TW201311831A - Salt and colored curable composition - Google Patents

Abstract

The present invention provides a salt comprising at least one anion selected from the group consisting of formulae (I), (II), (III) and (IV), and a cation having xanthene skeleton: wherein X1 and X2 each independently represent a fluorine atom or a fluorinated alkyl group, or X1 and X2 bond to form a fluorinated alkanediyl group having 2 to 4 carbon atoms; wherein X3 - X5 each independently represent a fluorine atom or a fluorinated alkyl group; wherein Y1 represents a fluorinated alkanediyl group having 1 to 4 carbon atoms; wherein Y2 represents a fluorinated alkyl group having 1 to 4 carbon atoms.

Description

Salt and color hardening composition

The present invention relates to a salt suitable as a dye, and a color hardening composition containing the same.

Dyes are used in the fields of, for example, fiber materials, liquid crystal display devices, ink jets, and recording materials. As such a dye, for example, a compound represented by the following formula (h-1) (JP2011-100114-A) is known.

The above-mentioned salt which has been conventionally known has not been able to sufficiently satisfy the solubility in an organic solvent.

The present invention contains the inventions described in the following [1] to [11].

[1] a salt containing at least one anion selected from the group consisting of the anions represented by the formulas (I), (II), (III) and (IV), respectively (xanthene) a cation of the skeleton; [wherein, X ¹ and X ² are each independently represented by a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or X ¹ and X ^{2 are} bonded to each other to form a fluorinated alkanediyl group having 2 to 4 carbon atoms], [wherein, X ³ to X ⁵ are each independently shown as a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms], [wherein Y ¹ is represented by a fluorinated alkanediyl group having 1 to 4 carbon atoms], [wherein Y ² is represented by a fluorinated alkyl group having 1 to 4 carbon atoms].

[2] [1] of a salt, wherein the metal further comprises n-valent organic anion M ^n-, the n-valent organic metal M ^n- is an anion formed containing at least divalent metal atom of the metal ion.

[3] The salt according to [2], wherein the n-valent organometallic anion M ^{n- is} a compound represented by the formula (1), which satisfies the following requirement a; M ^n- nZ ⁺ (1) [Formula (1) In the above, M ^n- is represented by the above organometallic anion, Z ⁺ is represented by a hydrogen cation or an alkali metal cation, n is an integer of 1 to 3, and when n is an integer of 2 or more, a plurality of Z ⁺ are mutually The same or different]; A: The absorbance measured by the concentration of the compound represented by the formula (1) of 0.028 g / L of the solution is 0.05 or less over the entire range of the wavelength of 400 to 900 nm.

[4] The salt of [2] or [3], wherein the aforementioned n-valent organometallic anion M ^n- is an organometallic anion having a structure derived from salicylic acid which may have a substituent, or from And a compound having a plurality of carboxymethyl groups bonded to an amine group.

[5] The salt according to any one of [2] to [4] wherein the metal atom which may form a divalent or higher metal ion in the n-valent organic metal anion M ^n- is Al, Cr or Co.

[6] A dye comprising the salt according to any one of [1] to [5] as an active ingredient.

[7] A colored curable composition comprising the dye of [6] and a polymerizable compound.

[8] The color hardening composition according to [7], which further contains a pigment.

[9] The colored curable composition according to [7] or [8], which further comprises at least one selected from the group consisting of a resin and a polymerization initiator.

[10] A color filter formed by the color hardening composition according to any one of [7] to [9].

[11] A display device having the color filter of [10].

The salt of the present invention is excellent in solubility in an organic solvent.

[Best Mode for Carrying Out the Invention]

The salt of the present invention contains at least one anion selected from the group consisting of the anions represented by the formulas (I), (II), (III) and (IV), respectively. The cation of the skeleton.

[In the formula (I), X ¹ and X ² are each independently represented by a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or X ¹ and X ^{2 are} bonded to each other to form a fluorinated alkane having a carbon number of 1 to 4. base].

[In the formula (II), X ³ to X ⁵ are each independently represented by a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms].

[In the formula (III), Y ¹ is represented by a fluorinated alkanediyl group having 1 to 4 carbon atoms].

[In the formula (IV), Y ² is represented by a fluorinated alkyl group having 1 to 4 carbon atoms].

In the above formulae (I) and (II), as the fluorinated alkyl group having 1 to 4 carbon atoms represented by X ¹ to X ⁵ , a perfluoroalkyl group is preferred, and for example, -CF ₃ , CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ or the like.

In the above formula (I), the fluorinated alkanediyl group having 2 to 4 carbon atoms formed by bonding X ¹ and X ^{2 is} preferably a perfluoroalkanediyl group, for example, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, and the like.

In the above formula (III), the fluorinated alkanediyl group having 1 to 4 carbon atoms represented by Y ^{1 is} preferably a perfluoroalkanediyl group, and examples thereof include -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, and the like.

In the above formula (IV), the fluorinated alkyl group having 1 to 4 carbon atoms represented by Y ^{2 is} preferably a perfluoroalkyl group, and examples thereof include -CF ₃ , -CF ₂ CF ₃ , and -CF ₂ CF. ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ and the like.

Examples of the anion represented by the above formula (I) (hereinafter also referred to as "anion (I)") include, for example, the following anions (I-1) to (I-6).

The anion represented by the above formula (II) (hereinafter also referred to as "anion (II)") is exemplified by the following anion (II-1).

Examples of the anion represented by the above formula (III) (hereinafter also referred to as "anion (III)") include, for example, the following anions (III-1) to (III-4).

Examples of the anion represented by the above formula (IV) (hereinafter also referred to as "anion (IV)") include, for example, the following anions (IV-1) to (IV-4).

By containing an anion selected from the group consisting of anion (I), anion (II), anion (III), and anion (IV) (hereinafter also referred to as "anion (I) to (IV)" ), the salt of the invention can be maintained as a source of cations The color properties of the dye can also improve the solubility of the organic solvent. Among them, an anion (II) is preferred, and an anion (II-1) is more preferred.

The cation contained in the salt of the present invention has skeleton. Preferably from The cation of the dye. So-called Dye, having intramolecular The general name for the dye of the skeleton. Preferably this The skeleton has at least one amine group, and more preferably has two amine groups. The cation contained in the salt of the present invention is preferably such that the nitrogen atom of the amine group is a cation having a positively charged structure, more preferably an iminium cation.

As this The dye may, for example, be an Eosin dye, a Fluorescein dye, a Rhodamine dye, a Pyronine dye, a Rosamin dye or the like. Further, as described in Synlett, 2010, No. 1, p. 89-92, for example, The oxygen atom of the skeleton is a Rhodamine dye or a Rosaamine dye which is substituted by a sulfur atom, a selenium atom or a ruthenium atom.

The dye is usually an anion other than an anion (I) to (IV) (preferably Cl ^- or PF ₆ ^- ) or has a carboxylate group (-COO ^- ) or a sulfonate group (-SO) in the molecule. An anionic group such as ₃ ^- ). In the case of the former, The dye is a so-called basic dye from The cation of the dye, usually from A cation in which a part or all (preferably all) of an anion other than the anion (I) to (IV) is removed. In the latter case, The dye is a so-called internal salt, which comes from The cation of the dye is usually a cation having a structure in which a part or all (preferably all) of an anionic group possessed by the inner salt is neutralized. Here, as the anionic group, for example, a carboxylate group (-COO ^- ) is a carboxyl group (-COOH) or a salt thereof (-COONa or the like) to be neutralized, and a sulfonate group (-SO ₃ ^- ) It is a sulfonic acid group (-SO ₃ H) or a salt thereof (-SO ₃ Na, etc.) to be neutralized.

As Specific examples of the basic dye in the dye include, for example, CIBasic Red 1, CIBasic Red 2, CIBasic Red 3, CIBasic Red 4, Basic Red 8, Basic Red 11, CIBasic Violet 10, CIBasic Violet 11, CIBasic Violet 25, and Dyes and the like represented by the formulas (h-1) to (h-82), respectively.

As Specific examples of the inner salt in the dye include, for example, CIMordant Red 27 and dyes represented by the following formulas (h-100) to (h-118).

The salt of the present invention contains the above anions (I) to (IV) and A combination of cations of dyes. Specific examples of the combination are shown in Tables 1 to 3. In addition, it is described in the cation column of Tables 1 and 2 as its source. A basic dye in the dye. As described above, the cation contained in the salt of the present invention is a cation from which Cl ^- or PF ₆ ^{- is} removed from the basic dye. Moreover, the cation column of Table 3 describes that it is the source thereof. The inner salt in the dye. As described above, the cation contained in the salt of the present invention is such that the anion group of the inner salt is a cation having a neutralized structure.

When the salt of the present invention further contains an n-valent organometallic anion M ^n- (which contains a metal atom capable of forming a metal ion of a divalent or higher metal), that is, a so-called mixed salt, solubility is further improved. When the n-valent organometallic anion M ^{n- is} a compound represented by the formula (1) (hereinafter referred to as "the compound (1)"), it is more preferable to satisfy the following requirements a, M ^n- nZ ⁺ ( 1) In the formula (1), M ^n- is represented by the above organometallic anion, Z ⁺ is represented by a hydrogen cation or an alkali metal cation, n is an integer of 1 to 3, and when n is an integer of 2 or more, a plurality of Z ⁺ can be the same or different from each other].

Requirement a: The absorbance measured by the concentration of the compound (1) of 0.028 g/L is 0.05 or less over the entire range of the wavelength of 400 to 900 nm.

In the element a, the compound (1) is dissolved in at least one selected from the group consisting of ethyl lactate, chloroform, N,N-dimethylformamide, ion-exchanged water, methanol, ethanol and toluene. In one of the solvents, a solution having a concentration of 0.028 g/L was prepared, and the absorbance at a wavelength of 400 to 900 nm was measured for the solution. The absorbance is 0.05 or less, preferably 0.035 or less, and more preferably 0.005 or less in the entire region spanning the wavelength of 400 to 900 nm.

The salt of the present invention can remain as a source of cations as long as the compound (1) satisfies the requirement a. The color properties of the dye, and at the same time, have a tendency to improve the solubility of the organic solvent, and are therefore preferred.

In the formula (1), examples of the alkali metal represented by Z ⁺ include sodium and potassium.

In the formula (1), the organometallic anion represented by ^Mn- has a structure in which a metal atom capable of forming a divalent or higher metal ion and an organic compound are bonded by an ionic bond or a coordinate bond. The organic compound may, for example, be a salicylic acid which may have a substituent, a compound having a plurality of carboxymethyl groups bonded to an amine group, a diphenylglycolic acid which may have a substituent, a mandelic acid which may have a substituent, and A 2-picolinic acid or the like having a substituent. The organometallic anion ^{Mn- is} preferably an organometallic anion having a structure derived from a salicylic acid which may have a substituent or a compound derived from a carboxymethyl group having a plurality of groups bonded to an amine group. .

As the salicylic acid which may have a substituent, for example, salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, 4-bromosalicylic acid, 3-methoxysalicylic acid, 2-hydroxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butyl Salicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5,6-trichlorosalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid Wait.

The compound having a plurality of carboxymethyl groups bonded to an amine group is exemplified by the following.

Examples of the diphenylglycolic acid which may have a substituent include the following.

Examples of the mandelic acid which may have a substituent include the following.

Examples of the 2-picolinic acid which may have a substituent include the following.

Examples of the metal atom capable of forming a divalent or higher metal ion include Al, Cr, Co, Fe, Cu, Ni, Co, Zn, Mg, Ca, and Ba.

Among them, Al, Cr, and Co are preferred.

Examples of the organometallic anion M ^n- include the following anions (c-1) to anions (c-72).

Among them, as an anion M ^n- , preferably an anion (c-2), an anion (c-6) to an anion (c-9), an anion (c-14) to an anion (c-17), an anion (c- 21), anion (c-22), anion (c-24) ~ anion (c-26), anion (c-28), anion (c-32) ~ anion (c-35), anion (c-40 ) anion (c-43), anion (c-47), anion (c-48), anion (c-50) ~ anion (c-62), anion (c-65) and anion (c-67) More preferably anion (c-2), anion (c-21), anion (c-22), anion (c-26), anion (c-28), anion (c-47), anion (c- 48), anion (c-52); more preferably anion (c-28). As long as these anions are present, the salt of the present invention tends to have more excellent solubility in an organic solvent.

Specific examples of the salt (mixed salt) of the present invention containing the organometallic anion M ^n- are shown in Table 13.

By Dyes, and compounds containing anions (I) to (IV) and hydrogen cations, or Dyes, with anions (I)~(IV) and not from The salt of the cation of the dye (preferably an alkali metal cation) is mixed in a solvent to produce the salt of the present invention. Further, as long as the compound (1) is further mixed, a mixed salt in the salt of the present invention can be produced.

The ratio of the anions contained in the mixed salt can be appropriately adjusted by changing the ratio of the mixed anions (I) to (IV) to the compound (1).

As a solvent to be used for mixing, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, acetonitrile, ethyl acetate , toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, dioxane, water and chloroform.

Preferred among them are N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, methanol, ethanol, isopropanol and water. . As long as it is such a solvent, it contains The dye, the compound or salt of the anion (I) to (IV), and the compound (1) have a tendency to have high solubility.

If the solvent is water, in order to contain The dye, the compound or salt of the anion (I) to (IV), and the compound (1) are dissolved, and an acid such as acetic acid or hydrochloric acid may be added.

The mixing of the dye and the anion (I) to (IV) may be carried out by dissolving both in the above solvent or in an undissolved manner. However, when both are used as a solvent to be dissolved, and the dissolution is carried out, the salt of the present invention can be obtained in a high yield.

The mixing temperature of the dye and the anion (I) to (IV) is preferably from 0 ° C to 150 ° C, more preferably from 10 ° C to 120 ° C, and even more preferably from 20 ° C to 100 ° C.

Further, the mixing time is preferably from 1 hour to 72 hours, more preferably from 2 hours to 24 hours, and still more preferably from 3 hours to 12 hours.

When the mixed solvent and water are compatible solvents, water is added to the solution, and after stirring for 1 to 3 hours, the precipitate is obtained by filtration to obtain the salt of the present invention. The salt obtained can be washed with water according to the requirements.

When the mixed solvent and water are incompatible solvents, water is added to the solution and stirred for 1 to 3 hours. Thereafter, a solution containing the salt of the present invention can be obtained by simply obtaining an organic layer by liquid separation. The resulting solution containing the salt of the present invention can be washed with water as required. The salt of the present invention can be obtained by removing the solvent from the solution containing the salt of the present invention.

Further, the salt of the present invention is dissolved in a solvent such as acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone or chloroform, and can be purified by recrystallization.

For the dyes, commercially available products can also be used, or for example, Hiroshi Hiroshi, "Theory for the manufacture of dye chemistry", Takubun Do, 369-377, and Matsui Masahiro, "Synthesis and Application Technology of Functional Pigments", CMC Publishing, 89~ Produced by a conventional method described in 96 pages, Synlett, 2010, No. 1, p. 89-92, J. Organic Chemistry, 2008, Vol. 73, 8711-8718, and the like.

The compound (1) can also be used as a commercial product, or, for example, as described in JP-A-8-10360 (JPH8-10360-B) or JP2002-258537-A, and Experimental Chemistry Lecture 5, Vol. 22, pp. 312-313. Chemicalization The compound can be produced by reacting with a sulfate or a salt of a metal.

The salt of the present invention thus obtained is suitable as a dye. Further, the salt of the present invention is particularly suitable as a color filter dye for a display device such as a liquid crystal display device because of its high solubility in an organic solvent.

The dye of the present invention contains the salt of the present invention as an active ingredient.

The colored curable composition of the present invention contains the dye of the present invention as a coloring agent (hereinafter also referred to as "coloring agent (A)"), and further contains a polymerizable compound (C). The coloring agent preferably further contains a pigment (A1).

The colored curable composition of the present invention preferably further contains at least one selected from the group consisting of the resin (B) and the polymerization initiator (D), and more preferably contains the solvent (E).

The color hardening composition of the present invention may contain a dye different from the salt of the present invention (hereinafter also referred to as "dye (A2)") as a coloring agent, or may be selected as required At least one selected from the group consisting of a polymerization starting aid (D1) and a surfactant (F).

<Pigment (A1)>

As the pigment (A1), for example, a compound classified as a pigment in the Colour Index (published by The Society of Dyers and Colourists) is exemplified.

As the pigment (A1), for example, CIPigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117 , 125, 128, 137, 138, Yellow pigments of 139, 147, 148, 150, 153, 154, 166, 173, 180, 194, 214, etc.; CIPigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61 Orange pigments of 64, 65, 71, 73, etc.; CIPigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, Red pigments of 242, 254, 255, 264, 265, etc.; blue pigments of CIPigment Blue 15, 15:3, 15:4, 15:6, 60, etc.; CIPigment Violet 1, 14, 19, 23, 29 , purple pigments such as 32, 33, 36, 37, 38; CIPigment Green 7, 10, 15, 25, 36, 47, 58 and other green pigments; CIPigment brown 23, 25, etc. brown pigment; CIPigment black Black pigments such as 1, 7, etc.

These pigments may be used alone or in combination of two or more.

As the pigment (A1), a red pigment is preferred, and C.I. Pigment Violet 254 is more preferred. By including the above-mentioned pigment, the transmission spectrum is optimized, and the light resistance and chemical resistance of the color filter are improved.

The pigment (A1) may be subjected to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment on a pigment surface by a polymer compound or the like, Micronization treatment such as sulfuric acid micronization method, or treatment by washing with an organic solvent or water for removing impurities, ion exchange method by ionic impurities, or the like Processing and so on.

The pigment (A1) preferably has a uniform particle size. By performing the dispersion treatment by containing the pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more. As a pigment dispersing agent, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), Solspers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), and Ajisper are mentioned. (Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK Co., Ltd.), and the like.

When the pigment dispersant is used, the amount of the pigment dispersant used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less based on the pigment (A1). As long as the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained.

<dye (A2)>

As the dye (A2), for example, a dye such as an oil-soluble dye, an acid dye, a basic dye, a direct dye, a mordant dye, an amine salt of an acid dye or a sulfonamide derivative of an acid dye, for example, in the Colour Index (for example) The Society of Dyers and Colourists publishes a compound classified as a dye or a conventional dye described in a dyeing note (color dyeing company). Further, depending on the chemical structure, for example, an azo dye, a cyanine dye, a triphenylmethane dye, Dyes, phthalocyanine dyes, naphthoquinone dyes, anthraquinone dyes, quinone imine dyes, methine dyes, methine azo dyes, squarylium dyes, acridine dyes, styryl dyes, Coumarin dyes, quinoline dyes and nitro dyes. Among these, an organic solvent-soluble dye is preferred.

Specific examples are as follows, CISolvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, only the number is described), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CISolvent Red 24, 45, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218; CISolvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CISolvent Blue 35, 37, 59, 67; CISolvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.; Acid dyes such as CIAcid 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; CIAcid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52 , 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183 1,195,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277,280 , 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; CIAcid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CIAcid Blue 1, 7, 9, 15, 18, 23, 25, 27 , 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171 , 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CIAcid Violet 6B, 7, 9, 17, 19 102; CIAci d Green 1, 3, 5, 9, 16, 25, 27, 28, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc.; as a direct dye, for example, CIDirect Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CIDirect 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; CIDirect Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CIDirect Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119 , 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194 , 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256 , 257, 259, 260, 268, 274, 275, 293; CIDirect Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89 90, 93, 95, 96, 103, 104; CIDirect Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.; as mordant Dyes, for example, CIMordant dyes, such as CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CIMordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CIMordant 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; CI Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI Mordant Green 1, 3, 4, 5 , 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and so on.

Further, the following dyes can also be exemplified.

C.I. Reactive Yellow 2,76,116; C.I. Disperse Yellow 54,76; C.I. Reactive Orange 16; C.I. Basic Green 1; C.I. Vat Green 1 et al.

Further, the dye (A2) may, for example, be a compound represented by the formula (3) described in JP2011-118369-A.

[In the formula (3), R ^a1 to R ^a18 are each independently represented by a hydrogen atom, a halogen atom, a carbon number of 1 to 8 monovalent aliphatic hydrocarbon group, a nitro group, a phenyl group, -SO ₂ NHR ^a30 , -SO ₃ ^- , -COOR ^a30 or -SO ₂ R ^a30 .

R ^a19 and R ^a20 are each independently represented by a hydrogen atom, a methyl group, an ethyl group or an amine group.

R ^{a30 is} independently represented by a hydrogen atom and a monovalent hydrocarbon group having 1 to 10 carbon atoms, and -CH ₂ - contained in the hydrocarbon group may be substituted by -O- or -CO-.

M ^{1 is} shown as Cr or Co.

n ^{1 is} shown as an integer from 1 to 5.

D ^{1 is} shown as a hydrogen cation, a monovalent metal cation or from a monovalent cation of a compound of the skeleton].

Among the compounds represented by the formula (3), as described in JP2011-118369-A, it is preferred that the respective formulas (3a-1), (3a-5), (3a-7), (3a-8) The compound represented by (3a-13), (3a-16), (3a-23) or (z-1) is more preferably a red dye represented by the formula (3a-23).

Among these dyes, a red dye is preferable, and a compound represented by C.I. Solvent Red 130 and the above formula (3) is more preferable.

These dyes may be appropriately selected in accordance with the spectral spectrum of the desired color filter. These dyes may be used singly or in combination of two or more.

The content of the salt of the present invention and the total amount of the pigment (A1) and the dye (A2) is preferably from 5% to 60% by mass, more preferably from 8 to 55% by mass, based on the total amount of the solid content. It is preferably 10 to 50% by mass, and as long as it is in the above range, the color density when the color filter is formed is sufficient, and the necessary amount of the resin (B) or the polymerizable compound (C) can be contained in the composition. Therefore, a pattern having sufficient mechanical strength can be formed. Here, the "total amount of solid content" as used herein means the amount by which the content of the solvent is removed from the total amount of the colored curable composition. The total amount of the solid content and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>

As the resin (B), any resin is not particularly limited. The resin (B) is preferably an alkali-soluble resin, more preferably contains (a) The resin of the structural unit derived from acrylic acid. Here, (meth)acrylic acid means acrylic acid and/or methacrylic acid.

Preferred resins (B) include, for example, the following resins [K1] to [K6].

The resin [K1] is selected from at least one of the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (a) (hereinafter also referred to as "(a)") and having a carbon number of 2 to 4. A copolymer of a cyclic ether structure and an ethylenically unsaturatedly bonded monomer (b) (hereinafter also referred to as "(b)").

Resin [K2] (a) and (b) copolymer, (a) and copolymerizable monomer (c) (except that (a) and (b) are different) (hereinafter also referred to as " Copolymer of (c)"

Copolymer of resin [K3] (a) and (c)

Resin [K4] A resin obtained by reacting the copolymer of (a) and (c) with (b).

Resin [K5] A resin obtained by reacting the copolymer of (b) and (c) with (a).

Resin [K6] A resin obtained by reacting the copolymer of (b) and (c) with (a) and further reacting with a carboxylic 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, and citraconic acid; , meconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrofurfuric acid, 1,2,3,6-tetrahydrofurfuric acid, dimethyl An unsaturated dicarboxylic acid such as tetrahydrofurfuric acid or 1, 4-cyclohexene dicarboxylic acid; Methyl-5-northene-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[ 2.2.1] Hetero-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds; maleic anhydride, citraconic anhydride, and itanic anhydride , 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6 - an unsaturated dicarboxylic acid anhydride such as dicarboxybicyclo[2.2.1]hept-2-ene anhydride (norbornene dianhydride/Himic anhydride); mono [2-(methyl) propylene methoxyethyl] amber Unsaturated mono[(meth)acryloxyalkyl]ester of a divalent or higher polyvalent carboxylic acid such as an acid ester or a mono[2-(methyl)acryloxyethyl) phthalate An unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable in terms of point of copolymerization reactivity or solubility to an aqueous alkali solution.

(b) is, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) A polymerizable compound bonded to an ethylenic unsaturated group. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

In addition, in this specification, the so-called "(meth)acrylic acid" is a table. It is at least one selected from the group consisting of acrylic acid and methacrylic acid. The descriptions of "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

(b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"), having an oxypropylene group and ethylene Monounsaturated bonded monomer (b2) (hereinafter also referred to as "(b2)"), monomer having tetrahydrofuranyl group and ethylenically unsaturated bond (b3) (hereinafter also referred to as "( B3)") and so on.

(b1), for example, a monomer (b1-1) having a structure in which a linear or branched chain unsaturated aliphatic hydrocarbon is epoxidized (hereinafter also referred to as "(b1-1)") A monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter also referred to as "(b1-2)").

(b1-1), for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidylethylene Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-A Base-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-double (shrinkage) Glyceryloxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-parameter (shrinkage) Glyceryloxymethyl)styrene, 2,3,5-gin (glycidyloxy) Styrene, 2,3,6-gin (glycidoxymethyl)styrene, 3,4,5-gin (glycidoxymethyl)styrene, 2,4,6-gin (shrink Glyceroxymethyl)styrene and the like.

(b1-2), for example, vinylcyclohexene oxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), (methyl) 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; Daicel) A chemical industry (manufactured by the company), a compound represented by the formula (V), a compound represented by the formula (VI), and the like.

[In the formulae (V) and (VI), R ^a and R ^b are represented by a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group; X ^a and X; ^b show a single ^{bond, -R c -, * - R} c -O -, * - R c -S- or * -R ^c -NH-; R ^c shown alkanediyl group having a carbon number of 1 to 6; * Shown as the key with O].

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

The hydrogen atom is an alkyl group substituted with a hydroxyl group, and examples thereof include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. Hydroxy-1-methylethyl, 2-hydroxy-1-methyl Base, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

As R ¹ and R ² , for example, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group is preferable, and a hydrogen atom or a methyl group is more preferable.

As the alkanediyl group, for example, methylene, ethyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5- Dibasic, hexane-1,6-diyl and the like.

As X ^a and X ^b , for example, a single bond, a methylene group, an exoethyl group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O- are preferable, and more preferably, for example, a single bond, *-CH ₂ CH ₂ -O- (* is shown as a bond with O).

The compound represented by the formula (V) is, for example, a compound represented by the formula (V-1) to the formula (V-15). Preferably, for example, the formula (V-1), the formula (V-3), the formula (V-5), the formula (V-7), the formula (V-9), the formula (V-11) and the formula (V- 15). More preferably, for example, the formula (V-1), the formula (V-7), the formula (V-9), and the formula (V-15).

The compound represented by the formula (VI) is, for example, a compound represented by the formula (VI-1) to the formula (VI-15). Preferably, for example, formula (VI-1), formula (VI-3), formula (VI-5), formula (VI-7), formula (VI-9), formula (VI-11)-form (VI- 15). More preferably, it is a formula (VI-1), Formula (VI-7), Formula (VI-9), Formula (VI-15).

The compound represented by the formula (V) and the compound represented by the formula (VI) can be used alone. Also, these can be mixed in any ratio. When mixing, the mixing ratio formula (V): formula (VI) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80. :20.

The monomer (b2) having an propylene oxide group and an ethylenically unsaturated bond is more preferably a monomer having an oxypropylene group and a (meth)acryloxy group. As (b2), for example, 3-methyl-3-methylpropenyloxymethyl propylene oxide, 3-methyl-3-propenyloxymethyl propylene oxide, 3-ethyl-3- Methyl propylene methoxymethyl propylene oxide, 3-ethyl-3-propenyl methoxymethyl propylene oxide, 3-methyl-3-methyl propylene methoxyethyl propylene oxide, 3- Methyl-3-propenyloxyethyl propylene oxide, 3-ethyl-3-methylpropenyloxyethyl propylene oxide, 3-ethyl-3-propenyloxyethyl propylene oxide Wait.

The monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(b) is preferable as (b), in that the reliability of heat resistance and chemical resistance of the obtained color filter can be further improved. Further, it is more preferably (b1-2) in terms of the excellent storage stability of the coloring composition.

As (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, (meth)acrylic acid Tert-butyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, (methyl) Cyclopentyl acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (In the technical field, the conventional name is called "dicyclopentanyl (meth) acrylate". Also, it is called "tricyclodecyl (meth) acrylate".), (meth)acrylic acid Tricyclo [5.2.1.0 ^2,6 ]nonene-8-yl ester (in the technical field, the conventional name is called "dicyclopentenyl (meth) acrylate)", dicyclopentyl (meth) acrylate Oxyethyl ester, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, (meth) acrylate such as naphthyl (meth) acrylate or benzyl (meth) acrylate; a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, and itaconic acid Dicarboxylic acid diester of ethyl ester; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]heptane- 2-ene, 5-hydroxybicyclo[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-bis(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-hydroxyl -5-Methylbicyclo[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- Phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2 a bicyclic unsaturated compound such as a olefin, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmalay Yttrium imine, N-benzyl maleimide, N-butylenediamine-3-maleimide benzoate, N-butanediamine-4-malaya Aminobutyrate, N-butylenediamine-6-maleimide caproate, N-butylenediamine-3-maleimide propionate, N-(9-吖Dicarbonyl quinone imine derivatives such as pyridine, maleimide, etc.; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-甲Oxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2, 3-dimethyl-1,3-butadiene and the like.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmalay are preferred. Yttrium, bicyclo [2.2.1] hept-2-ene, and the like.

In the resin [K1], the ratio derived from the respective structural units is preferably in the range below the total structural unit constituting the resin [K1].

Preferably, the structural unit derived from (a): 2 to 60 mol%, the structural unit derived from (b): 40 to 98 mol %; more preferably: the structural unit derived from (a): 10 ~50 mol%, from (b) structural unit: 50~90 mol%.

When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable composition, the developability at the time of pattern formation, and the solvent resistance of the obtained pattern tend to be excellent.

The resin [K1] can be referred to, for example, in the method described in the "Experimental Method for Polymer Synthesis" (Otsuya Ryokan, Ltd., 1st Edition, 1st Edition, 1st March, 1972). The references are made for manufacturing.

Specifically, for example, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel. For example, oxygen is replaced by nitrogen to form a deoxidizing atmosphere, and heating is performed while stirring. The method of insulation. Further, the polymerization initiator, solvent and the like used herein are not particularly limited, and those which are generally used in the field can be used. For example, as a polymerization initiator, for example, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic The solvent (such as a benzamidine peroxide) may be used as the solvent, and the solvent of the coloring curable composition may be, for example, a solvent (E) to be described later.

Further, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) may be taken out by a method such as reprecipitation. In particular, in the case of this polymerization, by using the solvent (E) described below as a solvent, the solution after the reaction can be used as it is, and the production steps can be simplified.

In the resin [K2], the ratio from the respective structural units, in the total structural unit constituting the resin [K2], is preferably: the structural unit derived from (a): 2 to 45 mol%, from (b) Structural unit: 2 to 95 mol%, structural unit derived from (c): 1 to 65 mol%; more preferably: structural unit derived from (a): 5 to 40 mol%, The structural unit derived from (b): 5 to 80 mol%, and the structural unit derived from (c): 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance and mechanical strength of the obtained pattern are obtained. Has an excellent tendency.

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

In the resin [K3], the ratio from the respective structural units, in the total structural unit constituting the resin [K3], is preferably: structural unit derived from (a): 2 to 60 mol%, derived from (c) structural unit: 40 to 98 mol%; more preferably: structural unit derived from (a): 10 to 50 mol% from (c) structural unit: 50 to 90 mol%.

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

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

First, a copolymer of (a) and (c) is produced in the same manner as the method described in the method for producing the resin [K1]. In this case, the ratio derived from the respective structural units is preferably the same ratio as exemplified in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms which is contained in (b) is copolymerized with the above A portion of the carboxylic acid and/or carboxylic anhydride derived from (a) is reacted.

After the manufacture of the copolymer of (a) and (c), the atmosphere in the flask is replaced by nitrogen to air, and the reaction catalyst of (b), a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, reference (two) The methylaminomethyl phenol or the like and a polymerization inhibitor (for example, hydroquinone) are placed in a flask, and the resin [K4] can be produced, for example, by reacting at 60 to 130 ° C for 1 to 10 hours.

The amount of (b) used is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. By setting this range, the storage stability of the colored curable composition, the developability at the time of pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern have a good tendency. . The cyclic ether has high reactivity, and since it is hard to remain unreacted (b), it is preferably used as the resin (K4), and is preferably (b1), more preferably (b1-1).

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibiting agent used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).

The reaction conditions such as the method of introduction, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment or the heat generation amount of the polymerization. Further, the implantation method or the reaction temperature can be appropriately adjusted in consideration of the polymerization equipment or the heat generation amount of the polymerization, in the same manner as the polymerization conditions.

The resin [K5] is obtained in the same manner as the above-mentioned method for producing the resin [K1] as the first step, and a copolymer of (b) and (c) is obtained. In the same manner as described above, the obtained copolymer may be directly used as a solution after the reaction, or may be used. The concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is preferably in the range below the total number of moles of the total structural unit constituting the copolymer.

Preferably, the structural unit derived from (b): 5 to 95 mol%, the structural unit derived from (c): 5 to 95 mol%; more preferably: the structural unit derived from (b): 10 ~90 mol%, structural unit from (c): 10 to 90 mol%.

Further, the same conditions as in the production method of the resin [K4] are used, and the copolymer of (a) having a carboxylic acid or a carboxylic acid anhydride and (b) and (c) has a ring derived from (b). The ether reaction gives the resin [K5].

The amount of (a) used to react with the above copolymer is preferably from 5 to 80 moles per 100 moles of (b). The cyclic ether has high reactivity, and since it is hard to remain unreacted (b), it is preferably (b1), more preferably (b1-1), as the resin (K5).

The resin [K6] is a resin which further reacts the carboxylic acid anhydride with the resin [K5]. The carboxylic acid anhydride is reacted with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

As the carboxylic acid anhydride, for example, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic 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 (norbornene dianhydride/Himic anhydride) and the like. The amount of the carboxylic anhydride used is 1 mole, preferably 0.5 to 1 mole, relative to the amount used in (a).

Specific examples of the resin (B) include a (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer and an acrylic-3,4-epoxytricyclo[5.2.1.0 ^2.6 ]. Resin of oxime ester/(meth)acrylic copolymer, etc. [K1]; 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 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3 a resin such as methyl-3-(meth)acryloxymethyl propylene oxide/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid Copolymer, styrene/(meth)acrylic acid copolymer, (meth)acrylic acid/benzyl (meth)acrylate/styrene copolymer, (meth)acrylic acid/benzyl (meth)acrylate/(methyl) a resin such as an isomeric decyl acrylate copolymer, a (meth)acrylic acid/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymer [K3]; a (meth)acrylic acid Glycidyl ester addition to benzyl (meth) acrylate / (meth) acrylic acid copolymerization a resin, a resin obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic copolymer, and glycidyl (meth)acrylate is added thereto. a resin such as tricyclodecyl methacrylate/benzyl methacrylate/(meth)acrylic acid copolymer [K4]; (meth)acrylic acid and tricyclodecyl (meth)acrylate a resin reacted with a copolymer of glycidyl (meth)acrylate, a resin which reacts a copolymer of (meth)acrylic acid with tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate Resin [K5]; a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, and further reacting tetrahydrophthalic anhydride with the aforementioned resin Resin such as resin [K6].

These resins may be used singly or in combination of two or more.

Among them, the resin (B) is preferably a resin [K1], a resin [K2], and a resin [K3].

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is increased, and the residual film ratio is also high. Since the solubility of the unexposed portion with respect to the developer is good, the resolution tends to be improved.

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

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

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the total amount of the solid content. As long as the content of the resin (B) is in the above range, it has a pattern Type, or the tendency to increase the resolution and the residual film rate of the pattern.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound polymerizable by heat or an active radical and/or an acid generated by the polymerization initiator (D), and is exemplified by, for example, a polymerizable ethylenically unsaturated bond. A compound or the like is preferably a (meth) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(methyl). Acrylate, dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, tetrakis pentaerythritol IX (methyl) Acrylate, ginseng (2-(methyl) propylene methoxyethyl) isocyanate, 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, caprolactone modified dipentaerythritol hexa (methyl) ) Acrylate and the like. The photopolymerizable compound (C) may be used alone or in combination of two or more.

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

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

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, still more preferably from 17 to 55% by mass, based on the total amount of the solid content. When the content of the polymerizable compound (C) is in the above range, the residual film ratio at the time of pattern formation and the chemical resistance of the pattern tend to be improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by polymerization of light or heat, and a known polymerization initiator can be used.

As the polymerization initiator (D), it is preferred to contain a compound selected from the group consisting of alkyl ketone compounds and triterpenoids. a polymerization initiator which is at least one selected from the group consisting of a compound, an acylphosphine oxide compound, an O-mercapto fluorene compound, and a biimidazole compound, more preferably a polymerization initiator containing an O-mercapto fluorene compound .

The O-indenyl hydrazine compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * indicates a keying key.

As the O-indenyl ruthenium compound, for example, N-benzylideneoxy-1-(4-phenylsulfonylphenyl)butan-1-one-2-imine, N-benzidine Oxy-1-(4-phenylsulfonylphenyl)octane-1-one-2-imine, N-benzylformamide 1-(4-phenylsulfonylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-ethyloxy-1-[9-ethyl-6-( 2-Methylbenzylidene)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-{2-methyl- 4-(3,3-Dimethyl-2,4-dioxolanylmethoxy)benzylidenyl}-9H-indazol-3-yl]ethane-1-imine, N- Ethyloxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N- Benzylmethoxy-1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2- Imine and the like. Commercial products such as Irgacure OXE01, OXE02 (above, BASF) and N-1919 (made by ADEKA) can also be used.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). These partial structures may also have a benzene ring.

As the compound having a partial structure represented by the formula (d2), for example, 2-methyl-2-morpholinyl-1-(4-methylsulfonylphenyl)propan-1-one, 2- Dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and the like. Commercial products such as Irgacure 369, 907, and 379 (manufactured by BASF Corporation) can also be used.

As the compound having a partial structure represented by the formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4] -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl Ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, benzyldimethylcondensation Ketones, etc.

In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

As three A compound, for example, 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-sunflower-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)vinyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like. Commercial products such as Irgacure 819 (manufactured by Ciba Japan Co., Ltd.) can also be used.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to, for example, JPH06-75372-A, JPH06-75373-A, 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'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorobenzene Base)-4,4',5,5'-four (three Alkoxyphenyl)biimidazole (refer to, for example, JPS48-38403-B, JPS62-174204-A, etc.), an imidazole compound substituted with a phenylhydroxyalkoxycarbonyl group at the 4,4'5,5'-position (reference For example, JPH07-10913-A, etc.).

Further, as the polymerization initiator (D), for example, a benzoin compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether or the like; benzophenone, o-benzoyl benzoic acid A Ester, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) a benzophenone compound such as benzophenone or 2,4,6-trimethylbenzophenone; a quinone compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone or the like; 10-butylene -2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.

As the acid generator for generating an acid, for example, p-toluenesulfonic acid-4-hydroxyphenyldimethylhydrazine salt, hexafluoroantimonic acid-4-hydroxyphenyldimethylhydrazine salt, p-toluenesulfonic acid -4-Ethyloxyphenyl dimethyl sulfonium salt, hexafluoroantimonate-4-ethenyloxyphenyl. methyl. Benzyl sulfonium salt, p-toluenesulfonic acid-triphenylsulfonium salt, triphenylsulfonium hexafluoroantimonate, diphenylsulfonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate, etc. Salts, or nitrobenzyl tosylates, benzoin tosylates, and the like.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is in the above range, the sensitivity is high, and since the exposure time is shortened, the productivity is improved. The polymerization initiator (D) may further contain a polymerization initiation aid (D1). The polymerization initiation aid (D1) is a compound or a sensitizer which is used to promote polymerization of a photopolymerizable compound which starts polymerization by a polymerization initiator.

As the polymerization initiation aid (D1), for example, an amine compound, an alkoxy ruthenium compound, and 9-oxygen sulphur Compounds, carboxylic acid compounds, and the like.

As the amine compound, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylamine Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as mickleone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylamino)benzophenone or the like, among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

As the alkoxy ruthenium compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9 , 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

9-oxosulfur a compound such as 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

As the carboxylic acid compound, for example, phenylsulfonyl acetic acid, methylphenylsulfonyl acetic acid, ethylphenylsulfonyl acetic acid, methyl ethyl phenylsulfonyl group Acetic acid, dimethylphenylsulfonyl acetic acid, methoxyphenylsulfonyl acetic acid, dimethoxyphenylsulfonyl acetic acid, chlorophenylsulfonyl acetic acid, dichlorophenylsulfonyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

The polymerization initiation aid (D1) may be used alone or in combination of two or more.

When the polymerization initiator (D1) is used, the amount of use is preferably 0.1 to 30 parts by mass, more preferably 1 to 20, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Parts by mass. As long as the amount of the polymerization starting aid (D1) is in this range, the pattern can be formed with higher sensitivity, and the productivity of the pattern tends to increase.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent which is generally used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule but not containing -O-), an ether solvent (a solvent containing -O- in the molecule but not containing -COO-), an ether ester solvent (in the molecule, a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule but not containing -COO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent , dimethyl hydrazine and the like are selected for use.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, butyl orthoacetate, butyl isobutylate, amyl formate, and amyl isophthalate. Butyl propionate, propyl isobutyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexane Alcohol acetate and Γ-butyrolactone and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethyl ether. 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 ether, diethylene glycol dipropyl ether, diethylene glycol II Butyl ether, anisole, phenethyl ether and methyl anisole.

As the ether ester solvent, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate Ester and the like.

As the ketone solvent, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone and isophorone.

As the alcohol solvent, for example, methanol, ethanol, propanol, butanol, and Alcohol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like.

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

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

These solvents may be used alone or in combination of two or more.

Among the above solvents, in terms of coatability and drying property, an organic solvent having a boiling point of 1 atm of 120 ° C or more and 180 ° C or less is preferable. As the solvent (E), preferred is 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, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide; more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, lactic acid Ethyl ester and ethyl 3-ethoxypropionate.

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

<Interacting Agent (F)>

As the surfactant (F), a surfactant having a fluorine atom or a ruthenium atom is suitable. Specifically, it is selected from the group consisting of a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. At least one of the group.

The polyfluorene-based surfactant is, for example, a surfactant having a siloxane coupling. Specific examples include Toray Silicone DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, polyether modified oyster sauce SH8400 (trade name: Toray Silicone; Dow Corning Toray), KP321, KP322 KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

The fluorine-based surfactant is, for example, a surfactant having a fluorocarbon chain. Specifically, for example, Fluorad (trade name) FC430, FC431 (Sumitomo 3M (share) system), Megaface (trade name) F142D, same F171, same F172, same F173, same F177, same F183, same F489, same F554, same R30 (made by DIC), Eftop (trade name) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronic Chemicals), Surflon (trade name) S381, same S382, same SC101, same as SC105 (Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Institute of Precision Chemistry), BM-1000, BM-1100 (all are trade names: BM Chemia).

The polyfluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a siloxane coupling or a fluorocarbon chain. Specific examples Megaface (registered trademark) R08, with BL20, with F475, with F477, with F443 (DIC).

These surfactants may be used alone or in combination of two or more types.

The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, even more preferably the total amount of the coloring curable composition. 0.01% by mass or more and 0.05% by mass or less. Further, the content of the pigment dispersant is not contained in the content. When the content of the surfactant (F) is in the above range, the flatness of the coating film can be made good.

<Other ingredients>

In the colored hardening composition of the present invention, various additives such as a filler, other polymer compound, adhesion promoter, antioxidant, light stabilizer, and chain transfer agent may be added as needed.

<Method for Producing Colored Curable Composition>

The colored hardening composition of the present invention can be obtained, for example, by using the dye of the present invention and the polymerizable compound (C), and the resin (B), polymerization initiator (D), polymerization initiation used in response to the reaction. The auxiliary (D1), the surfactant (F), and other components are mixed with the solvent (E) to produce.

When the pigment (A1) is contained, the pigment (A1) and the solvent (E) are mixed in advance, and it is preferred to disperse the average particle diameter of the pigment to a level of 0.2 μm or less by using a bead mill or the like. At this time, part or all of the aforementioned pigment dispersant and resin (B) which are required for the reaction may be blended. For what is obtained By mixing the salt of the present invention, the residue of the resin (B), and the polymerizable compound (C), and the polymerization initiator (D) and solvent used in response to the desired concentration of the pigment dispersion liquid. The color-curable composition for the purpose can be produced by the residue of (E), the surfactant (F), and other components.

When the salt of the present invention and the dye (A2) are contained, the dye (A2) can be dissolved in the solvent (E) in advance. The solution is preferably filtered using a filter having a pore diameter of about 0.01 to 1 μm.

It is preferable to use a filter having a pore diameter of about 0.01 to 10 μm for filtration after mixing the color-curable composition.

<Method of manufacturing pattern>

A method of producing a pattern of a color filter using the colored photosensitive composition of the present invention is, for example, a photolithography method, an inkjet method, a printing method, or the like. Among them, photolithography is preferred. The photolithography method is a method in which the coloring photosensitive composition is applied onto a substrate and dried to form a composition layer, and the composition layer is exposed and developed through a photomask. In the photolithography method, a coating film can be formed by not using a photomask and/or not performing development at the time of exposure.

The film thickness of the pattern to be produced is not particularly limited, and may be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda-lime glass coated with vermiculite, or polycarbon can be used. A resin plate or the like of an acid ester, polymethyl methacrylate or polyethylene terephthalate or the like, and an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.

The formation of the respective color pixels by the photolithography method can be carried out using conventional or conventional devices or conditions. For example, it can be produced as follows.

First, the colored photosensitive composition is applied onto a substrate, and dried by heating (prebaking) and/or drying under reduced pressure to remove a volatile component such as a solvent to dry, thereby obtaining a smooth composition layer.

Examples of the coating method include a spin coating method, a slit coating method, a slit, and a spin coating method.

The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferably carried out at a temperature of from 50 to 150 Pa and at a temperature of from 20 to 25 °C.

The film thickness of the composition layer is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and is, for example, 0.1 to 20 μm, preferably 0.5 to 6 μm.

Next, the composition layer is exposed through a mask that forms a pattern for the purpose. The pattern on the photomask is not particularly limited, and a pattern suitable for the purpose of use can be used.

As the light source used in the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, it is possible to use light that is less than 350 nm. A filter in the wavelength field is intercepted, or light in the vicinity of 436 nm, near 408 nm, and around 365 nm is selectively extracted by using a band pass filter that extracts the wavelength fields. Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like.

Since a uniform parallel light can be irradiated to the entire exposed surface, or the correct alignment of the mask and the substrate can be performed, it is preferable to use an exposure apparatus such as a photomask alignment machine and a stepper.

The pattern can be formed on the substrate by performing development by bringing the exposed composition layer into contact with the developer. By development, the unexposed portion of the composition layer is dissolved in the developer to be removed. As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

The developing method may be any one of a mixing method, a dipping method, and a spraying method. Further, the substrate can be tilted at an arbitrary angle during development.

It is preferred to carry out water washing after development.

More preferably, post-baking is performed on the resulting pattern. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 0.5 to 10 minutes, more preferably from 1 to 5 minutes.

The pattern thus obtained is suitable as a color filter.

According to the colored photosensitive composition of the present invention, in particular, a color filter excellent in brightness can be produced. The color filter is suitable for use as a display device A color filter such as a liquid crystal display device or an organic EL device, or an electronic paper or a solid-state imaging device.

Example

Hereinafter, the colored photosensitive composition of the present invention will be described in more detail by way of examples. The "%" and "parts" in the examples are not specifically marked as mass % and mass parts.

In the following examples, elemental analysis (VARIO-EL; (Elementar)) was used to confirm the composition of the compound.

Example 1

A solution (s1) was prepared by dissolving 1.00 part of potassium (trifluoromethanesulfonyl)methylate ((CF ₃ SO ₂ ) ₃ CK, manufactured by Central Glass Co., Ltd.) in 60 parts of water. Separately, 1.36 parts of the compound represented by the formula (h-1) was dissolved in 100 parts of water to prepare a solution (t1). The solution (s1) was mixed with the solution (t1) at room temperature and stirred for 2 hours. 500 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 100 parts of ion-exchanged water to obtain 1.50 parts of a salt (X-3).

Example 2

A solution (s2) was prepared by dissolving 1.30 parts of potassium (trifluoromethanesulfonyl)methylate ((CF ₃ SO ₂ ) ₃ CK, manufactured by Central Glass Co., Ltd.) in 30 parts of water. Separately, 1.64 parts of the compound represented by the formula (h-2) was dissolved in 300 parts of water to prepare a solution (t2). The solution (s2) was mixed with the solution (t2) at room temperature and stirred for 4 hours. The precipitate was obtained by suction filtration, and washed with 100 parts of ion-exchanged water to obtain 2.20 parts of a salt (X-6).

Example 3

A solution (s3) was prepared by dissolving 1.50 parts of potassium (trifluoromethanesulfonyl)methylate ((CF ₃ SO ₂ ) ₃ CK, manufactured by Central Glass Co., Ltd.) in 50 parts of water. Separately, 1.78 parts of the compound represented by the formula (h-3) was dissolved in 100 parts of water to prepare a solution (t3). The solution (s3) was mixed with the solution (t3) at room temperature, and then the temperature was raised to 80 ° C and stirred for 6 hours. After the mixture was cooled to room temperature, 900 parts of ion-exchanged water was added, and the mixture was further stirred for 1 hour. The precipitate was obtained by suction filtration, and washed with 100 parts of ion-exchanged water and 50 parts of hexane to obtain 2.50 parts of a salt (X-9).

Example 4

A solution (s4) was prepared by dissolving 0.91 part of CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ K (EF-42, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) in 60 parts of a 5 wt% aqueous acetic acid solution. 1.50 parts of the compound represented by (h-1) was added to the solution (s4) at room temperature, and stirred for 3 hours. The precipitate was obtained by suction filtration, and washed with 100 parts of ion-exchanged water for 3 times to obtain 1.74 parts of a salt (X-2).

Example 5

1.70 parts of a compound (BONTRON (registered trademark) E-108, manufactured by Orient Chemical Industries) of the formula (f-1) was dissolved in 77 parts of N,N-dimethylformamide to prepare a solution ( S5). 3.00 parts of the compound of the formula (h-1) and 0.20 parts of (trifluoromethanesulfonyl)methylated potassium ((CF ₃ SO ₂ ) ₃ CK, manufactured by Central Glass) were added at room temperature. In solution (s5), and stirred for 8 hours. 306 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed three times with 20 parts of ion-exchanged water. The obtained solid matter was added to 51 parts of hexane, and stirred for 1 hour. Insoluble matter was obtained by suction filtration, and washed with 15 parts of hexane for 3 times to obtain 2.10 parts of a salt (X-104).

Example 6

36.8 parts of the compound represented by the formula (h-1) was dissolved in 730 parts of N,N-dimethylformamide to prepare a solution (s6). 8.6 parts of lithium bis(trifluoromethanesulfonyl) ruthenium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution (s6) at room temperature, and stirred for 4 hours. Furthermore, the formula (f-1) is shown A compound (BONTRON (registered trademark) E-108, manufactured by Orient Chemical Industries Co., Ltd.) was added in an amount of 24.3 parts, and stirring was continued for 8 hours. 3649 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 182 parts of ion-exchanged water for 3 times. The obtained solid matter was added to 486 parts of hexane, and stirred for 1 hour. Insoluble matter was obtained by suction filtration, and washed with 97 parts of hexane for 3 times, and then washed with 91 parts of ion-exchanged water for 3 times to obtain 36.7 parts of a salt (X-100).

Still, the (f-1) was dissolved 0.35g of the compound of formula feedstock used as shown in set chloroform and a volume of 250cm ^3, using chloroform to make 2cm ³ becomes diluted in 100cm ^3, adjusted to a concentration of 0.028 a solution of g/L, for which the ultraviolet absorption spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm) was used to determine the maximum absorption wavelength at 400 to 900 nm and The absorbance at the maximum absorption wavelength results in a maximum absorption wavelength of 425 nm and an absorbance of 0.0019.

Example 7

Lithium bis(trifluoromethanesulfonyl) ruthenium (Tokyo Chemical Industry) 1.70 parts of a compound of the formula (h-66) dissolved in 45 parts of N,N-dimethylformamide (method described in Example A50 according to JPH10-97732-A) The obtained solution was stirred at room temperature for 4 hours in a solution of 3.00 parts. 225 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 20 parts of ion-exchanged water for 3 times to obtain 3.80 parts of a salt (X-33).

Example 8

A solution of 2.79 parts of a compound represented by the formula (h-1) dissolved in 110 parts of water is added to 20 parts of water to dissolve bis(fluorosulfonyl) quinone imide potassium salt (Mitsubishi Materials Electronic Chemicals) 1.00 part of the solution was stirred at room temperature for 2 hours. The precipitate was obtained by suction filtration, and washed with 20 parts of ion-exchanged water for 3 times to obtain 1.50 parts of a salt (X-54).

Example 9

A solution of 1.48 parts of the compound of the formula (h-1) dissolved in 250 parts of N,N-dimethylformamide was added to 50 parts of N,N-dimethylformamide to dissolve the double A solution of 1.90 parts of (nonafluorobutylsulfonyl) quinone imide potassium salt (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) was stirred at room temperature for 2 hours. 300 parts of 10% saline solution was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 20 parts of ion-exchanged water for 3 times to obtain 1.29 parts of a salt (X-55).

Example 10

A solution of 3.04 parts of a compound of the formula (h-1) dissolved in 130 parts of water was added to 70 parts of water to dissolve 1,1,2,2,3,3-hexafluoropropane-1,3. To a solution of 1.40 parts of potassium diimide (manufactured by Tokyo Chemical Industry Co., Ltd.), the mixture was stirred at room temperature for 2 hours. The precipitate was taken by suction filtration, and washed with 20 parts of ion-exchanged water for 3 times to obtain 3.60 parts of a salt (X-56).

Example 11

In the mixing, the temperature of the mixture was changed to 30 ° C or less, and 7.83 parts of 2-(4-diethylamino-2-hydroxybenzhydryl)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added thereto. 50 parts of 98% sulfuric acid was mixed and mixed. The resulting solution was cooled to 5 ° C, at which time 3.37 parts of 3-(isopropylamino)phenol (obtained according to the method described in JPH 09-169708-A) was added. Thereafter, the mixture was stirred at 5 ° C for 65 hours. The reaction mixture was added to 250 parts of ice water, and a precipitate was obtained by suction filtration. The residue was dissolved in 180 parts of chloroform, and 300 parts of ion-exchanged water was added thereto, and the aqueous layer was further set to pH 10 using a 10% aqueous sodium hydroxide solution, and stirred for 1 hour. The chloroform layer was separated, washed with 200 parts of ion-exchanged water, and dehydrated with magnesium sulfate. Magnesium sulfate was removed and chloroform was distilled off from the obtained solution under reduced pressure to give 5.50 parts of the compound of formula (hx-83).

30 parts of dehydrated chloroform was added to 3.00 parts of a compound represented by the formula (hx-83), 3.36 parts of triethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), and dimethylaminopyridine (Wako Pure Chemical Industries Co., Ltd.) Into 0.18 parts of (1S)-(+)-10-camphorsulfonic acid (manufactured by Kanto Chemical Co., Ltd.), the mixture was stirred at room temperature for 1 hour. In a solution of 7.2 parts of dehydrated chloroform, dissolved in 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (within 30 °C) The prepared 1.83 parts of the solution was dropped, and stirred at room temperature for 5 hours. The chloroform solution was subjected to liquid separation using 300 parts of 1N hydrochloric acid, followed by 200 parts of 10% saline, and dehydrated with magnesium sulfate. Remove Magnesium sulfate was distilled off from the obtained solution under reduced pressure to give 3.59 parts of the compound of the formula (h-83).

A solution of 2.90 parts of the compound of the formula (h-83) dissolved in 280 parts of water was added to 35 parts of water to dissolve 1,1,2,2,3,3-hexafluoropropane-1,3. To a solution of 1.00 parts of dipotassium diborate (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), the mixture was stirred at room temperature for 2 hours. The precipitate was obtained by suction filtration, and washed with 20 parts of ion-exchanged water for 3 times to obtain 2.23 parts of a salt (X-57).

Example 12

A solution of 8.49 parts of lithium bis(trifluoromethanesulfonyl) rutheide (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50 parts of water was taken in 30 parts of water for 30 minutes to dissolve CIBasic Violet 11 (Aizen Cathilon Brilliant Pink CD-BH, manufactured by Hodogaya Chemical Industry Co., Ltd.) 15.00 parts of the solution, and stirred at room temperature for 3 hours. The precipitate was taken by suction filtration, and washed with 600 parts of ion-exchanged water for 3 times to obtain 18.10 parts of a salt (X-58).

Example 13

5.00 parts of C.I. Basic Violet 11 (Aizen Cathilon Brilliant Pink CD-BH, manufactured by Hodogaya Chemical Industry Co., Ltd.) was dissolved in 62 parts of N,N-dimethylformamide to prepare a solution (s13). 1.70 parts of lithium bis(trifluoromethanesulfonyl) rutheide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution (s13) at room temperature, and stirred for 3 hours. Further, 3.10 parts of a compound (BONTRON (registered trademark) E-108, manufactured by Orient Chemical Industries Co., Ltd.) shown in (f-1) was added to the mixed liquid, and stirring was continued for 8 hours. The mixture was added to 497 parts of ion-exchanged water, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed three times with 50 parts of ion-exchanged water. The obtained solid matter was added to 20 parts of hexane and stirred for 1 hour. Insoluble matter was obtained by suction filtration, and washed with 50 parts of hexane for 3 times, and then washed with 50 parts of ion-exchanged water for 1 time to obtain 7.40 parts of a salt (X-126).

Example 14

120 parts of dehydrated chloroform was added to Basic Violet 10 (Rose Red B, manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 parts of methanol (manufactured by Wako Pure Chemical Industries, Ltd.), 2.14 parts, dimethylaminopyridine (Wako Pure Chemical Co., Ltd.) Industrial Co., Ltd.) 0.77 parts of (1S)-(+)-10-camphorsulfonic acid (manufactured by Kanto Chemical Co., Ltd.) was stirred at room temperature for 1 hour. Study on the dissolution of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride in 49.3 parts of dehydrated chloroform at a temperature of not more than 30 ° C The prepared 5.80 parts of the solution was dropped, and stirred at room temperature for 3 hours. The chloroform solution was subjected to liquid separation using 107 parts of 1N hydrochloric acid, followed by 171 parts of 10% brine, and dried over magnesium sulfate. Magnesium sulfate was removed and chloroform was distilled off from the obtained solution under reduced pressure to give 8.70 parts of the compound of formula (h-4).

A solution of 1.46 parts of lithium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 10 parts of water was taken in 50 parts of water for 30 minutes to dissolve the formula (h- 4) A solution of 2.50 parts of the compound shown was stirred at room temperature for 3 hours. The precipitate was taken by suction filtration, and washed with 100 parts of ion-exchanged water for 3 times to obtain 3.10 parts of a salt (X-59).

Example 15

50 parts of dehydrated chloroform and 3.05 parts of N,N-dimethylformamide were added to 10.00 parts of Basic Violet 10 (Rose Red B, manufactured by Tokyo Chemical Industry Co., Ltd.) under ice bath, and stirred in an ice bath. 1 hour. 5.46 parts of sulfinium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped under an ice bath, and then the temperature was raised to 40 ° C and stirred for 3 hours. After cooling to room temperature, 5.94 parts of pyrrolidine (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped in an ice bath, and then the temperature was raised to 40 ° C and stirred for 2 hours. After the mixture was cooled to room temperature, 100 parts of ion-exchanged water and 150 parts of chloroform were added to carry out liquid separation, and the chloroform layer was separated. To the aqueous layer, 150 parts of chloroform was added for liquid separation, and the chloroform layer was separated. The two chloroform layers were combined and dehydrated with magnesium sulfate. Magnesium sulfate was removed, and chloroform was distilled off from the obtained solution under reduced pressure, and the obtained solid was washed with ethyl acetate (142) to give 10.76 parts of the compound of the formula (h-65). .

1.88 parts of lithium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 35 parts of N,N-dimethylformamide to dissolve the formula (h-65). Show the compound in a solution of 3.50 parts and stir at room temperature Mix for 3 hours. The mixture was added to 280 parts of ion-exchanged water and stirred for further 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed three times with 30 parts of ion-exchanged water to obtain 10.20 parts of a salt (X-32).

Example 16

A solution (s16) was prepared by dissolving 3.00 parts of the compound represented by the formula (h-65) in 30 parts of N,N-dimethylformamide. 1.29 parts of lithium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution (s16) at room temperature, and stirred for 30 minutes. Further, 0.62 parts of a compound represented by the formula (f-8) (BONTRON (registered trademark) E-81, manufactured by Orient Chemical Industries) was added to the mixed solution, and stirring was continued for 8 hours. The mixture was added to 240 parts of ion-exchanged water and stirred for further 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed three times with 30 parts of ion-exchanged water. The obtained solid matter was added to 20 parts of hexane and stirred for 1 hour. Insoluble matter was obtained by suction filtration, and washed with 20 parts of hexane for 3 times, and then washed with 20 parts of ion-exchanged water for 1 time to obtain 3.70 parts of a salt (X-127).

Example 17

A solution (s17) was prepared by dissolving 3.00 parts of the compound represented by the formula (h-66) in 30 parts of N,N-dimethylformamide. 1.26 parts of lithium bis(trifluoromethanesulfonyl) rutheide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution (s17) at room temperature, and stirred for 30 minutes. Further, 0.60 parts of a compound represented by the formula (f-8) (BONTRON (registered trademark) E-81, manufactured by Orient Chemical Industries Co., Ltd.) was added to the mixed solution, and stirring was continued for 3 hours. The mixture was added to 240 parts of ion-exchanged water and stirred for further 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed three times with 30 parts of ion-exchanged water. The obtained solid matter was added to 20 parts of hexane and stirred for 1 hour. Insoluble matter was obtained by suction filtration, and washed with 20 parts of hexane for 3 times, and then washed with 20 parts of ion-exchanged water for 1 time to obtain 4.10 parts of a salt (X-128).

Example 18

0.68 parts of 1,1,2,2,3,3-hexafluoropropane-1,3-didecanoic acid dipotassium salt (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) was added to 20 parts of water to dissolve the formula ( A solution of 2.00 parts of the compound shown in h-2) was stirred at room temperature for 3 hours. The mixture was added to 160 parts of ion-exchanged water and stirred for further 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed three times with 30 parts of ion-exchanged water to obtain 1.80 parts of a salt (X-60).

Example 19

8.30 parts of potassium hexafluorobutyl sulfonate (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) was added to 300 parts of water to dissolve a solution of 15.00 parts of the compound represented by the formula (h-1), and stirred at room temperature. hour. The mixture was added to 1500 parts of ion-exchanged water and stirred for further 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 300 parts of ion-exchanged water for 3 times to obtain 17.10 parts of a salt (X-61).

[Measurement of absorbance]

The mixture 0.35g of Examples 1 to 19 were obtained salt or dissolved in chloroform and a set volume of 250cm ^3, using chloroform to make 2cm ³ becomes diluted in 100cm ^3, adjusted to a concentration of 0.028g / L Solution. For this solution, an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz unit cell, optical path length: 1 cm) was used to measure the maximum absorption wavelength (λ _max ) and the maximum absorption wavelength (λ _{max ).} ) absorbance. The results are shown in Table 14.

[Evaluation of Solubility]

The salts obtained in each of Examples 1 to 6, and the compounds shown in the formulas (h-1), (h-2) and (h-3), respectively, were determined as follows for propylene glycol monomethyl ether B. Acid ester (hereinafter abbreviated as PGMEA), propylene glycol monomethyl ether (hereinafter abbreviated as PGME), ethyl lactate (hereinafter abbreviated as EL), N,N-dimethylformamide (hereinafter abbreviated as DMF) Solubility.

In a 50 mL sample tube, the compound was mixed with the above solvent at the following ratio, after which the sample tube was sealed and shaken at 30 ° C for 3 minutes using an ultrasonic vibration machine. Then, after allowing to stand at room temperature for 30 minutes, it was filtered and the residue was visually observed. When the insoluble matter cannot be confirmed in the residue, the solubility is judged to be good, and when the insoluble matter is confirmed, the solubility is judged to be poor. In Table 15, the solubility is the maximum concentration judged to be good. The results are shown in Table 15. × means that 1% is bad.

1% salt or mixture 0.01g, solvent 1g

3% salt or mixture 0.03g, solvent 1g

5% salt or mixture 0.05g, solvent 1g

7% salt or mixture 0.07g, solvent 1g

10% salt or mixture 0.10g, solvent 1g

15% salt or mixture 0.15g, solvent 1g

20% salt or mixture 0.20g, solvent 1g

The same solubility evaluation was carried out for the salts obtained in Examples 7 to 19 and the compounds represented by the formulas (h-66), (h-83), (h-4), (h-65), and Basic Violet II. . The results are shown in Table 16.

Example 20 [Preparation of colored curable composition]

The following components are mixed to obtain a colored curable composition:

[Production of color filter]

The colored curable composition obtained above was applied onto the glass by a spin coating method to volatilize the volatile component. After cooling, light irradiation was performed using a quartz glass reticle and an exposure machine having a pattern. After the light irradiation, development was carried out with an aqueous potassium hydroxide solution, and heating was carried out at 230 ° C using a baking oven to obtain a color filter.

Example 21

The same procedure as in Example 20 except that the salt (X-3) synthesized in Example 1 was replaced with a mixture of salts (X-104) synthesized in Example 5. The operation was carried out to obtain a colored composition and a color filter.

Example 22

A colored composition and a color filter were obtained in the same manner as in Example 20 except that the salt (X-3) synthesized in Example 1 was replaced with a mixture of salts (X-100) synthesized in Example 56. .

As can be seen from the results of Tables 15 and 16, the salt of the examples exhibited high solubility for the organic solvent. Further, the colored composition containing the salt has a small amount of foreign matter, and a high-quality color filter can be produced.

Synthesis Example 1 <Synthesis of Resin Solution B-2>

In a 1 L flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was passed at 0.02 L/min, and a nitrogen atmosphere was set, and 305 parts by mass of ethyl 2-hydroxypropanoate was placed, and the mixture was heated and heated to 70°C. °C so far. Next, 60 parts by mass of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the following formula (V-1) and the formula (VI-1) were used. The compound shown was dissolved in a molar ratio of 50:50, 240 parts by mass, and 140 parts by mass of ethyl 2-hydroxypropanoate, and the solution was dissolved in a dropping funnel for 4 hours at 70 ° C. Inside the flask. On the other hand, 225 parts by mass of ethyl 2-hydroxypropanoate as a polymerization initiator is a solution in which 30 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved. It took 4 hours to drip into the flask using another dropping funnel. After the completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.3 × 10 ⁴ , a solid content of 33% by mass, and a solid content of 34 mg KOH / g. Resin solution (B-2).

The measurement of the polystyrene-equivalent weight average molecular weight of the above resin was carried out under the following conditions using a GPC method.

Device: HLC-8120GPC (Tosoh system)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0mL/min

Solid concentration of the tested liquid: 0.001~0.01%

Injection volume: 50μL

Detector: RI

Device: HLC-8120GPC (Tosoh system)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0mL/min

Solid concentration of the tested liquid: 0.001~0.01%

Injection volume: 50μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (made by Tosoh)

The components used in the present embodiment are as follows, and the following is abbreviated as follows.

(A-1) Colorant: Salt obtained in Example 6 (X-100)

(A-2) Colorant: red dye represented by formula (3a-23)

(A-3) A coloring agent: a compound represented by the formula (z-1) described in JP-A-2011-118369

(A-4) Colorant: C.I. Pigment. Red 254

(A-5) Colorant: Salt obtained in Example 7 (X-33)

(B-2) Resin: Resin solution obtained in Synthesis Example 1.

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

(D-2) Polymerization initiator: N-1919 (made by ADEKA)

(D1-1) Polymerization start aid: DETX (2,4-diethyl 9-oxosulfur ;Nippon Chemical Co., Ltd.)

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

(E-3) Solvent: propylene glycol monomethyl ether

(F-1) Surfactant: MegafaceF554 (made by DIC)

Example 23 [Modulation of Colored Curable Composition 1]

Mix the following And using a bead mill to sufficiently disperse the pigment to obtain a dispersion.

Also, mix the following And get a solution.

Again, will be as follows

The coloring curable composition 1 is obtained by mixing with the above dispersion liquid and a solution.

Example 24 [Modulation of Colored Curable Composition 2]

Mix the following (A-4) 79.4 parts by mass And using a bead mill to sufficiently disperse the pigment to obtain a dispersion.

Also, mix the following And get a solution.

Again, will be as follows The coloring curable composition 2 is obtained by mixing with the above dispersion liquid and a solution.

Example 25 [Modulation of Colored Curable Composition 3]

Mix the following A bead mill was used to sufficiently disperse the pigment to obtain a dispersion.

Also, mix the following And get a solution.

Again, will be as follows The coloring curable composition 3 is obtained by mixing with the above dispersion liquid and a solution.

Example 26

In the same manner as in Example 25 except that (A-2) was used instead of (A-3), the colored curable composition 4 was obtained.

Example 27

In the same manner as in Example 24 except that (A-3) was used instead of (A-2), the colored curable composition 5 was obtained.

Example 28 [Modulation of Colored Curable Composition 6]

Mix the following And using a bead mill to sufficiently disperse the pigment to obtain a dispersion.

Also, mix the following And get a solution.

Again, will be as follows The coloring curable composition 6 is obtained by mixing with the above dispersion liquid and a solution.

[Formation of the pattern]

The colored curable composition 1 was applied onto a 2" square glass substrate (Eagle XG; manufactured by Corning) using a spin coating method, and then prebaked at 100 ° C for 3 minutes. After cooling, the distance between the substrate coated with the colored curable composition and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used under an air atmosphere. Light exposure was performed at an exposure amount of 150 mJ/cm ² (365 nm reference). After the light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 80 seconds, washed with water, and then subjected to 230 ° C in a baking oven. Bake in minutes. After cooling, the film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 2.3 μm.

[Color Evaluation]

For the pattern on the obtained glass substrate, a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) was used to measure the spectroscopic light, and an isochromatic function of the C light source was used to measure the xy in the XYZ color system of the CIE. Chromaticity coordinates (Bx, By) and lightness. The results are shown in Table 17.

[comparative evaluation]

In the same manner as [formation of the pattern], the same operation as in the formation of the pattern was carried out, and a contrast color measuring machine (CT-1, manufactured by Husui Electric Co., Ltd.) was used for the coating film on the obtained glass substrate. , Detector: BM-5A, light source: F-10), set the blank value to 30000 to measure the contrast. The coating film on the glass substrate was used as a sample by a polarizing film (POLAX-38S; manufactured by Luceo Corporation). The results are shown in Table 17.

[Evaluation]

The colored curable coating film was produced in the same manner as the obtained colored curable compositions 2 to 6, and evaluated for chromaticity, lightness, and contrast. The results are shown in Table 17.

The salt of the present invention is excellent in solubility in an organic solvent.

The salt of the present invention is suitable as a dye, and is particularly suitable as a color filter dye for a display device such as a liquid crystal display device because it has a high absorption coefficient and exhibits high solubility to an organic solvent.

Further, the color hardening group containing the salt of the present invention and a polymerizable compound The manufacture of a machine including a display device having a color filter as a part of the component (for example, a conventional liquid crystal display device, an organic EL device, or the like), and a solid image capturing device When you can use the familiar form.

Claims (11)

a salt comprising at least one anion selected from the group consisting of anions represented by the formulae (I), (II), (III) and (IV), respectively Cation of the skeleton; formula (I) [wherein, X ¹ and X ² are each independently represented by a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or X ¹ and X ^{2 are} bonded to each other to form a fluorinated alkanediyl group having 2 to 4 carbon atoms], Formula (II) [wherein, X ³ to X ⁵ are each independently shown as a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms], and formula (III) [wherein, Y ^{1 is} shown as a fluorinated alkanediyl group having a carbon number of 1 to 4], and the formula (IV) [wherein Y ² is represented by a fluorinated alkyl group having 1 to 4 carbon atoms]. The salt of the first aspect of the patent application, further comprising an n-valent organometallic anion M ^n- , wherein the n-valent organometallic anion M ^n- is a metal atom containing a metal ion capable of forming a divalent or higher metal. The salt of the second aspect of the invention, wherein the n-valent organometallic anion M ^{n- is} a compound represented by the formula (1), satisfies the following requirement M ^n- nZ ⁺ (1) [in the formula (1) , M ^{n - is} shown as the above-mentioned organometallic anion, Z ⁺ is represented as a hydrogen cation or an alkali metal cation, n is an integer of 1 to 3, and when n is an integer of 2 or more, plural Z ⁺ may be the same or different from each other The requirement a: The absorbance measured by the concentration of the compound represented by the formula (1) of 0.028 g/L is 0.05 or less over the entire range of the wavelength of 400 to 900 nm. The salt of claim 2 or 3, wherein the n-valent organometallic anion M ^n- is an organometallic anion having a structure derived from a salicylic acid which may have a substituent, or derived from A plurality of compounds bonded to an amino group of a carboxymethyl group. The salt of any one of the above-mentioned n-valent organic metal anions ^Mn- , wherein the metal atom which can form a divalent or higher metal ion is Al, Cr or Co. A dye comprising the salt of any one of claims 1 to 5 as an active ingredient. A colored hardening composition comprising the dye and the polymerizable compound of claim 6 of the patent application. The color hardening composition of claim 7, which further contains a pigment. The colored curable composition according to the seventh or eighth aspect of the invention, which further comprises at least one selected from the group consisting of a resin and a polymerization initiator. A color filter formed by the color hardening composition according to any one of claims 7 to 9. A display device having a color filter of claim 10 of the patent application.