 4H), 8.93(s, 1H)

4.4 parts of the compound represented by the formula (a-2) obtained above, 0.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-butanol 90.0 parts and 60.0 parts of toluene were mixed. The resulting mixture was stirred at 125°C for 3 hours while removing the generated water using a Dean-Stark tube. After completion|finish of reaction, the solvent was distilled off, and after adding 15 parts of acetic acid, it was dripped at 100 parts of 18% saline, and the precipitated solid was obtained by filtration. The solid obtained by filtration was washed with hexane. The obtained solid was dried under reduced pressure at 60 degreeC for 24 hours, and 4.9 parts of compounds represented by Formula (AI-1) were obtained.

[Formula 24]

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ) of the compound represented by formula (AI-1)

δ 0.87 (m, 12H), 1.21-1.57 (m, 16H), 1.72 (br, 2H), 2.05 (s, 6H), 2.36 (s, 6H), 3.37 (br, 2H), 3.78 (br, 2H) ), 6.00(br, 4H), 6.97-7.12(m, 6H), 7.77-7.95(m, 2H), 11.35(s, 1H), 12.06(s, 1H)

[Colorant Synthesis Example 2]

After dissolving 50 parts of m-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) in 500 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.), cooled to 0 ° C. , 48 parts of tert-butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise. After completion|finish of dripping, it heated up at 23 degreeC, and stirred for 16 hours. After completion of the reaction, water was added to extract the organic layer, and the solvent was concentrated and purified by silica gel column chromatography to obtain 74 parts of the compound represented by the formula (1-10). In the following, the structure of the compound was confirmed by mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; Model LC/MSD manufactured by Agilent).

Identification (同定): (Mass Spec.) Ionization mode = ESI +: m / z = [M + H] + 287.0

Exact Mass : +286.0

[Formula 25]

45 parts of 4-amino-3,5-xylenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 400 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.). To this solution, 127 parts of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and dissolved. The reaction was stirred at 23°C for 16 hours. After completion of the reaction, the solvent was distilled off to obtain 51 parts of a crude product. The obtained crude product was purified by stirring at 23° C. for 2 hours in a mixed solvent of 90 parts of ethyl acetate (manufactured by Kanto Chemical Co., Ltd.) and 272 parts of n-hexane (manufactured by Kanto Chemical Co., Ltd.) to give formula (1-33) 47 parts of the compound shown was obtained.

Identification: (mass spectrometry) ionization mode=ESI+:m/z=[M+H] ⁺ 238.3

Exact Mass : +237.1

[Formula 26]

20 parts of 2-bromoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 333 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.). To this solution, 32.4 parts of triethylamine (manufactured by Kanto Chemical Co., Ltd.) and 0.156 parts of 4-dimethylaminopyridine (manufactured by Kanto Chemical Co., Ltd.) were added, and while stirring, tert-butyldimethylsilyl chloride (Tokyo Chemical Industry Co., Ltd.) Article) 28.95 parts were added and dissolved. The reaction was stirred at 23°C for 16 hours. The solvent was distilled off to obtain 20 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of a compound represented by the formula (1-34).

Identification: (mass spectrometry) ionization mode=ESI+:m/z=[M+H] ⁺ 239.1

Exact Mass : +238.0

[Formula 27]

47 parts of the compound represented by the formula (1-33) were dissolved in 141.5 parts of the bromo compound represented by the formula (1-34) and 447 parts of dimethylformamide (manufactured by Kanto Chemical Co., Ltd.). 138.2 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.) was put into this solution, and the mixture was stirred and reacted at 70°C for 16 hours. After completion of the reaction, the solvent was distilled off and extraction was performed with an organic solvent to obtain 49 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 41 parts of a compound represented by the formula (1-35).

Identification: (mass spectrometry) ionization mode=ESI+:m/z=[M+Ht-Bu ⁺ ] ⁺ 339.2

Exact Mass : +395.3

[Formula 28]

41 parts of the compound represented by formula (1-35) were dissolved in 424 parts of 1,4-dioxane (manufactured by Kanto Chemical Co., Ltd.), and hydrogen chloride (about 4 mol/L 1,4-dioxane solution) (Tokyo Chemical Industry Co., Ltd.) 263 parts of Co., Ltd. product were thrown in, and it deprotected by stirring at 23 degreeC for 1 hour. After completion of the reaction, the solvent was distilled off to obtain 36 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 22 parts of a compound represented by the formula (1-36).

Identification: (mass spectrometry) ionization mode=ESI+:m/z=[M+H] ⁺ 182.2

Exact Mass: +181.1

[Formula 29]

22 parts of the compound represented by Formula (1-36) were dissolved in 293 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.). To this solution, 10.8 parts of imidazole (manufactured by Kanto Chemical Co., Ltd.) and 22 parts of tert-butyldimethylsilyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved. The reaction was stirred at 23°C for 16 hours. The solvent was distilled off to obtain 23 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of a compound represented by the formula (1-37).

Identification: (mass spectrometry) ionization mode=ESI+:m/z=[M+H] ⁺ 296.3

Exact Mass: +295.2

[Formula 30]

15 parts of the compound represented by the formula (1-10) were dissolved in 14.5 parts of the compound represented by the formula (1-37) and 130 parts of toluene (manufactured by Kanto Chemical Co., Ltd.), and potassium hydroxide (Kanto Chemical Co., Ltd.) in this solution ) agent) 5.7 parts, water 15 parts, tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 parts, bis(tri-tert-butylphosphine) palladium (0) (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.26 mixed wealth. After heating up to 90 degreeC and stirring for 20 minutes, the organic layer was acquired by extraction, the solvent was distilled off, and 15 parts of crude products were obtained. The obtained crude product was separated and purified by column chromatography to obtain 12 parts of a compound represented by the formula (1-38).

Identification: (mass spectrometry) ionization mode=ESI+:m/z=[M+H] ⁺ 502.4

Exact Mass : +501.3

[Formula 31]

12 parts of the compound represented by formula (1-38), 11.9 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 41.6 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) are mixed, and 90°C heated with stirring for 1 hour. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 5.9 parts of a compound represented by the formula (1-39).

Identification: (mass spectrometry) ionization mode=ESI+:m/z=[M+H] ⁺ 616.3

Exact Mass : +615.3

[Formula 32]

5.9 parts of the compound represented by the formula (1-39) were dissolved in 52.4 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and cooled to 0° C., followed by a 1M tetrahydrofuran solution of tetrabutylammonium fluoride (Tokyo Chemical Industries, Ltd.) 11 parts of manufacture) were dripped, and it stirred at 23 degreeC after completion|finish of dripping for 2 hours. After completion of the reaction, water was added, and the crude product obtained by distilling off the tetrahydrofuran solvent was subjected to extraction with an organic solvent to obtain 4.3 parts of the compound represented by the formula (1-40) after concentration.

Identification: (mass spectrometry) ionization mode=ESI+:m/z=[M+H] ⁺ 388.2

Exact Mass : +387.2

[Formula 33]

4.3 parts of a compound represented by formula (1-40), 56.4 parts of a 1M borane solution (manufactured by Kanto Chemical Co., Ltd.), and 38.2 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) are mixed at 0°C and 23°C It heated up to and stirred for 16 hours. After completion of the reaction, water was added and quenched, followed by extraction with an organic solvent. The solvent was distilled off, and the obtained crude product was refine|purified by silica gel column chromatography, and 2.3 parts of compounds represented by Formula (1-41) were obtained.

Identification: (mass spectrometry) ionization mode=ESI+:m/z=[M+H] ⁺ 346.3

Exact Mass: +345.2

[Formula 34]

2.3 parts of the compound represented by formula (1-41) and 0.38 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) toluene (Kanto Chemical Co., Ltd.) ) agent) and 19 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.), and heated at 120°C for 4 hours while stirring. After completion of the reaction, the crude product obtained by distilling off the solvent was separated and purified by silica gel column chromatography to obtain 1.3 parts of the compound represented by the formula (AI-15).

Identification: (mass spectrometry) ionization mode=ESI+:m/z=[M+H] ⁺ 769.8

Exact Mass: +768.4

[Formula 35]

[Resin Synthesis Example]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was poured and replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was put, and it heated to 80 degreeC, stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylic The mixed solution of 289 parts of the mixture (mixing ratio of 1:1) of the rate and 125 parts of propylene glycol monomethyl ether acetate was dripped over 5 hours. On the other hand, the mixed solution which melt|dissolved 33 parts of 2, 2- azobis (2, 4- dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was dripped over 6 hours. After completion of the dropwise addition, the flask was kept at 80°C for 4 hours, cooled at room temperature, and a solution of a copolymer (resin (B-1)) having a type B viscosity (23°C) of 125 mPa·s and a solid content of 35.1%. got The produced copolymer had a weight average molecular weight (Mw) of 9200, a dispersion degree of 2.08, and a solid content acid value of 77 mg-KOH/g. Resin (B-1) has the following structural unit.

[Formula 36]

[Examples 1 to 15, Comparative Examples 1 to 3]

[Preparation of colored curable resin composition]

Each component was mixed so that it might become a composition shown in Table 3, and the colored curable resin composition was obtained. In addition, in Table 3, the unit of content of each composition is "part".

In Table 3, each component shows the following compounds.

Colorant (A-1): a compound represented by formula (AI-1)

Colorant (A-2): a compound represented by the formula (AI-15)

Resin (B-1): Resin (B-1) (in terms of solid content)

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

Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (PBG-327; oxime compound; Sangju Strong Electronic New Materials) (subject)

Antioxidant (E-1): 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol) (adecastab (registered trademark) AO -30; manufactured by ADEKA Co., Ltd.)

Antioxidant (E-2): 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol (adekastave (registered trademark) AO-40; manufactured by ADEKA Corporation)

Antioxidant (E-3): 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2, 4,8,10-tetraoxaspiro [5.5] undecane (Sumilizer (registered trademark) GA-80; manufactured by Sumitomo Chemical Co., Ltd.)

Antioxidant (E-4): pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (adekastave (registered trademark) AO-60; ADEKA Corporation My)

Antioxidant (E-5): 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H, 3H, 5H)-trion (ADEKA STAB (registered trademark) AO-20; manufactured by ADEKA Corporation)

Antioxidant (E-6): 2-tert-butyl-6-methyl-4-{3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3, 2]dioxaphosphepin-6-yl)oxy]propyl}phenol (Sumilizer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Antioxidant (E-7): 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl=acrylate (Sumilizer (registered) Trademark) GS; Sumitomo Chemical Co., Ltd.)

Antioxidant (E-8): 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (adecastab (registered trademark) LA82; manufactured by ADEKA Corporation)

Antioxidant (E-9): 2,2,6,6-tetramethyl-4-piperidyl methacrylate (adecastab (registered trademark) LA87; manufactured by ADEKA Corporation)

Solvent (F-1): diacetone alcohol

Solvent (F-2): propylene glycol monomethyl ether acetate

Leveling agent (G-1): polyether-modified silicone oil (“Toray Silicone SH8400” manufactured by Toray Dow Corning Co., Ltd.)

[Production of colored coating film]

On a 5 cm horizontal glass substrate (Eagle 2000; manufactured by Corning), a colored curable resin composition was applied by spin coating so that the post-baking film thickness was 2.0 μm, and then pre-baked at 100° C. for 3 minutes to color composition. layer was formed. After standing to cool, the coloring composition layer was irradiated with light at an exposure amount (based on 365 nm) of 100 ^{mJ/cm 2 in} an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). Then, it post-baked at 230 degreeC in oven for 30 minutes, and obtained the colored coating film.

[evaluation]

1. Absorbance retention rate

After pre-baking and post-baking, the maximum absorbance in the visible region was obtained from the spectrum measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the retention of the maximum absorbance was calculated according to the following formula. . A result is shown in Table 4.

Absorbance retention rate (ΔAbs.Max)=Maximum absorbance after post-bake/Maximum absorbance after pre-bake

It means that the aptitude in a film-forming process is so high that the absorbance retention is high.

2. Color change (ΔEab*)

After pre-baking and post-baking, spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) and the stimulus value (Y) were measured. From the measured value, the color difference (ΔEab*) was calculated by the method described in JIS Z 8730:2009 (7. Color difference calculation method), and the results are shown in Table 4. The smaller ΔEab*, the smaller the color change.

ADVANTAGE OF THE INVENTION According to this invention, since the colored curable resin composition with high aptitude in a film-forming process can be provided, it is useful as a colored curable resin composition used for the color filter of a display apparatus or a solid-state image sensor.

Claims (9)

a colorant, a resin, a polymerizable compound, a polymerization initiator, and an antioxidant;
The colorant includes a squarylium dye having a maximum absorption in the visible region,
The colored curable resin composition in which the said antioxidant contains a phenolic antioxidant. The method of claim 1,
The colored curable resin composition in which the said phenolic antioxidant is a compound which does not have a vinyl group and an ethene-1,1-diyl group. 3. The method according to claim 1 or 2,
The colored curable resin composition in which the said phenolic antioxidant is a compound which a tertiary alkyl group couple|bonds with one carbon atom among two ortho positions of a phenolic hydroxyl group, and a hydrogen atom or an alkyl group couple|bonds with the other carbon atom. 4. The method according to any one of claims 1 to 3,
The phenolic antioxidant is a compound in which a tertiary alkyl group is bonded to one carbon atom among two ortho positions of the phenolic hydroxyl group and a hydrogen atom, a methyl group, or a primary alkyl group is bonded to the other carbon atom. Curable resin composition. 5. The method according to any one of claims 1 to 4,
The colored curable resin composition in which mass ratio (antioxidant/squarylium dye) of the said antioxidant and the said squarylium dye is 0.8 or more. 6. The method according to any one of claims 1 to 5,
The colored curable resin composition in which the said squarylium dye is a compound represented by Formula (AI).

[of formula (AI),
R ¹ to ^{R 4} each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.
R ⁵ to ^{R 8} each independently represent a hydrogen atom or a hydroxyl group.
Ar ¹ and Ar ² each independently represent a group represented by formula (i).

[In formula (i),
R ¹² represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxy group, or a carboxy group, and m is an integer of 0 to 5 indicates The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, some R ¹² may be the same or different, respectively. * indicates a bond with a nitrogen atom.]
R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by formula (i). The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.] 7. The method according to any one of claims 1 to 6,
The colored curable resin composition in which the said squarylium dye is a compound represented by Formula (AII).

[In formula (AII),
R ¹ to ^{R 4} each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.
R ⁵ to ^{R 8} each independently represent a hydrogen atom or a hydroxyl group.
Ar ¹ and Ar ² each independently represent a group represented by formula (i).

[In formula (i),
R ¹² represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxy group, or a carboxy group, and m is an integer of 0 to 5 indicates The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, some R ¹² may be the same or different, respectively. * indicates a bond with a nitrogen atom.]
R ¹³ and R ¹⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group or a carboxy group, and the methylene group constituting the monovalent saturated hydrocarbon group is substituted with -O- or -S- There may be.] The color filter formed from the colored curable resin composition in any one of Claims 1-7. A display device comprising the color filter according to claim 8 .