KR101932769B1 - Salt and colored curable composition - Google Patents

Abstract

[식 (I) 중, X¹ 및 X² 는 각각 독립적으로 불소 원자 또는 탄소수 1 ∼ 4 인 불화알킬기를 나타내거나, 또는, X¹ 과 X² 가 결합하여 탄소수 2 ∼ 4 인 불화알칸디일기를 형성한다]

[식 (Ⅱ) 중, X³ ∼ X⁵ 는 각각 독립적으로 불소 원자 또는 탄소수 1 ∼ 4 인 불화알킬기를 나타낸다]

[식 (Ⅲ) 중, Y¹ 은 탄소수 1 ∼ 4 인 불화알칸디일기를 나타낸다]

[식 (Ⅳ) 중, Y² 는 탄소수 1 ∼ 4 인 불화알킬기를 나타낸다]The present invention provides salts containing at least one anion selected from the group consisting of anions represented by formulas (I), (II), (III) and (IV) and a cation having a xanthene skeleton do.

[In the formula (I), X ¹ and X ² Each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or X ¹ And X ² Form a fluorinated alkanediyl group having 2 to 4 carbon atoms]

[In the formula (II), X ³ to X ⁵ Each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms]

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

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

Description

SALT AND COLORED CURABLE COMPOSITION [0001]

The present invention relates to a salt useful as a dye and a colored curable composition containing the same.

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

Conventionally known salts mentioned above can not sufficiently satisfy the solubility in an organic solvent.

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

[1] A salt containing at least one anion selected from the group consisting of anions represented by formulas (I), (II), (III) and (IV) and a cation having a xanthene skeleton.

The formula (I)

Wherein X ¹ and X ² Each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or X ¹ And X ² Form a fluorinated alkanediyl group having 2 to 4 carbon atoms]

The formula (II)

Wherein X ³ to X ⁵ Each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms]

The formula (III)

Wherein Y < ^{1 >} Represents a fluorinated alkanediyl group having 1 to 4 carbon atoms]

The formula (IV)

Wherein Y < ^{2 >} Represents a fluorinated alkyl group having 1 to 4 carbon atoms]

[2] The salt according to [1], further comprising an n-valent organometallic anion M ^{n -} containing a metal atom capable of forming a divalent or higher valent metal ion.

[3] The n-valent organometallic anion M ^{n -}

[In the formula (1), M ^{n -} represents an organic metal anion as described above. Z ⁺ represents a hydron or an alkali metal cation. and n represents an integer of 1 to 3. and when n is an integer of 2 or more, plural Z ^& lt ^{; + > s} may be mutually the same or different.] The salt according to [2], wherein the compound satisfies the following requirement a.

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

[4] The organic metal anion of [2] or [3], wherein the n-valent organometallic anion M ^{n -} is derived from a compound having a plurality of carboxymethyl groups bonded to salicylic acid or an amino group, Lt; / RTI >

[5] The salt according to any one of [2] to [4], wherein the metal atom capable of forming a divalent or higher valent metal ion contained in the n-valent organometallic 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 containing the dye according to [6] and a polymerizable compound.

[8] The colored curable composition according to [7], further comprising a pigment.

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

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

[11] A display device comprising the color filter according to [10].

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

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

[In the formula (I), X ¹ and X ² Each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or X ¹ And X ² To form a fluorinated alkanediyl group having 1 to 4 carbon atoms]

[In the formula (II), X ³ to X ⁵ Each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms]

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

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

As the fluorinated alkyl group having 1 to 4 carbon atoms represented by X ¹ to X ⁵ in the formulas (I) and (II), a perfluoroalkyl group is preferable, 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 and -C (CF ₃ ) ₃ .

In the above formula (I), X ¹ And X ² Is preferably a perfluoroalkanediyl group, and examples thereof include -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ - and the like.

As the fluorinated alkanediyl group having 1 to 4 carbon atoms represented by Y ¹ in the above formula (III), a perfluoroalkanediyl group is preferable, and for example, -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.

As the fluorinated alkyl group having 1 to 4 carbon atoms represented by Y ² in the above formula (IV), a perfluoroalkyl group is preferable, and for example, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF and the like _{(CF 3) 2, -CF 2} CF 2 CF 2 CF 3, -CF 2 CF (CF 3) 2, -C (CF 3) 3.

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

Examples of the anion represented by the above formula (II) (hereinafter sometimes referred to as "anion (II)") include the following anion (II-1).

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

Anion selected from the group consisting of anion (I), anion (II), anion (III) and anion (IV) (hereinafter sometimes referred to as "anion (I) - (IV) , The salt of the present invention can improve the solubility in an organic solvent while maintaining the color performance of the xanthan gum that is the origin of the cation. Among them, anion (II) is preferable, and anion (II-1) is more preferable.

The cation contained in the salt of the present invention has a xanthene skeleton. Preferably, it is a cation derived from a xanthene dye. A xanthene dye is a generic name of a dye having a xanthene skeleton in a molecule. It is preferable that the xanthene skeleton has at least one amino group and more preferably two amino groups. The cation contained in the salt of the present invention is preferably a cation having a structure in which the nitrogen atom of the amino group has an electrostatic charge, more preferably iminium cation.

Examples of such xanthene dyes include eosin dyes, fluorescein dyes, rhodamine dyes, pyronine dyes, and rosamine dyes. . Also, as described in Synlett, 2010, No. 1, p. 89-92, rhodamine-based dyes in which the oxygen atom of the xanthene skeleton is substituted with a sulfur atom, a selenium atom or a tellurium atom, ) Based dyes.

Xanthene dyes are typically anionic (I) ~ (Ⅳ) anion other than (preferably, C1 ^- or PF ₆ ^-) or have a, carboxylate group (-COO ^-) in the molecule or sulfonate group (-SO ₃ ^-) it has an anionic and the like. In the case of the former, the xanthene dyes are so-called basic dyes, and the cation derived from the xanthene dyes usually contains some or all of the anions other than anions (I) to (IV) (preferably all ). In the latter case, the xanthene dyes are so-called internal salts, and the cation derived from the xanthene dyes is usually a cationic structure in which some or all (preferably all) of the anionic groups of such internal salts are neutralized . Here, not, for example, a carboxylate group (-COO ^-), an ionic ^group-the neutralization the neutralized group is a carboxyl group (-COOH) or its salt (-COONa, etc.), sulfonate group (-SO ₃₎ The group is sulfo group (-SO ₃ H) or its salt (-SO ₃ Na etc.).

Specific examples of the basic dyes in the xanthene dyes include C.I. Basic Red 1, C.I. Basic Red 2, C.I. Basic Red 3, C.I. Basic Red 4, Basic Red 8, Basic Red 11, C.I. Basic Violet 10, C.I. Basic Violet 11, C.I. Basic Violet 25, and dyes represented by the following formulas (h-1) to (h-82).

Specific examples of the internal salt in the xanthene dye include C.I. Mordant Red 27, and dyes represented by the following formulas (h-100) to (h-118), and the like.

The salt of the present invention contains a combination of anions (I) to (IV) and a cation derived from a xanthene dye. Specific examples of such combinations are shown in Tables 1 to 3. In the cartion columns of Tables 1 and 2, the basic dyes in the xanthene dyes from which they are derived are described. As described above, the cation contained in the salt of the present invention is a cation other than Cl ^- or PF ₆ ^- from such a basic dye. In the cartion column of Table 3, the inner salt of the xanthene dyes from which they are derived is described. As described above, the cation contained in the salt of the present invention is a cation of a structure in which the anionic group possessed by the inner salt is neutralized.

The salt of the present invention is preferably a so-called mixed salt containing an n-valent organometallic anion M ^{n -} containing a metal atom capable of forming a divalent or higher metal ion, because the solubility is further improved. These n is the organometallic anion M ^{n -} (1)

[In the formula (1), M ^{n -} represents an organic metal anion as described above. Z ⁺ represents a hydron or an alkali metal cation. and n represents an integer of 1 to 3. when n is an integer of 2 or more, plural Z ^& lt ^{; + > s} may be mutually the same or different)

(Hereinafter may be referred to as " compound (1) "), anion satisfying the following requirement a is more preferable.

Requirement a: The absorbance measured with a 0.028 g / l solution of Compound (1) is 0.05 or less over the entire range of wavelengths from 400 to 900 nm.

In this requirement a, the compound (1) is dissolved in at least one solvent selected from the group consisting of ethyl lactate, chloroform, N, N-dimethylformamide, ion exchange water, methanol, ethanol and toluene to give a concentration of 0.028 g / L solution is prepared, and the absorbance at a wavelength of 400 to 900 nm is measured for this solution. The absorbance is 0.05 or less, preferably 0.035 or less, more preferably 0.0005 or less over the entire wavelength range of 400 to 900 nm.

When the compound (1) satisfies the requirement (a), the salt of the present invention is preferable because it tends to further improve the solubility in an organic solvent while maintaining the color performance of the xanthene dye originating from the cation.

Examples of the alkali metal represented by Z ⁺ in the formula (1) include sodium and potassium.

The organometallic anion represented by M ^{n -} in the formula (1) has a structure in which a metal atom capable of forming a divalent or higher valent metal ion and an organic compound are bonded by ionic bonding or coordination bonding. Examples of such organic compounds include salicylic acid which may have a substituent, a compound having a plurality of carboxymethyl groups bonded to the amino group, benzylic acid which may have a substituent, mandelic acid which may have a substituent, and picolinic acid which may have a substituent have. As the organic metal anion M ^{n -} , an organic metal anion having a structure derived from a salicylic acid which may have a substituent or a compound having a plurality of carboxymethyl groups bonded to an amino group is preferable.

Examples of the salicylic acid which may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, 4-bromosalicylic acid, 3- 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, 3,5-dibromosalicylic acid, 3,5-dibromosalicylic acid, 6-trichlorosalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, and the like

As the compound having a plurality of carboxymethyl groups bonded to the amino group, for example,

And the like.

As the benzylic acid which may have the above substituent, for example,

And the like.

As the above-mentioned mandelic acid which may have a substituent, for example,

And the like.

As the above-mentioned picolinic acid which may have a substituent, for example,

And the like.

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 preferable.

Examples of the organic metal anion M ^{n -} include anion (c-1) to anion (c-72) shown below.

Among them, anion M ^{n -} includes anion c-2, anion c-6 to anion c-9, anion c-14 to anion c- Anion (c-21), Anion (c-22), Anion (c-24) to Anion (c-26), Anion (c-28) anion (c-40), anion (c-43), anion (c-47), anion (c-48) Anion (c-2), anion (c-21), anion (c-22), anion more preferably anion (c-28), anion (c-28), anion (c-28), anion desirable. If they are anionic, the salt of the present invention tends to be more soluble 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.

The salt of the present invention can be prepared by reacting a xanthene dye with a compound containing anions (I) - (IV) and a hydron, or a cation not derived from an anion (I) - (IV) Can be produced by mixing a salt containing an alkali metal cation in a solvent. When the compound (1) is further mixed, a mixed salt in the salt of the present invention may be prepared.

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

As the solvent to be used for the mixing, there may be mentioned N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, , Tetrahydrofuran, dioxane, water and chloroform.

Among these, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, methanol, ethanol, isopropanol and water are preferable. These solvents tend to have a high solubility of the xanthene dyes, the compounds or salts containing anions (I) to (IV), and the compound (1).

When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added to dissolve the compound or salt containing xanthan dyes, anions (I) to (IV), and the compound (1).

The mixture of xanthan dyes and anions (I) to (IV) may be carried out by dissolving both of them in the above-described solvent, or without dissolving them. However, the salt of the present invention can be obtained in a high yield by using and dissolving a solvent in which both are dissolved.

The mixing temperature of the xanthan dyes and anions (I) to (IV) is preferably 0 ° C to 150 ° C, more preferably 10 ° C to 120 ° C, and still more preferably 20 ° C to 100 ° C.

The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 24 hours, and further preferably 3 hours to 12 hours.

When the solvent used in the mixing is a solvent compatible with water, water is added to the solution, and after stirring for another 1 to 3 hours, the precipitate is collected by filtration to obtain the salt of the present invention. The obtained salt may be washed with water as necessary.

When the solvent used in the mixing is a solvent which is incompatible with water, water is added to the solution and the mixture is stirred for another 1 to 3 hours. Thereafter, an organic layer is separated by liquid separation to obtain a solution containing the salt of the present invention. The obtained solution containing the salt of the present invention may be washed with water as required. By removing the solvent from the solution containing the salt of the present invention, the salt of the present invention can be obtained.

The salt of the present invention may be purified by recrystallization after dissolving the salt in a solvent such as acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, or chloroform.

The xanthan dyes may be those commercially available, for example, in Hosoda Yutaka, " Theoretical Preparation Dye Chemistry ", Giboda, pp. 369-377, supervised by Masaki Matsui, " Synthesis and Application of Functional Dyes, , Pages 89 to 96, Synlett, 2010, No. 1, p.89-92, J.0rganic Chemistry, 2008, Vo1.73, 8711-8718, or the like.

The compound (1) may be a commercially available product. For example, as described in JP-A-8-10360 JPH8-10360-B, JP2002-258537-A and Experimental Chemistry Lecture 5, Vol. 22, , By reacting a compound which is a ligand with a sulfate or chloride of a metal.

The salt of the present invention thus obtained is useful as a dye. In addition, the salt of the present invention is useful as a dye used in a color filter of a display device such as a liquid crystal display device, particularly in view of 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 colorant (hereinafter sometimes referred to as "colorant (A)") and further contains a polymerizable compound (C). It is preferable to further contain the pigment (A1) as a coloring agent.

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 further preferably contains the solvent (E) .

The color-curable composition of the present invention may contain a dye (hereinafter sometimes referred to as "dye (A2)") different from the salt of the present invention as a colorant and may contain a polymerization initiator (D1) and a surfactant ). ≪ / RTI >

≪ Pigment (A1) >

As the pigment (A1), there can be mentioned, for example, a compound classified as pigment in the color index (The Society of Dyers and Colourists).

As the pigment (A1), for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 180, 194 and 214;

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

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

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; Violet pigments such as CI Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38;

C.I. Green pigments such as Pigment Green 7, 10, 15, 25, 36, 47, 58;

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

C.I. Pigment black 1, pigment black 7, and the like.

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

As the pigment (A1), a red pigment is preferable, and C.I. Pigment violet 254 is more preferable. By containing the above pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter can be improved.

If necessary, the pigment (A1) may be subjected to surface treatment using a rosin treatment, a pigment derivative into which an acidic group or a basic group has been introduced, graft treatment on the surface of the pigment with a polymer compound or the like, atomization treatment using a sulfuric acid atomization method, A cleaning treatment with an organic solvent or water for removing the ionic impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

It is preferable that the pigment A1 has a uniform particle size. By containing the pigment dispersant and carrying out the dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, polyamine surfactants, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyowa Chemical Industry Co., Ltd.), Sorusparse (manufactured by Zeneca), EFKA (manufactured by CIBA) (Manufactured by Ajinomoto Fine Techno Co., Ltd.) and Disperbyk (manufactured by Big Chemical).

When a pigment dispersant is used, its amount to be used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the pigment (A1). When the amount of the pigment dispersant is in the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

≪ Dye (A2) >

Examples of the dye (A2) include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes and sulfonamide derivatives of acid dyes. of Dyers and Colourists) or known dyes described in Dyeing Note (Color Dyeing). In addition, according to the chemical structure, it is possible to use an azo dye, a cyanine dye, a triphenylmethane dye, a xanthene dye, a phthalocyanine dye, a naphthoquinone dye, an anthraquinone dye, a quinoneimine dye, a methine dye, an azomethine dye, Acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89 (hereinafter abbreviated as CI Solvent Yellow) , 94, 98, 99, 162; C.I. Solvent Red 24, 45, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;

C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

C.I. Solvent Blue 35, 37, 59, 67;

C.I. Solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35,

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

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

C.I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 1, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 335, 340;

C.I. Acid Violet 6B, 7, 9, 17, 19, 102;

C.I. Acid green 1, 3, 5, 9, 16, 25, 27, 28, 50, 58, 63, 65, 80, 104,

C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 108, 109, 129, 132, 136, 138, 141;

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

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

C.I. Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 173, 181, 172, 173, 188, 189, 190, 192, 193, 163, 164, 166, 167, 170, 171, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

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

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

C. I. as a mordant dye. Modand dyes, such as C.I. Modanth Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modal Tread 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;

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

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

C.I. Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. Modand Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc.

The following dyes may also be mentioned.

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. Bat Green 1st.

Also, as the dye (A2), a compound represented by the formula (3) described in JP2011-118369-A is also exemplified.

[In the formula (3), R ^a1 to R ^a18 A halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a phenyl group, -SO ₂ NHR ^a30 , -SO ₃ ^- , -COOR ^a30 or -SO ₂ R ^a30 .

R ^a19 and R ^a20 Each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

R ^a30 each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms, and -CH ₂ - contained in the hydrocarbon group may be substituted with -O- or -CO-.

M ¹ Represents Cr or Co.

n ¹ Represents an integer of 1 to 5.

D ¹ Quot; refers to a monovalent cation derived from a compound having a hydron, a monovalent metal cation or a xanthene skeleton]

Among the compounds represented by the formula (3), the compounds represented by the formulas (3a-1), (3a-5), (3a-7), (3a-8) (3a-16), (3a-23) or (z-1) are preferable, and the red dye represented by the formula (3a-23) is more preferable.

Of these dyes, red dyes are preferable, and C.I. Solvent Red 130 and the compound represented by the formula (3) are more preferable.

These dyes can be appropriately selected in accordance with the spectral spectrum of a desired color filter. These dyes may be used alone 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 5 to 60 mass%, more preferably 8 to 55 mass%, and still more preferably 10 To 50% by mass. When it is in the above range, the color density of the color filter is sufficient and the resin (B) or the polymerizable compound (C) can be contained in a required amount in the composition. Can be formed. Here, the "total amount of solid content" in the present specification means the amount excluding the content of the solvent in the total amount of the colored curable composition. The total amount of the solid content and the content of each component in the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

≪ Resin (B) >

The resin (B) is not particularly limited, and any resin may be used. The resin (B) is preferably an alkali-soluble resin, more preferably a resin containing a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

As the preferable resin (B), the following resins [K1] to [K6] and the like can be mentioned.

(A) (hereinafter also referred to as "(a)") selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having a carbon number of 2 to 4 And a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)").

(A) and (b)) (hereinafter, sometimes referred to as "(c)") which is copolymerizable with the resin (K2) / RTI >

Resin [K3] The copolymer of (a) and (c)

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

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

Resin [K6] A resin obtained by reacting (a) a copolymer of (b) and (c) with a carboxylic acid anhydride.

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

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- Cyclo [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride (hymic acid anhydride);

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] ] Esters;

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

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

(b) can be obtained, for example, by reacting a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of oxiran ring, oxetane ring and tetrahydrofuran ring) and an ethylenically unsaturated bond ≪ / RTI > (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Quot ;, " (meth) acryloyl ", and " (meth) acrylate "

(b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, (Hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)") and the like.

(b1-1) (hereinafter also referred to as "(b1-1)") having a structure obtained by epoxidizing a linear or branched unsaturated aliphatic hydrocarbon, an unsaturated And a monomer (b1-2) having a structure in which an alicyclic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexyl (Meth) acrylate (for example, Cychroma A400, manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate , Compounds represented by the formula (V) and compounds represented by the formula (VI).

[In the formulas (V) and (VI), R ^a and R ^b Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

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

R ^c Represents an alkanediyl group having 1 to 6 carbon atoms.

* Indicates a binding hand with O]

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

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

As R ¹ and R ² , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, , 6-diyl group, and the like.

X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, more preferably a single bond, * - CH ₂ CH ₂ -O- (wherein * represents a bond with O)

Examples of the compound represented by the formula (V) include compounds represented by the formulas (V-1) to (V-15). (V-1), V-3, V-5, V-7, V-9, ). More preferably, the formula (V-1), the formula (V-7), the formula (V-9) and the formula (V-15) can be mentioned.

Examples of the compound represented by the formula (VI) include compounds represented by the formulas (VI-1) to (VI-15). (VI-1), (VI-3), VI-5, VI-7, VI- ). More preferably, the formula (VI-1), the formula (VI-7), the formula (VI-9) and the formula (VI-15) can be mentioned.

The compound represented by the formula (V) and the compound represented by the formula (VI) may be used alone. In addition, they can be mixed at an arbitrary ratio. In the case of mixing, the mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, and even more preferably from 20: 80 to 80:20.

As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-methacryloyloxymethyloxetane, 3-methyl- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

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

(meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1. O ^2,6] decan-8-yl (meth) acrylate (in the art, as the trivial name "dicyclopentanyl (meth) acrylate", the can is also known. The "tricyclo decyl (meth) acrylate" (Tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (referred to in the art as "dicyclopentenyl (meth) acrylate" (Meth) acrylate, propyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (Meth) acrylates such as acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

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

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

2,2-hept-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] 2,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'- hydroxyethyl) bicyclo [2.2.1] 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 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- Cycarbonylbicyclo [ 2,1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) Cyclo [2.2.1] hept-2-ene and the like;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferable from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [K1], the ratio of the structural units derived from each of the resins [K1] is preferably within the following range among the total structural units constituting the resin [K1]

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

(b); , More preferably 40 to 98 mol%

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

(b); And more preferably 50 to 90 mol%.

When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that the storage stability of the colored curable composition, developability in forming the pattern, and solvent resistance of the obtained pattern are excellent.

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by the Chemical Society of Japan, 1st Edition, 1st Edition, March 1, 1972, Can be prepared by reference to the literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, and a solvent are placed in a reaction vessel and heated and maintained in a deoxidizing atmosphere with stirring, for example, by replacing oxygen with nitrogen Method. The polymerization initiator, solvent and the like used herein are not particularly limited, and those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and organic peroxides such as benzoyl peroxide ). The solvent may be one which dissolves the respective monomers, and the solvent (E) to be described later as a solvent of the colored curable composition may, for example, be mentioned.

The solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by re-precipitation or the like. In particular, by using the solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the proportion of the structural unit derived from each of the resins [K2]

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

(b); 2 to 95 mol%

(c); It is preferably 1 to 65 mol%

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

(b); 5 to 80 mol%

(c); And more preferably 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is within the above range, there is a tendency that the storage stability of the colored curing composition, the developability in forming the pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained pattern are excellent.

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

In the resin [K3], the ratio of the structural unit derived from each of the resins [K3]

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

(c); , More preferably 40 to 98 mol%

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

(c); And more preferably 50 to 90 mol%.

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

The resin [K4] is obtained by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid and / or carboxylic acid anhydride having (a) Can be manufactured.

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

Next, a cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer.

Subsequently to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air in nitrogen, and (b) a reaction catalyst of a carboxylic acid or carboxylic anhydride and a cyclic ether The resin [K4] is produced by putting a polymerization inhibitor (for example, hydroquinone or the like) or the like in a flask, for example, at 60 to 130 ° C for 1 to 10 hours .

(b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting this range, there is a tendency that the balance between the storage stability of the colored curable composition, the developability in forming the pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are improved. (B1) is preferably used as the resin (K4), and (b1-1) is preferable because the reactivity of the cyclic ether is high and unreacted (b)

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the injection method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization. In addition, the injection method and the reaction temperature can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization, as in the case of the polymerization conditions.

Resin [K5] is a first step, and a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production of resin [K1]. As the copolymer obtained in the same manner as above, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by re-precipitation or the like.

the proportion of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of the total structural units constituting the copolymer.

(b); 5 to 95 mol%

(c); , More preferably 5 to 95 mol%

(b); 10 to 90 mol%

(c); And more preferably 10 to 90 mol%.

In the same manner as in the production of the resin (K4), the cyclic ether derived from the copolymer (b) having the copolymer (b) and the copolymer (c) is reacted with the carboxylic acid or carboxylic acid anhydride To obtain a resin [K5].

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). (B1) is preferably used as the resin (K5), and (b1-1) is preferable because the reactivity of the cyclic ether is high and the unreacted (b)

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. A carboxylic acid anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

Examples of the carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride). The amount of the carboxylic acid anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate / (meth) Resin [K1] such as a copolymer; (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) resins such as acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymer [K2]; Benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, styrene / (meth) acrylic acid copolymer, A resin [K3] such as a (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, or an isobornyl (meth) acrylate copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (meth) ) Resin, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting a (meth) acrylic acid with a copolymer; A resin [K6] such as a resin obtained by reacting a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride .

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

Among them, resin [K1], resin [K2] and resin [K3] are preferable as resin (B).

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and 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 1.1 to 6, and more preferably 1.2 to 4.

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

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total amount of the solid components. When the content of the resin (B) is in the above range, a pattern can be formed and the residual film ratio of resolution and pattern tends to be improved.

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound capable of polymerizing with heat or an active radical and / or an acid generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenic unsaturated bond And is preferably a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol Ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra Propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, There may be mentioned acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) 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 from 150 to 2,900, more preferably from 25 to 1,500.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total 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 far as it is a compound capable of initiating polymerization by generating an active radical or an acid by the action of light or heat, and a known polymerization initiator can be used.

As the polymerization initiator (D), a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, 0-acyloxime compounds and imidazole compounds is preferable, and O- A polymerization initiator containing an acyloxime compound is more preferable.

The O-acyloxime compound is a compound having a partial structure represented by formula (d1). Herein, * denotes a combined hand.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- - ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] (3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ -9-ethyl-6- (2-methylbenzoyl) -9H-carbazole < / RTI > -3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used.

The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). Of these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -1-butanone, and the like. IRGACURE 369, 907, 379 (manufactured by BASF), and the like may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, an oligomer of 2-hydroxy- ,?,? -diethoxyacetophenone, and benzyl dimethyl ketal.

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

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. A commercially available product such as Irgacure 819 (manufactured by Chiba Japan) may be used.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, see JPH06-75372-A, JPH06-75373-A and the like), 2,2'-bis ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'- , 5,5'-tetra (trialkoxyphenyl) biimidazole (for example, see JPS48-38403-B, JPS62-174204-A and the like), 4,4'5,5'- An imidazole compound substituted by an alkoxy group (for example, JPH07-10913-A, etc.), and the like.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone, etc .; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiator (D1) (particularly amines) to be described later.

Examples of the acid generator generating an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p - onium salts such as toluene sulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyltosylates, 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, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is in the above range, the sensitivity is improved and the exposure time is shortened, thereby improving the productivity.

The polymerization initiator (D) may further contain a polymerization initiator (D1). The polymerization initiator (D1) is a compound or sensitizer used for promoting polymerization of the photopolymerizable compound initiated by the polymerization initiator.

Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, '-Bis (ethylmethylamino) benzophenone, among which 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,1O-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, Ethoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Oakstone, and the like.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chloro Phenylsulfanyl acetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

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

When these polymerization initiation assistants (D1) are used, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Wealth. When the amount of the polymerization initiator (D1) is within the above range, the pattern can be formed with higher sensitivity and the productivity of the pattern tends to be improved.

≪ Solvent (E) >

The solvent (E) is not particularly limited, and a solvent commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent, aromatic hydrocarbon solvent, amide solvent, dimethyl Sulfoxide, and the like.

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

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, diethylene glycol monobutyl ether, propylene Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, And the like.

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

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

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

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

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

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

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 占 폚 or more and 180 占 폚 or less at 1 atm is preferable from the viewpoint of coatability and dryness. As the solvent (E), 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, -Hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferable .

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 color-curable composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color characteristics are not insufficient when the color filter is formed, so that the display characteristics tend to be good.

≪ Surfactant (F) >

As the surfactant (F), a surfactant having a fluorine atom or a silicon atom is suitable. Specifically, at least one selected from the group consisting of a silicone surfactant, a fluorine surfactant, and a silicon surfactant having a fluorine atom can be enumerated.

Examples of the silicone surfactant include a surfactant having a siloxane bond. Concretely, it is possible to use a silicone oil such as Torensilicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Polyether Modified Silicon Oil SH8400 (trade name: Toresilicon, Toray Dow Corning) KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (Momentive Performance Matrix Manufactured by Japan Joint Corporation).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Concretely, F412, F171, F172, F173, F177, F183, F489, F554 (trade names) FC430 and FC431 (manufactured by Sumitomo 3M Ltd.) (Trade name) S381, S382, SC101 (trade name) manufactured by Mitsubishi Materials Corporation), EF301, EF301, EF351 and EF352 , SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.), BM-1000 and BM-1100 (all trade names, manufactured by BM Chemie).

Examples of the silicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, Megapox (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by DIC) can be used.

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

The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more relative to the total amount of the colored curable composition 0.05% by mass or less. The content of the pigment dispersant is not included in the content. When the content of the surfactant (F) is in the above range, the flatness of the coated film can be improved.

≪ Other components >

The colored curable composition of the present invention may contain various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, if necessary.

≪ Process for producing colored curable composition >

The colored curable composition of the present invention can be obtained, for example, by mixing the dye of the present invention and the polymerizable compound (C), and the resin (B), the polymerization initiator (D), the polymerization initiator (D1) (F) and other components with the solvent (E).

When the pigment (A1) is contained, it is preferable that the pigment (A1) is previously mixed with the solvent (E) and dispersed with a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. To the obtained pigment dispersion are added the salt of the present invention, the remainder of the resin (B) and the polymerizable compound (C) and the polymerization initiator (D) to be used if necessary, the remainder of the solvent (E), the surfactant (F) The desired colored curable composition can be prepared by mixing the components such as the above-mentioned components and the like so as to have a predetermined concentration.

The salt of the present invention and the dye (A2) containing the dye (A2) may be respectively dissolved in the solvent (E) beforehand. The solution is preferably filtered through a filter having a pore diameter of about 0.01 to 1 mu m.

The colored curable composition after mixing is preferably filtered with a filter having a pore diameter of about 0.01 to 10 mu m.

≪ Pattern production method >

Examples of a method for producing a pattern of a color filter using the colored photosensitive composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Among them, a photolithographic method is preferable. The photolithographic method is a method in which the above-mentioned colored photosensitive composition is applied to a substrate, followed by drying to form a composition layer, and the composition layer is exposed through a photomask to develop. In the photolithographic method, a coating film may be formed by not using a photomask at the time of exposure and / or by not developing it.

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

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass whose surface is coated with a silica, a resin plate such as polycarbonate, polymethylmethacrylate or polyethylene terephthalate, silicon, , Silver, a silver / copper / palladium alloy thin film, or the like is formed. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be carried out by a known apparatus or condition. For example, it can be produced as follows.

First, the colored photosensitive composition is coated on a substrate and dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent and drying to obtain a smooth composition layer.

Examples of the application method include a spin coat method, a slit coat method, and a slit and spin coat method.

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

In the case of performing the reduced-pressure drying, it is preferably carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa.

The film thickness of the composition layer is not particularly limited and can be appropriately adjusted depending on the materials to be used, applications, etc., and is, for example, 0.1 to 20 탆, preferably 0.5 to 6 탆.

Next, the composition layer is exposed through a photomask for forming a desired pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.

As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of less than 350 nm is cut using a filter that cuts the wavelength band, or a band-pass filter for extracting light in the vicinity of 436 nm, around 408 nm, and around 365 nm, Or may be selectively taken out. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps.

It is preferable to use an exposure apparatus such as a mask aligner or a stepper because it is possible to uniformly irradiate the entire exposure surface with a parallel light beam or to precisely align the photomask with the substrate.

A pattern is formed on the substrate by bringing the exposed composition layer into contact with a developing solution. By the development, the unexposed portion of the composition layer is dissolved and removed in the developer. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant.

The developing method may be any of a paddle method, a dipping method, and a spray method. Further, the substrate may be inclined at an arbitrary angle during development.

It is preferable to rinse after development.

In addition, post-baking is preferably performed on the obtained pattern. The post bake temperature is preferably 150 to 250 DEG C, more preferably 160 to 235 DEG C. The post-baking time is preferably 0.5 to 10 minutes, more preferably 1 to 5 minutes.

The pattern thus obtained is useful as a color filter.

From the colored photosensitive composition of the present invention, a color filter having particularly excellent brightness can be produced. The color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, etc.), an electronic paper, a solid-state image pickup device and the like.

Example

Hereinafter, the colored photosensitive composition of the present invention will be described in more detail by examples. In the examples, "% " and " part " are parts by mass and parts by mass unless otherwise specified.

In the following examples, the composition of the compound was confirmed by elemental analysis (VARIO-EL; manufactured by Elementer Co.).

Example 1

(S1) prepared by dissolving 1.00 parts of potassium tris (trifluoromethanesulfonyl) methane ((CF ₃ SO ₂ ) ₃ CK, Central Glass Co., Ltd.) in 60 parts of water was prepared. Separately, a solution (t1) in which 1.36 parts of the compound represented by the formula (h-1) was dissolved in 100 parts of water was prepared. At room temperature, solution (s1) and solution (t1) were mixed 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, the precipitate was collected by suction filtration and washed with 100 parts of ion-exchanged water to obtain 1.50 parts of salt (X-3).

Example 2

(S2) was prepared by dissolving 1.30 parts of potassium tris (trifluoromethanesulfonyl) methane ((CF ₃ SO ₂ ) ₃ CK, Central Glass Co., Ltd.) in 30 parts of water. Separately, a solution (t2) in which 1.64 parts of the compound represented by the formula (h-2) was dissolved in 300 parts of water was prepared. The solution (s2) and the solution (t2) were mixed at room temperature and stirred for 4 hours. The precipitate was collected by suction filtration and washed with 100 parts of ion-exchanged water to obtain 2.20 parts of salt (X-6).

Example 3

(S3) was prepared by dissolving 1.50 parts of potassium tris (trifluoromethanesulfonyl) methane ((CF ₃ SO ₂ ) ₃ CK, Central Glass Co., Ltd.) in 50 parts of water. Separately, a solution (t3) in which 1.78 parts of the compound represented by the formula (h-3) was dissolved in 100 parts of water was prepared. The solution (s3) and the solution (t3) were mixed at room temperature, then heated to 80 占 폚 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 collected by suction filtration, washed with 100 parts of ion-exchanged water and 50 parts of hexane to obtain 2.50 parts of salt (X-9).

Example 4

(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 Corporation) in 60 parts of 5 wt% acetic acid aqueous solution. At room temperature, 1.50 parts of the compound represented by (h-1) was added to the solution (s4) and stirred for 3 hours. The precipitate was collected by suction filtration and washed three times with 100 parts of ion-exchanged water to obtain 1.74 parts of salt (X-2).

Example 5

A solution (s5) in which 1.70 parts of a compound represented by the formula (f-1) (BONTRON (registered trademark) E-108, Orient Chemical Industries, Ltd.) was dissolved in 77 parts of N, N-dimethylformamide. 3.00 parts of a compound represented by the formula (h-1) and 0.22 parts of potassium tris trifluoromethanesulfonyl methide ((CF ₃ SO ₂ ) ₃ CK, Central Glass Co., Ltd.) were added to a solution (s5) And the mixture was stirred for 8 hours. The mixture was added to 306 parts of ion-exchanged water, and the mixture was stirred for another 1 hour. Thereafter, the precipitate was collected by suction filtration and washed three times with 20 parts of ion-exchanged water. The resulting solid was added to 51 parts of hexane and stirred for 1 hour. The insoluble material was collected by suction filtration and washed with 15 parts of hexane three times to obtain 2.10 parts of salt (X-104).

Example 6

A solution (s6) in which 36.8 parts of the compound represented by the formula (h-1) was dissolved in 730 parts of N, N-dimethylformamide was prepared. At room temperature, 8.6 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution (s6) and the mixture was stirred for 4 hours. 24.3 parts of a compound represented by the formula (f-1) (BONTRON (registered trademark) E-108, Orient Chemical Industries Ltd.) was further added to the mixture, followed by stirring for 8 hours. The mixture was added to 3649 parts of ion-exchanged water, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was collected by suction filtration and washed with 182 parts of ion-exchanged water three times. The resulting solid was added to 486 parts of hexane and stirred for 1 hour. Insoluble materials were obtained by suction filtration, washed with 97 parts of hexane three times and then once with 91 parts of ion-exchanged water to obtain 36.7 parts of salt (X-100).

0.35 g of the compound represented by the formula (f-1) used as a raw material was dissolved in chloroform to make a volume of 250 cm 3, 2 cm 3 of the solution was diluted with chloroform to 100 cm 3, and a solution with a concentration of 0.028 g / (V-650DS, manufactured by Nippon Spectroscopy) (quartz cell, optical path length: 1 cm) was used to adjust the maximum absorption wavelength and the maximum absorption wavelength at 400 to 900 nm in the ultraviolet visible spectrophotometer , The maximum absorption wavelength was 425 nm and the absorbance was 0.0019.

Example 7

To a solution prepared by dissolving 3.00 parts of the compound represented by the formula (h-66) (obtained according to the method described in Example A50 of JPH10-97732-A) in 45 parts of N, N-dimethylformamide, bis (trifluoromethane Sulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 4 hours. 225 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was collected by suction filtration and washed three times with 20 parts of ion-exchanged water to obtain 3.80 parts of salt (X-33).

Example 8

2.79 parts of the compound represented by the formula (h-1) was dissolved in 110 parts of water in a solution of 1.00 parts of bis (fluorosulfonyl) imide potassium salt (manufactured by Mitsubishi Chemical Corporation) in 20 parts of water And the mixture was stirred at room temperature for 2 hours. The precipitate was collected by suction filtration and washed three times with 20 parts of ion-exchanged water to obtain 1.50 parts of salt (X-54).

Example 9

(H-1) shown below was added to a solution prepared by dissolving 1.50 parts of bis (nonafluorobutanesulfonyl) imide potassium salt (manufactured by Mitsubishi Chemical Corporation) in 50 parts of N, N-dimethylformamide Was dissolved in N, N-dimethylformamide (250 parts), and the mixture was stirred at room temperature for 2 hours. 300 parts of 10% saline was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was collected by suction filtration and washed three times with 20 parts of ion-exchanged water to obtain 1.29 parts of salt (X-55).

Example 10

(H-1) was added to a solution prepared by dissolving 1.40 parts of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfone imidazolium potassium (manufactured by Tokyo Chemical Industry Co., Ltd.) ) Was dissolved in 130 parts of water, and the mixture was stirred at room temperature for 2 hours. The precipitate was collected by suction filtration and washed three times with 20 parts of ion-exchanged water to obtain 3.60 parts of salt (X-56).

Example 11

7.83 parts of 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added to 50 parts of 98% sulfuric acid so that the temperature of the mixture was 30 DEG C or less during mixing . The resulting solution was cooled to 5 占 폚, and 5.37 parts of 3- (isopropylamino) phenol (prepared according to the method described in Japanese Patent Application Laid-Open No. 9-169708) was added thereto. Thereafter, this mixture was stirred at 5 DEG C for 65 hours. The reaction mixture was added to 250 parts of ice water, and the precipitate was collected by suction filtration. The residue was dissolved in 180 parts of chloroform, 300 parts of ion-exchanged water was added, and the aqueous layer was adjusted to pH 10 with 10% aqueous sodium hydroxide solution and stirred for 1 hour. The chloroform layer was collected, washed with 200 parts of ion-exchanged water, and dehydrated with magnesium sulfate. From the solution obtained by removing magnesium sulfate, chloroform was distilled off under reduced pressure to obtain 5.50 parts of a compound represented by the formula (hx-83).

, 3.00 parts of a compound represented by the formula (hx-83), 3.16 parts of triethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.24 parts of dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, -10-camphorsulfonic acid (manufactured by Kanto Chemical Co., Ltd.) (0.18 parts) was added 30 parts of dehydrated chloroform, and the mixture was stirred at room temperature for 1 hour. A solution prepared by dissolving 1.83 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tojin Chemical Industry Co., Ltd.) in 7.2 parts of dehydrated chloroform was added dropwise at 30 ° C for 5 hours Lt; / RTI > The chloroform solution was diluted with 300 parts of 1 N hydrochloric acid and then with 200 parts of 10% brine, followed by dehydration with magnesium sulfate. Chloroform was distilled off from the solution obtained by removing magnesium sulfate under reduced pressure to obtain 3.59 parts of a compound represented by the following formula (h-83).

To a solution prepared by dissolving 1.00 parts of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonic acid dipotassium salt (manufactured by Mitsubishi Chemical Corporation) in 35 parts of water, h-83) in 280 parts of water was added thereto, and the mixture was stirred at room temperature for 2 hours. The precipitate was collected by suction filtration and washed three times with 20 parts of ion-exchanged water to obtain 2.23 parts of salt (X-57).

Example 12

C.I. (Trifluoromethanesulfonyl) imide lithium (commercially available from Tokyo Chemical Industries Co., Ltd.) was added to a solution prepared by dissolving 15.00 parts of Basic Violet 11 (Aizen Cathilon Brilliant Pink CD-BH, Hodogaya Chemical Co., ) In 50 parts of water was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 3 hours. The precipitate was collected by suction filtration and washed three times with 600 parts of ion-exchanged water to obtain 18.10 parts of salt (X-58).

Example 13

C.I. (S13) was prepared by dissolving 5.00 parts of Basic Violet 11 (Aizen Cathilon Brilliant Pink CD-BH, Hodogaya Chemical Co., Ltd.) in 62 parts of N, N-dimethylformamide. 1.70 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution (s13) at room temperature, followed by stirring for 3 hours. To the resulting mixture was further added 3.10 parts of a compound represented by the formula (f-1) (BONTRON (registered trademark) E-108, Orient Chemical Industries Ltd.), followed by stirring for 8 hours. The mixed solution was added to 497 parts of ion-exchanged water, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was collected by suction filtration and washed three times with 50 parts of ion-exchanged water. The resulting solid was added to 20 parts of hexane and stirred for 1 hour. Insoluble materials were obtained by suction filtration, washed with 50 parts of hexane three times and then once with 50 parts of ion-exchanged water to obtain 7.40 parts of salt (X-126).

Example 14

, 10.00 parts of Basic Violet 10 (Rhodamine B, manufactured by Tokyo Chemical Industry Co., Ltd.), 2.14 parts of methanol (manufactured by Wako Pure Chemical Industries, Ltd.), 0.77 parts of dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, 1S) - (+) - 10-camphorsulfonic acid (manufactured by Kanto Chemical Co., Ltd.) (0.58 part) was added 120 parts of dehydrated chloroform, and the mixture was stirred at room temperature for 1 hour. A solution prepared by dissolving 5.80 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tojin Chemical Industry Co., Ltd.) in 49.3 parts of dehydrated chloroform was added dropwise at 30 ° C for 3 hours Lt; / RTI > The chloroform solution was separated into 107 parts of 1N hydrochloric acid and then 171 parts of 10% brine, followed by dehydration with magnesium sulfate. From the solution obtained by removing magnesium sulfate, chloroform was distilled off under reduced pressure to obtain 8.70 parts of a compound represented by the following formula (h-4).

A solution prepared by dissolving 1.46 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 parts of water was added to a solution of 2.50 parts of the compound represented by the formula (h-4) Was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 3 hours. The precipitate was collected by suction filtration and washed three times with 100 parts of ion-exchanged water to obtain 3.10 parts of 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 (Rhodamine B, Tokyo Chemical Industry Co., Ltd.) in an ice bath, and the mixture was stirred for 1 hour in an ice bath. 5.46 parts of thionyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise in an ice bath, and the mixture was heated 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 added dropwise in an ice bath, and then the temperature was raised to 40 占 폚 and stirred for 2 hours. After cooling the mixture to room temperature, 100 parts of ion-exchanged water and 150 parts of chloroform were added, and the chloroform layer was separated by separating. To the aqueous layer was added 150 parts of chloroform, and the solution was separated to separate a chloroform layer. The two chloroform layers were combined and dehydrated with magnesium sulfate. The chloroform was distilled off from the solution obtained by removing magnesium sulfate under reduced pressure, and the resulting solid was washed with 142 parts of ethyl acetate to obtain 10.76 parts of a compound represented by the following formula (h-65).

1.89 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a solution of 3.50 parts of the compound represented by the formula (h-65) in 35 parts of N, N- dimethylformamide And the mixture was stirred at room temperature for 3 hours. The mixture was added to 280 parts of ion-exchanged water and stirred for another 1 hour. Thereafter, the precipitate was collected by suction filtration and washed three times with 30 parts of ion-exchanged water to obtain 10.20 parts of salt (X-32).

Example 16

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

Example 17

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

Example 18

To a solution prepared by dissolving 2.00 parts of the compound represented by the formula (h-2) in 20 parts of water was added 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonic acid dipotassium salt (Mitsubishi Materiel Electronics Co., 0.68 part) was added, and the mixture was stirred at room temperature for 3 hours. And the mixture was added to 160 parts of ion-exchanged water, followed by stirring for another 1 hour. Thereafter, the precipitate was collected by suction filtration and washed three times with 30 parts of ion-exchanged water to obtain 1.80 parts of salt (X-60).

Example 19

8.30 parts of nonafluorobutanesulfonic acid potassium (manufactured by Mitsubishi Materials Corporation) was added to a solution of 15.00 parts of the compound represented by the formula (h-1) in 300 parts of water, and the mixture was stirred at room temperature for 3 hours. The mixture was added to 1500 parts of ion-exchanged water, and the mixture was stirred for another 1 hour. Thereafter, the precipitate was collected by suction filtration and washed three times with 300 parts of ion-exchanged water to obtain 17.10 parts of salt (X-61).

[Measurement of absorbance]

0.35 g of the salt or salt mixture obtained in each of Examples 1 to 19 was dissolved in chloroform to make a volume of 250 cm 3 and 2 cm 3 of the solution was diluted with chloroform to 100 cm 3 to prepare a solution having a concentration of 0.028 g / . (? _Max ) and a maximum absorption wavelength (? _Max ) using an ultraviolet visible spectrophotometer (V-650DS, manufactured by Nippon Gosei Co., Ltd.) (quartz cell, optical path length: Was measured. Table 14 shows the results.

[Evaluation of Solubility]

Propyleneglycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) was added to the salts respectively obtained in Examples 1 to 6 and the compounds respectively represented by formulas (h-1), (h-2) and (h- ), Propylene glycol monomethyl ether (hereinafter abbreviated as PGME), ethyl lactate (hereinafter abbreviated as EL) and N, N-dimethylformamide (hereinafter abbreviated as DMF) Respectively.

In a 50 ml sample tube, the compound and the solvent were mixed at the following ratios. Thereafter, the sample tube was tightened and shaken with an ultrasonic shaker at 30 캜 for 3 minutes. Then, the mixture was allowed to stand at room temperature for 30 minutes, filtered, and the residue was visually observed. When the insoluble matter could not be identified as a residue, it was determined that the solubility was good. When the insoluble matter could be identified, it was determined that the solubility was bad. Table 15 shows the maximum concentration determined to be good in solubility. The results are shown in Table 15. X means 1% defective.

0.01% salt or mixture of 1%, 1 g of solvent

0.03 g of 3% salt or mixture, 1 g of solvent

0.05% of a 5% salt or mixture, 1 g of a solvent

0.07 g of 7% salt or mixture, 1 g of solvent

0.10 g of 10% salt or mixture, 1 g of solvent

0.15 g of 15% salt or mixture, 1 g of solvent

0.20 g of 20% salt or mixture, 1 g of solvent

The solubility of the salt obtained in Examples 7 to 19 and the compound represented by Formulas (h-66), (h-83), (h-4) . The results are shown in Table 16.

Example 20

[Preparation of colored curable composition]

(A) Colorant: Salt (X-3): 20 parts of the salt synthesized in Example 1

(B-1) Resin: 70 parts of methacrylic acid / benzyl methacrylate copolymer (molar ratio: 30/70, weight average molecular weight: 10700, acid value: 70 mgKOH / g)

(C-1) Polymerizable compound: 30 parts of dipentaerythritol hexaacrylate (manufactured by Nippon Yakuza)

(D-1) Polymerization initiator: benzyl dimethyl ketal (Irgacure 651; BASF Japan)

Part 15

(E-1) Solvent: N, N-dimethylformamide 680 parts

To obtain a colored curable composition.

[Production of color filter]

On the glass, the colored curable composition obtained above is applied by spin coating to volatilize the volatile components. After cooling, light is irradiated using a quartz glass photomask having a pattern and an exposure machine. After the irradiation with light, it is developed with an aqueous solution of potassium hydroxide and heated at 230 DEG C in an oven to obtain a color filter.

Example 21

A coloring 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 changed to the salt mixture (X-104) synthesized in Example 5.

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 changed to the salt mixture (X-100) synthesized in Example 6.

From the results of Tables 15 and 16, it can be seen that the salts of the examples show a high solubility with respect to the organic solvent. In addition, the coloring composition containing the salt has less occurrence of foreign matter, and it is possible to produce a high-quality color filter.

Synthesis Example 1

<Synthesis of Resin Solution B-2>

In a 1 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 305 parts by mass of ethyl 2-hydroxypropanoate was added and heated to 70 deg. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (a compound represented by the following formula (V-1) and a compound represented by the formula (VI- : 50) and 140 parts by mass of ethyl 2-hydroxypropanoate to prepare a solution. The solution was added dropwise to a flask heated at 70 占 폚 for 4 hours using a dropping funnel Respectively. On the other hand, a solution prepared by dissolving 30 parts by mass of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl 2-hydroxypropanoate was added over 4 hours using another dropping funnel Lt; / RTI &gt; After completion of the dropwise addition of the polymerization initiator solution, the mixture was maintained at 70 占 폚 for 4 hours and then cooled to room temperature to obtain a copolymer having a weight average molecular weight Mw of 1.3 占⁰⁴ , a solid content of 33 mass% and a solid acid value of 34 mgKOH / g To obtain a resin solution (B-2).

The polystyrene reduced weight average molecular weight of the resin was measured by the GPC method under the following conditions.

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

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 ml / min

Solid concentration of the test solution; 0.001 to 0.01%

Dose; 50 μl

Detector; RI

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

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 ml / min

Solid concentration of the test solution; 0.001 to 0.01%

Dose; 50 μl

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The components used in this embodiment are as follows, and the following description may be omitted.

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

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

(A-3) Colorant: A compound represented by the formula (z-1) described in JP-A No. 2011-118369

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

(A-5) Colorant: The salt (X-33) obtained in Example 7,

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

(C-1) Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Yakuza)

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

(D1-1) Polymerization initiator: DETX (2,4-diethylthioxanthone, manufactured by NIPPON PHASE)

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

(E-3) Solvent: Propylene glycol monomethyl ether

(F-1) Surfactant: Megafac F554 (manufactured by DIC Corporation)

Example 23

[Preparation of colored curable composition 1]

(A-4) 75.6 parts by mass

Acrylic pigment dispersant 43.7 parts by mass

(E-2) 546 parts by mass

And the pigment was thoroughly dispersed using a bead mill to obtain a dispersion.

(A-1) 16.6 parts by mass

(E-2) 315 parts by mass

Were mixed to obtain a solution.

(B-2) 50 parts by mass (solid conversion)

(C-1) 50 parts by mass

(D-2) 18 parts by mass

(D1-1) 2 parts by mass

(E-2) 396 parts by mass

(E-3) 315 parts by mass

(F-1) 0.1 part by mass

Were mixed with the dispersion and the solution to obtain a colored curable composition 1.

Example 24

[Preparation of colored curable composition 2]

(A-4) 79.4 parts by mass

Acrylic pigment dispersant 45.9 parts by mass

(E-2) 574 parts by mass

And the pigment was thoroughly dispersed using a bead mill to obtain a dispersion.

(A-1) 12.1 parts by mass

(E-2) 231 parts by mass

Were mixed to obtain a solution.

(A-2) 1.9 parts by mass

(B-2) 50 parts by mass (solid conversion)

(C-1) 50 parts by mass

(D-2) 18 parts by mass

(D1-1) 2 parts by mass

(E-2) 470 parts by mass

(E-3) 319 parts by mass

(F-1) 0.1 part by mass

Was mixed with the dispersion and the solution to obtain a colored curable composition 2.

Example 25

[Preparation of colored curable composition 3]

(A-4) 76.8 parts by mass

Acrylic pigment dispersant 44.4 parts by mass

(E-2) 555 parts by mass

And the pigment was thoroughly dispersed using a bead mill to obtain a dispersion.

(A-1) 11.1 parts by mass

(E-2) 211 parts by mass

Were mixed to obtain a solution.

(A-3) 4.6 parts by mass

(B-2) 50 parts by mass (solid conversion)

(C-1) 50 parts by mass

(D-2) 18 parts by mass

(D1-1) 2 parts by mass

(E-2) 497 parts by mass

(E-3) 316 parts by mass

(F-1) 0.1 part by mass

Was mixed with the dispersion and the solution to obtain a colored curable composition 3.

Example 26

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

Example 27

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

Example 28

[Preparation of colored curable composition 6]

(A-4) 75.9 parts by mass

Acrylic pigment dispersant 44.0 parts by mass

(E-2) 549 parts by mass

And the pigment was thoroughly dispersed using a bead mill to obtain a dispersion.

(A-5) 4.9 parts by mass

(E-2) 92 parts by mass

Were mixed to obtain a solution.

(B-2) 50 parts by mass (solid conversion)

(C-1) 50 parts by mass

(D-2) 18 parts by mass

(D1-1) 2 parts by mass

(E-2) 562 parts by mass

(E-3) 301 parts by mass

(F-1) 0.1 part by mass

Was mixed with the dispersion and the solution to obtain a colored curable composition 6.

[Formation of pattern]

The colored curable composition (1) was applied on a glass substrate (Igloo XG; Corning) having a size of 2 inches by 2 inches by spin coating, and then prebaked at 100 ° C for 3 minutes. After cooling, the space between the substrate coated with the colored curable composition and the quartz glass photomask having the pattern was set to 100 m, and an exposure light of 150 mJ (TME-150 RSK manufactured by Topcon Co., Ltd.) / Cm &lt; 2 &gt; (based on 365 nm). After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 DEG C for 80 seconds, washed with water, and then subjected to post-baking in an oven at 230 DEG C for 20 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 found to be 2.3 탆.

[Evaluation of color]

The obtained pattern on the glass substrate was measured for spectroscopy using a colorimeter (OSP-SP-200, manufactured by Olympus Corporation), and the xy chromaticity coordinates (B _x , B _y ) and brightness were measured. The results are shown in Table 17.

[Evaluation of contrast]

The same operation as that for formation of the pattern was carried out except that the exposure was performed without using a photomask. The resultant coating film on the glass substrate was irradiated with a contrast colorimeter (CT-1; manufactured by Tsubosaka Electric Co., Ltd., detector: BM-5A, light source: F -10) was used, and the blank value was set to 30000 to measure the contrast. A sample in which a coating film on a glass substrate was sandwiched by a polarizing film (POLAX-38S, manufactured by LuKeo Corporation) was used as a sample. The results are shown in Table 17.

[evaluation]

Table 17 shows the results of evaluating the color, lightness, and contrast of the obtained colored curable compositions 2 to 6 by preparing a colored curable coating film in the same manner.

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

The salt of the present invention is useful as a dye, and is useful as a dye used in a color filter of a display device such as a liquid crystal display, in particular, in that it has a high molar extinction coefficient and a high solubility in an organic solvent.

The colored curable composition containing the salt of the present invention and the polymerizable compound may be used in a display device (for example, a known liquid crystal display device, an organic EL device, etc.) having a color filter as a part of its components, And the like, in the production of a device related to various colored images such as a color image.

Claims (11)

At least one anion selected from the group consisting of anions represented by formulas (I), (II), (III) and (IV), a cation having a xanthene skeleton, h) a salt containing an organic metal anion M ^n- indicating that any of the.
The formula (I)

Wherein X ¹ and X ² are each independently a fluorine atom or an alkyl fluoride 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]
The formula (II)

[Wherein X ³ to X ⁵ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms]
The formula (III)

[Wherein Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms]
The formula (IV)

[Wherein Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms]

(a)
(In the formula (a), M ¹ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ represent the groups shown in Table (a)
Table (a)

(b)
(In the formula (b), M ² and n _a represent the groups shown in Table (b)).
Table (b)

(c)
(In the formula (c), M ³ and n _b represent the groups shown in the table (c)).
Table (c)

(d)
(In the formula (d), M ⁴ and n _c represent groups shown in Table (d)).
Table (d)

(e)
(In the formula (e), M ⁵ and n _d represent the groups shown in the table (e)).
Table (e)

(f)
(In the formula (f), M ⁶ and n _e represent the groups shown in the table (f)).
Table (f)

(g)
(In the formula (g), M ⁷ and n _f represent the groups shown in the table (g)).
Table (g)

(h)
(In the formula (h), M ⁸ and n _g represent a group shown in the table (h)).
Table (h)

delete delete delete The method according to claim 1,
Wherein the metal atom capable of forming a divalent or higher valent metal ion contained in the organic metal anion M ^n- is Al, Cr or Co. A dye comprising the salt of claim 1 as an active ingredient. A colored curable composition comprising the dye according to claim 6 and a polymerizable compound. 8. The method of claim 7,
Wherein the coloring curable composition further comprises a pigment. 9. The method according to claim 7 or 8,
And at least one member selected from the group consisting of a resin and a polymerization initiator. A color filter formed by the colored curable composition according to claim 7. A display device comprising the color filter according to claim 10.