KR102104008B1 - Salt for dye - Google Patents

Abstract

[식 (１)에서, Z₁ 및 Z₂는 각각 독립적으로 1가의 프로톤 공여성 치환기에서 프로톤을 방출하는 치환기를 2개 가지는 기를 나타냄].
상기 오늄 양이온이 시아닌 염료에서 유래하는 양이온, 트리아릴메탄 염료에서 유래하는 양이온, 크산텐 염료에서 유래하는 양이온 또는 안트라퀴논 염료에서 유래하는 양이온인 상기의 염. Salt of an anion represented by Formula (1) and an onium cation derived from a dye capable of forming a salt with the anion

[In formula (1), Z ₁ and Z ₂ each independently represent a group having two substituents that release protons from a monovalent proton donor substituent].
The above salt wherein the onium cation is a cation derived from a cyanine dye, a cation derived from a triarylmethane dye, a cation derived from a xanthene dye or a cation derived from an anthraquinone dye.

Description

Salt for dyeing {SALT FOR DYE}

The present invention relates to salts useful as dyes.

Dyes are used in fields such as fiber materials, liquid crystal display devices, inkjet and recording materials, for example.

As such dyes, for example, compounds represented by the following formula (d-1), compounds represented by the formula (d-2), and compounds represented by the formula (ｈ-1) are known (JP2008-106111-A, JP2011- 100114-A and Wuhan Daxue Xuebao, Lixueban, Vol. 51, Period 6, ps. 699-703, 2005).

In the case of the above-mentioned conventionally known compounds, solubility in an organic solvent may not necessarily be satisfactorily satisfactory.

The present invention provides the following [1] to [7].

[1] A salt of an anion represented by the formula (1) and an onium cation derived from a dye capable of forming a salt with the anion.

[In formula (1), Z ₁ and Z ₂ each independently represent a group having two substituents that release protons from a monovalent proton releasing substituent].

[2] The salt according to [1], wherein the onium cation is a cation derived from a cyanine dye, a cation derived from a triarylmethane dye, a cation derived from a xanthene dye, or a cation derived from an anthraquinone dye.

[3] The salts described in [1] or [2], wherein Z ₁ and Z ₂ are each independently one of the groups represented by the following formulas (a-1) to (a-10):

[Wherein, R ₂₁ and R ₂₂ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted, a cycloalkyl group having 3 to 7 carbon atoms which may be substituted, or a phenyl group which may be substituted, and R ₂₃ to R ₉₂ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an amino group, or a nitro group].

[4] The salt according to [3], wherein Z ₁ and Z ₂ are groups represented by formula (a-1), formula (a-5), formula (a-6) or formula (a-８).

[5] A group having two substituents that release a proton from a monovalent proton donor substituent is a group in which protons are released from each of the two proton donor substituents of a compound having two monovalent proton donor substituents, 1 A compound having two valent proton donor substituents may have a catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, and a substituent 3-hydroxy-2-naphthoic acid which may have, 2-hydroxy-1-naphthoic acid which may have substituent, 1-hydroxy-2-naphthoic acid which may have substituent, bi which may have substituent Naphthol, salicylic acid which may have a substituent, benzyl acid which may have a substituent, or mandelic acid which may have a substituent [1] to [ ] Salt according to any one of the.

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

[7] A coloring composition comprising the dye according to [6].

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

The salt of the present invention is a salt of an anion represented by formula (1) and an onium cation derived from a dye capable of forming a salt with the anion.

[In formula (1), Z ₁ and Z ₂ each independently represent a group having two substituents that release protons from a monovalent proton donor substituent]

The -charge and + charge of the salt of the present invention are the same.

As a dye capable of forming a salt with the anion, cyanine dye, anthraquinone dye, triarylmethane dye, xanthene dye, phthalocyanine dye, diarylmethane dye, acridine dye, azine dye, thiazine dye, oxazine dye , Azamethine dye and azo dye. Among these, cyanine dyes, triarylmethane dyes, xanthene dyes and anthraquinone dyes are preferred. Since the salt of the present invention is composed of cations derived from a dye, it exhibits useful color performance as a dye.

As an onium cation, an ammonium cation, an oxonium cation, a sulfonium cation, a phosphonium cation etc. respectively derived from the said dye are mentioned, for example.

Hereinafter, the cation constituting the salt of the present invention is specifically exemplified by a dye derived therefrom.

Examples of the cation derived from the cyanine dye include cations having a cyanine skeleton represented by formulas (1-1) to (1-4), respectively. Moreover, in the formula, "n-Pr" represents an n-propyl group, "n-Bu" represents an n-butyl group, and "s-Bu" represents a sec-butyl group.

As a cyanine dye, the salt of the cation represented by Formula (1-1)-Formula (1-4), respectively, and the anion corresponding to the above is mentioned. As the corresponding anion a halide ion (e.g. ^{Cl -, Br -, I -} ), perchlorate anion, a chlorate anion, a thiocyanate anion, a hexafluorophosphate of (phosphorus hexafluoride) anion, hexafluorophosphate antimony anion, 4 boron anion , C ₆ H ₅ SO ₃ ^-, and the like ^{_{-, CH 3 -C 6 H 4}} SO 3 -, CF 3 SO 3.

As a dye for inducing cations derived from a triarylmethane dye, C.I. Basic Red 9, C.I. Basic Violet 1, C.I. Basic Violet 2, C.I. Basic Violet 3, C.I. Basic Violet 4, C.I. Basic Violet 13, C.I. Basic Violet 14, C.I. Basic Violet 23, C.I. Basic Blue 1, C.I. Basic Blue 5, C.I. Basic Blue 7, C.I. Basic Blue 8, C.I. Basic Blue 11, C.I. Basic Blue 15, C.I. Basic Blue 18, C.I. Basic Blue 20, C.I. Basic Blue 21, C.I. Basic Blue 24, C.I. Basic Blue 26, C.I. Basic Green 1, C.I. Basic Green 4 etc., and dyes etc. which are represented by following formula (i-1)-formula (i-7), respectively. In addition, dyes which may be their precursors, for example C.I. Solvent Blue 5 (which may be a precursor to C.I. Basic Blue 7) and the like.

A dye that induces cations derived from a xanthene dye, that is, a xanthene dye is a generic term for a dye having a xanthene skeleton in a molecule. It is preferable to have one or more amino groups which may be substituted on the xanthene skeleton, and it is more preferable to have two amino groups which may be substituted. 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 which may be substituted has a positively charged structure, and more preferably a positively charged iminium.

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

Xanthene dyes typically Cl ^- or PF ₆ ^- or with an inorganic anion, such as, carboxylate group (-COO ^-) in the ^molecule has an acidic group such as a sulfonate or a group (-SO _3). In the former case, the xanthene dye is a so-called basic dye, and the cation derived from the xanthene dye is usually a cation excluding some or all (preferably all) of inorganic anions in the xanthene dye. In the latter case, the xanthene dye is a so-called internal salt, and the cation derived from the xanthene dye is usually a cation of a structure in which some or all (preferably all) of the acidic groups of these internal salts are neutralized. . Here, as the acidic group, for example a carboxylate group (-COO ^-) groups is neutralized carboxyl group (-COOH) or a salt thereof (-COONa, etc.), sulfonate group (-SO ₃ ^-) groups are neutralized Sulfo group (-SO ₃ H) or a salt thereof (-SO ₃ Na, etc.).

As a specific example of a basic dye among xanthene dyes, C.I. Basic Red 1, C.I. Basic Red 2, C.I. Basic Red 3, C.I. Basic Red 4, C.I. Basic Red 8, C.I. 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 formulas (ｈ-6), respectively.

Among xanthene dyes, C.I. Modern Red 27, and dyes represented by the following formulas (ｈ-10) to formulas (ｈ-12) are listed.

As a dye for inducing a cation derived from an anthraquinone dye, C.I. Basic Blue 22, C.I. Basic Blue 35, C.I. Basic Blue 45, C.I. And basic blue 47.

Equation (1)

[In formula (1), Z ₁ and Z ₂ each independently represent a group having two substituents that release protons from a monovalent proton donor substituent]

In the anion represented by, a group having two substituents that release a proton from a monovalent proton donor substituent is a group from which two proton donor substituents of a compound having two monovalent proton donor substituents release protons In the formula (1), Z ₁ and Z ₂ are each bonded to a boron atom through two bonding arms from which the proton is released. As a monovalent proton donor substituent, a carboxyl group, a hydroxyl group, etc. are mentioned.

Examples of Z ₁ and Z ₂ include groups represented by the following formulas (a-1) to (a-10).

[Wherein, R ₂₁ and R ₂₂ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted, a cycloalkyl group having 3 to 7 carbon atoms which may be substituted, or a phenyl group which may be substituted, and R ₂₃ to R ₉₂ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an amino group, or a nitro group]

Preferably it is a group represented by Formula (a-1), Formula (a-5), Formula (a-6), and Formula (a-８), More preferably, Formula (a-1) and Formula (a-) It is a group represented by (iii), and is still more preferably a group represented by formula (a-1). It is preferable that Z ₁ and Z ₂ are the same from the viewpoint of ease of manufacture. In addition, in Formula (1), it is preferable that Z ₁ and Z ₂ are each bonded to a boron atom to form a 5-membered ring, 6-membered ring or 7-membered ring containing the boron atom.

As a compound having two monovalent proton donor substituents, catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, and a substituent 3-hydroxy-2-naphthoic acid which may have, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent It is preferable that it is salicylic acid which may have a substituent, benzyl acid which may have a substituent, or mandelic acid which may have a substituent.

As the salicylic acid which may have the above substituents, for example, salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, 4-bromosalicylic acid, 3-methoxysalicylic acid, 3 -Nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5,6-trichlorosalicylic acid, 3 -Hydroxysalicylic acid (alias: 2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (alias: 2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (alias: 2,5-dihydroxy Benzoic acid), 6-hydroxysalicylic acid (nickname: 2,6-dihydroxybenzoic acid), and the like.

As benzyl acid which may have the said substituent, for example,

And the like.

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

And the like.

A specific example of a group having two substituents that release a proton from a monovalent proton donor substituent is for salicylic acid

As described above, in each example of the compound having two monovalent proton donor substituents, protons are removed from each of the two proton donor substituents.

Examples of the anion represented by the formula (1) include anion (XC-1) to anion (XC-2X) and the like.

Among them, as anions represented by formula (1), anions (FC-1), anions (FC-2), anions (FC-3), anions (FC-25), anions (FC-2026), anions (FCC-) 25) is preferable, anion (FC-1) and anion (FC-25) are more preferable, and anion (FC-1) is even more preferable. If it is such an anion, the salt of this invention tends to become excellent in solubility in an organic solvent.

Examples of the salt of the present invention include salts (I-1) to salts (I-Z0) and the like.

The salt of the present invention can be prepared by mixing a dye and an alkali metal salt of an anion represented by formula (1) in a solvent. Lithium, sodium, potassium, etc. are mentioned as an alkali metal.

Examples of the solvent used for mixing include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, And tetrahydrofuran, dioxane, water, and chloroform.

Among these, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, isopropanol and water are preferable. If it is such a solvent, the solubility of the dye and the alkali metal salt of the anion represented by formula (1) tends to increase.

When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added to dissolve the dye and the alkali metal salt of the anion represented by formula (1) in the solvent.

The mixing of the dye with the alkali metal salt of the anion represented by formula (1) may be carried out by dissolving both in the above solvent or without dissolving it. However, the salt of the present invention can be obtained with a high yield by using a solvent in which both are dissolved and further dissolving.

The mixing temperature of the dye and the alkali metal salt of the anion represented by formula (1) is preferably 0 ° C to 150 ° C, more preferably 10 ° C to 120 ° C, and even more preferably 20 ° C to 100 ° C.

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

When the solvent used for mixing is a solvent compatible with water, ion-exchanged water is added to the solvent and stirred for 1 hour to 3 hours. Thereafter, if the precipitate is obtained by filtration, the salt of the present invention can be obtained. You may wash with ion-exchange water as needed.

When the solvent used for mixing is a solvent that is not compatible with water, ion-exchanged water is added to the solvent and stirred for 1 hour to 3 hours. Thereafter, if the organic layer is obtained by separating, a solution containing the salt of the present invention can be obtained. You may wash with ion-exchange water as needed. The salt of the present invention can be obtained by removing the solvent from the solution containing the salt of the present invention.

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

You may use a commercially available dye, for example, Yutaka Hosoda, "Theory Manufacturing Dye Chemistry," Semiotics, 396-402, 357-366, 369-377 and 235-241 pages, Matsui Supervised by Masaki "Synthesis and Application Technology of Functional Pigments", CMC Publication, pages 89-96, Synlett, 2010, No. 1, p. 89-92, J. Organic Chemistry, 2008, Vol. You may use what was manufactured by the well-known method described in 73, 8711-8718, etc.

The alkali metal salt of the anion represented by formula (1) may be commercially available, for example, JP4097704-B or JP4341251-B and prepared according to the method described in Journal of The Electrochemical Society, Vol.148 Period 1, 2001. have.

The salt of the present invention thus obtained is useful as a dye. Further, the salt of the present invention has high solubility in an organic solvent, and is particularly useful as a dye used in color filters of display devices such as liquid crystal displays.

The dye of the present invention is a dye containing the salt of the present invention as an active ingredient.

It is preferable that the coloring composition of this invention contains the dye of this invention as a coloring agent (Hereinafter, it may be called "a coloring agent (A)"), and further contains a resin. It is more preferable that the colored composition of the present invention further contains a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

The coloring agent (A) may further contain the pigment and / or the dye different from the dye of this invention in addition to the dye of this invention.

As the dye different from the dye of the present invention, Solvent, Acid, Basic, Reactive, Direct in Color Index (published by The Society of Dyers and Colourists) ), A dye classified as a disperse or a bat, and the like. More specifically, dyes having the following color index (C.I.) numbers may be mentioned, but are not limited thereto.

C.I. Solvent yellow 25, 79, 81, 82, 83, 89;

C.I. Acid yellow 7, 23, 25, 42, 65, 76;

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

C.I. Direct yellow 4, 28, 44, 86, 132;

C.I. Disperse yellow 54, 76;

C.I. Solvent orange 41, 54, 56, 99;

C.I. Acid Orange 56, 74, 95, 108, 149, 162;

C.I. Reactive Orange 16;

C.I. Direct orange 26;

C.I. Solvent red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;

C.I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Acid violet 102;

C.I. Solvent green 1, 5;

C.I. Acid Green 3, 5, 9, 25, 28;

C.I. Basic Green 1;

C.I. Bat Green 1st.

Examples of the pigment include organic pigments or inorganic pigments commonly used in pigment dispersion resists. Examples of the inorganic pigment include metal oxides and metal compounds such as metal complex salts. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony or complex metal oxides Can be mentioned. Further, examples of the organic pigments and inorganic pigments include compounds classified as Pigments in the Color Index (published by The Society of Dyers and Colourists). More specifically, the following color index (C.I.) pigments may be mentioned, but are not limited to these.

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;

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

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

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58 etc.

The content of the coloring agent (A) is preferably 5 to 60 mass% with respect to the solid content in the coloring composition. Here, solid content means the sum of the components except the solvent in a coloring composition.

The content of the dye of the present invention contained in the colorant (A) is preferably 3 to 100% by mass.

The dyes and pigments different from the dyes of the present invention may be used alone or in combination of two or more of the dyes of the present invention.

The resin is not particularly limited, and any resin may be used. The resin (i) is preferably an alkali-soluble resin, and 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 resin (Ｂ), specifically, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzylmethacrylate / isobornyl methacrylate copolymer, meta And methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, and the like.

The weight average molecular weight of resin (i) in terms of polystyrene is preferably 5,000 to 35,000, and more preferably 6,000 to 30,000.

The acid value of the resin (i) is preferably 50 to 150 mg-KOH / g, more preferably 60 to 135 mg-KOH / g.

The content of the resin (i) is preferably 7 to 65 mass%, more preferably 13 to 60 mass% with respect to the solid content of the coloring composition.

The polymerizable compound (C) is not particularly limited as long as it is a compound capable of polymerizing with an active radical, acid, or the like generated from the polymerization initiator (D). For example, a compound etc. which have a polymerizable ethylenically unsaturated bond are mentioned.

It is preferable that it is a polymerizable compound which has three or more polymerizable groups as said polymerizable compound (C). As a polymerizable compound which has three or more polymerizable groups, for example, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythrate And itol hexaacrylate and dipentaerythritol hexamethacrylate. The polymerizable compounds (C) may be used alone or in combination of two or more.

It is preferable that content of a polymerizable compound (C) is 5 to 65 mass% with respect to solid content of a coloring composition, More preferably, it is 10 to 60 mass%.

As said polymerization initiator (D), an active radical generator, an acid generator, etc. are mentioned. Active radical generators generate active radicals by the action of heat or light. Examples of the active radical generator include alkylphenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-hydroxy-2-methyl-1-phenylpropane- 1-on, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, and the like. have.

As said thioxanthone compound, for example, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxycity oxanthone; and the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl). -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3, 5-triazine, etc. are mentioned.

Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N- Benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like.

Further, examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl -1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, campaquinone, methyl phenylglyoxylate, titanocene compound, etc. You may use

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p-toluene Sulfonate, 4-acetoxyphenyl, methyl, benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfo And onium salts such as nate and diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylates, and benzointosylates.

The above polymerization initiators may be used alone or in combination of two or more.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, with respect to 100 parts by mass of the total amount of the resin (iii) and the polymerizable compound (C). When the content of the polymerization initiator is in the above-mentioned range, it is preferable because it increases the sensitivity, shortens the exposure time and improves productivity.

Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones, alcohols, esters and amides.

Examples of the above ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and diethylene Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol di Butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, And the like can be mentioned ethylene glycol monobutyl ether acetate.

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

Examples of the ketones are acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, and 4-hydroxy-4-methyl-2- And pentanone, cyclopentanone, and cyclohexanone.

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

Examples of the above esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, lactic acid Methyl, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-e Methyl methoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy Methyl-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetoacetic acid Methyl, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylacetic acid, γ-butyrolactone, and the like.

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

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

The content of the solvent (E) in the coloring composition is preferably 70 to 95% by mass, more preferably 75 to 90% by mass relative to the coloring composition.

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

Salts of the present invention are useful as dyes. Since the molar extinction coefficient is high and exhibits high solubility in an organic solvent, it is particularly useful as a dye used in color filters of display devices such as liquid crystal displays.

In addition, the coloring composition containing the salt of the present invention is a variety of colors such as a display device (for example, a known liquid crystal display device, an organic EL device, etc.), a solid active element, and the like having a color filter as part of its component parts. It can be used in a form known to devices related to imaging.

Example

Hereinafter, the colored photosensitive resin composition of the present invention will be described in more detail according to Examples. In the example, "%" and "part" are mass% and mass parts, unless otherwise specified.

Synthesis example 1 of alkali metal salt of anion represented by formula (1)

13 parts of methanol was added to 1.30 parts of lithium hydroxide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and stirred at 60 ° C. Furthermore, a solution in which 1.92 parts of boric acid [manufactured by Wako Pure Chemical Industries, Ltd.] and 11.55 parts of 2,2'-biphenol [manufactured by Tokyo Chemical Industry Co., Ltd.] was dissolved in 67 parts of methanol was added, and 7 hours at 60 ° C. It was stirred. After the mixture was cooled to room temperature, the precipitate was obtained by suction filtration, washed with 70 parts of acetone, and 5.62 parts of a compound represented by formula (FC-26-Li) was obtained.

Synthesis example 2 of alkali metal salt of anion represented by formula (1)

100 parts of methanol was added and dissolved in 2.00 parts of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.). Moreover, 2,3-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) 16.02 parts and boric acid [manufactured by Wako Pure Chemical Industries, Ltd.] 3.09 parts were added, stirred at room temperature for 2 hours, and further at 65 ° C. for 8 hours. Did. After the mixture was cooled to room temperature, the precipitate was obtained by suction filtration, washed with 268 parts of ion-exchanged water, 331 parts of methanol, and 869 parts of acetonitrile to obtain 4.16 parts of the compound represented by formula (FC-25-Na).

Synthesis example 3 of alkali metal salt of anion represented by formula (1)

To 2.00 parts of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), 50 parts of methanol was added and dissolved. Furthermore, a solution in which 18.82 parts of 3-hydroxy-2-naphthoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50 parts of methanol was added, the temperature was raised to 65 ° C, and stirred for 15 minutes. Furthermore, 3.09 parts of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 65 ° C. for 6 hours. After the mixture was cooled to room temperature, the precipitate was obtained by suction filtration, washed with 607 parts of ion-exchanged water and 95 parts of methanol to obtain 15.34 parts of the compound represented by formula (FC-27-Na).

Synthesis example 4 of alkali metal salt of anion represented by formula (1)

19 parts of water was added to 1.30 parts of lithium hydroxide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and stirred at room temperature. Furthermore, 1.92 parts of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 9.56 parts of 2,4-dihydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 100 ° C for 1 hour. After the mixed solution was cooled to room temperature, the precipitate was obtained by suction filtration, washed with 50 parts of cold ion-exchanged water, and 5.90 parts of a compound represented by formula (FC-3-Li) was obtained.

Synthesis example 5 of alkali metal salt of anion represented by formula (1)

To 2.00 parts of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), 50 parts of methanol was added and dissolved. Furthermore, 15.41 parts of 2,5-dihydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.09 parts of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and stirred at room temperature for 3.5 hours, and further at 65 ° C. for 5 hours. Did. After the mixture was cooled to room temperature, the precipitate was obtained by suction filtration, washed with 15 parts of methanol, and 6.78 parts of a compound represented by formula (FC-2-Na) was obtained.

Synthesis example 6 of alkali metal salt of anion represented by formula (1)

To 2.00 parts of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), 50 parts of methanol was added and dissolved. Furthermore, 15.41 parts of 2,6-dihydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.09 parts of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at 65 ° C for 8.5 hours. After the mixed solution was cooled to room temperature, the precipitate was obtained by suction filtration, washed with 237 parts of ion-exchanged water, and 10.90 parts of a compound represented by the formula (FC-1-Na) was obtained.

Example 1

A solution in which 2.00 parts of the compound represented by (ｈ-1) was dissolved in 10 parts of N-methylpyrrolidone, and a solution of 1.26 parts of the compound represented by formula (FC-26-Li) in 19 parts of N-methylpyrrolidone It was added at room temperature and stirred for 8 hours. 116 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 4 hours. Thereafter, the precipitate was obtained by suction filtration, washed with 144 parts of ion-exchanged water, and 2.07 parts of a salt represented by formula (I-X3) was obtained.

Example 2

A solution in which 2.00 parts of the compound represented by (ｈ-1) was dissolved in 10 parts of N-methylpyrrolidone, and a solution of 1.15 parts of the compound represented by formula (FC-25-Na) in 5.7 parts of N-methylpyrrolidone It was added at room temperature and stirred for 6 hours. 63 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 64 parts of ion-exchanged water, and 2.65 parts of the salt represented by formula (I-665) was obtained.

Example 3

A solution in which 2.00 parts of the compound represented by (ｈ-1) was dissolved in 10 parts of N-methylpyrrolidone, and a solution of 1.33 parts of the compound represented by formula (XC-3-Li) in 6.7 parts of N-methylpyrrolidone was dissolved. It was added at room temperature and stirred for 7 hours. 67 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 67 parts of ion-exchanged water, and 2.76 parts of the salt represented by formula (I-X2) was obtained.

Example 4

A solution in which 2.00 parts of the compound represented by (ｈ-1) was dissolved in 10 parts of N-methylpyrrolidone, and a solution of 1.05 parts of the compound represented by formula (FC-2-Na) in 5.3 parts of N-methylpyrrolidone It was added at room temperature and stirred for 7 hours. 61 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 65 parts of ion-exchanged water, and 2.44 parts of the salt represented by formula (I-4) was obtained.

Example 5

A solution in which 2.00 parts of the compound represented by (ｈ-1) was dissolved in 10 parts of N-methylpyrrolidone, and a solution of 1.11 parts of the compound represented by formula (BC-1-1Na) in 5.5 parts of N-methylpyrrolidone was dissolved. It was added at room temperature and stirred for 7 hours. 124 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 124 parts of ion-exchanged water, and 1.02 parts of a salt represented by the formula (I-311) was obtained.

Example 6

A solution in which 2.00 parts of the compound represented by (ｈ-1) was dissolved in 10 parts of N-methylpyrrolidone, and a solution of 1.11 parts of the compound represented by formula (FC-27-Na) in 5.5 parts of N-methylpyrrolidone It was added at room temperature and stirred for 7 hours. 62 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 42 parts of ion-exchanged water, and 2.89 parts of the salt represented by formula (I-X4) was obtained.

Example 7

C.I. Basic Violet 11 [Aizen Cathilon Brilliant Pink CD-BH, manufactured by Hodogaya Chemical Industries, Ltd.] To a solution in which 2.00 parts were dissolved in 10 parts of N-methylpyrrolidone, 1.38 parts of the compound represented by the formula (XC-2-Na) The solution dissolved in 6.9 parts of N-methylpyrrolidone was added at room temperature and stirred for 7 hours. 68 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 145 parts of ion-exchanged water, and 2.83 parts of the salt represented by formula (I-1８) was obtained.

Example 8

C.I. Basic violet 11 [Aizen Cathilon Brilliant Pink CD-BH, manufactured by Hodogaya Chemical Industry Co., Ltd.] To a solution in which 2.00 parts were dissolved in 10 parts of N-methylpyrrolidone, 1.33 parts of the compound represented by the formula (XC-255-Na) The solution dissolved in 6.7 parts of N-methylpyrrolidone was added at room temperature and stirred for 7 hours. 67 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 50 parts of ion-exchanged water, and 2.50 parts of a salt represented by formula (I-2) was obtained.

Example 9

28 parts of N-methylpyrrolidone was added to 4.00 parts of the compound represented by formula (XA-1), and the mixture was stirred at room temperature. Furthermore, 6.85 parts of dibutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, the temperature was raised to 65 ° C., and the mixture was stirred for 1.5 hours. After the mixture was cooled to room temperature, it was added to 388 parts of 10% hydrochloric acid while maintaining at 25 ° C or lower, and stirred for 1 hour. The precipitate was obtained by suction filtration, washed with 388 parts of ion-exchanged water, and 3.01 parts of a compound represented by the formula (ｈ-12) was obtained.

To a solution in which 1.00 parts of the compound represented by formula (ｈ-12) was dissolved in 5 parts of N-methylpyrrolidone, 0.57 parts of the compound represented by formula (FC-1-1-Na) was added at room temperature, heated to 60 ° C, and 9 Stir for hours. The mixture was cooled to room temperature, and 20 parts of 10% saline was added, followed by further stirring for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 19 parts of ion-exchanged water, and 1.38 parts of the salt represented by formula (I-45) was obtained.

Example 10

10.0 parts of the compound represented by formula (XA-1), 40 parts of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, and 7.2 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the mixture. , Heated to 65 ℃ and stirred for 3 hours. After the reaction solution was cooled to room temperature, it was added to 280 parts of 0.5% saline. The obtained precipitate was obtained as a residue by suction filtration, washed with 200 parts of ion-exchanged water, and dried to obtain 8.0 parts of the compound represented by the formula (ｈ-10). The yield was 68%.

Identification of compound represented by formula (ｈ-10)

(Mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 479.3

                          Exact Mass: 478.2

To a solution in which 1.00 parts of the compound represented by the formula (ｈ-10) was dissolved in 5 parts of N-methylpyrrolidone, 0.71 part of the compound represented by the formula (XC-1-Na) was added at room temperature, heated to 60 ° C, and 9 Stir for hours. The mixture was cooled to room temperature, and 20 parts of 10% saline was added, followed by further stirring for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 19 parts of ion-exchanged water, and 1.30 parts of a salt represented by the formula (I-443) was obtained.

Example 11

To a solution in which 4.07 parts of the compound represented by the formula (ｈ-1) was dissolved in 20 parts of N-methylpyrrolidone, 3.54 parts of the compound represented by the formula (XC-1Ｎ-Na) was added at room temperature and stirred for 6 hours. 20 parts of 10% saline was added to the mixed solution, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 19 parts of ion-exchanged water, and 6.29 parts of a salt represented by formula (I-VII) was obtained.

Example 12

C.I. To a solution in which 3.94 parts of Basic Violet 11 was dissolved in 20 parts of N-methylpyrrolidone, 3.16 parts of the compound represented by the formula (FC-1) -Na was added at room temperature and stirred for 6 hours. 20 parts of 10% saline was added to the mixed solution, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 19 parts of ion-exchanged water, and 6.34 parts of a salt represented by formula (I-VII) was obtained.

Example 13

C.I. A solution of 4.00 parts of basic red 1 dissolved in 20 parts of N-methylpyrrolidone was heated to 60 ° C., and C.I. A solution in which 2.90 parts of Solvent Yellow 21 was dissolved in 14.5 parts of N-methylpyrrolidone was added, heated to 60 ° C., and stirred for 3 hours.

To the mixed solution, 2.44 parts of the compound represented by formula (FC-1) -Na was added and stirred at 60 ° C for 8 hours. The mixture was cooled to room temperature, 138 parts of ion-exchanged water was added, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration, washed with 213 parts of ion-exchanged water, a salt represented by formula (I-X0), and C.I represented by formula (IA--1). Basic Red 1 cations and C.I. 7.47 parts of the mixed salt with the salt of the anion of the solvent yellow 21 (hereinafter referred to as a mixed salt (I-XO-IA-1)) was obtained.

[Measurement of absorbance]

0.35 g of salt was dissolved in a solvent to make a volume of 250 cm 3, of which 2 cm 3 was diluted with a solvent to make 100 cm 3, and the solution was adjusted to a concentration of 0.028 g / L. For the solution, ultraviolet visible spectroscopy [V-650DS; Absorbance at the maximum absorption wavelength (λ _max ) and the maximum absorption wavelength (λ _max ) was measured by using Japan Spectroscopic Co., Ltd. (quartz cell, optical path length; 1 cm). Table 4 shows the results together with the solvent used. DMF is an abbreviation for N, N-dimethylformamide.

[Evaluation of solubility]

The salts obtained in Examples 1 to 12, the compounds represented by the formulas (ｈ-1), formulas (ｈ-1120), and formulas (ｈ-10), respectively, and C.I. For Basic Violet 11, the solubility in propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA), propylene glycol monomethyl ether (hereinafter abbreviated as PGME), and ethyl lactate (hereinafter abbreviated as EL) is as follows. It was calculated as follows.

In addition, for the mixed salt obtained in Example 13 (I--0-0-IA-1) and CI Basic Red 1, N, N -dimethylformamide (hereinafter abbreviated as DMF), diacetone alcohol (hereinafter referred to as DAA) Solubility) was determined as follows.

In a 50 mL sample tube, the compound and the solvent were mixed in the following proportions, after which the sample tube was sealed and vibrated with an ultrasonic vibrator at 30 ° C for 3 minutes. Subsequently, the mixture was left at room temperature for 30 minutes, filtered, and the residue thereof was visually observed. When the insoluble matter could not be identified as a residue, it was determined that the solubility was good, and when the insoluble matter could be confirmed, it was determined that the solubility was poor. Table 5 records the maximum concentrations judged to have good solubility. The results are shown in Table 5 and Table 6. × means 1% is defective.

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

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

0.05% 5% salt or compound, 1 g solvent

7% salt or compound 0.07 g, solvent 1 g

10% salt or compound 0.10 g, solvent 1 g

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

Example 14

[Preparation of coloring composition]

(A) Coloring agent: Salt (I-443): 20 parts of the salt synthesized in Example 10

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

(C-1) Polymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Chemical Industries, Ltd.) 30 parts

(D-1) Photopolymerization initiator: Benzyl dimethyl ketal [Mongacure 651; BASF Japan company) part 15

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

Mixing to obtain a coloring composition.

[Production of color filters]

On the glass, the coloring composition obtained above is applied by a spin coat method to volatilize volatile components. After cooling, light is irradiated using a patterned quartz glass photo mask and an exposure machine. After light irradiation, it was developed with an aqueous potassium hydroxide solution and heated in an oven to 200 ° C. to obtain a color filter.

Example 15

A coloring composition and a color filter were obtained in the same manner as in Example 11, except that the compound (I-43) synthesized in Example 10 was replaced with the compound (I-311) synthesized in Example 5.

It can be seen from the results of Tables 5 and 6 that the salts of the Examples show high solubility in organic solvents. In addition, the coloring composition containing the salt is less likely to produce foreign matter, it is possible to produce a high-quality color filter.

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

Claims (7)

In the salt of the anion represented by Formula (1) and the onium cation derived from the dye capable of forming a salt with the anion,

[In formula (1), Z ₁ and Z ₂ each independently represent a group having two substituents that release protons from a monovalent proton releasing substituent]
The onium cation is a cation derived from a xanthene dye,
The dye for inducing a cation derived from the xanthene dye is a compound represented by the following formula (ｈ-1), a compound represented by the following formula (ｈ-10), a compound represented by the following formula (ｈ-10), CI basic violet 11, or CI Basic Red 1 salt.

delete According to claim 1,
A salt in which Z ₁ and Z ₂ are each independently any one of the groups represented by the following formulas (a-1) to (a-10):

[Wherein, R ₂₁ and R ₂₂ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted, a cycloalkyl group having 3 to 7 carbon atoms which may be substituted, or a phenyl group which may be substituted, and R ₂₃ to R ₉₂ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an amino group, or a nitro group]. The method of claim 3,
Wherein Z ₁ and Z ₂ are of the formula (a-1), formula (a-5), due to salt represented by the formula (a-6) or a group represented by the formula (a-8). According to claim 1,
A group having two substituents that release a proton from the monovalent proton donor substituent is a group in which protons are released from each of the two proton donor substituents of a compound having two monovalent proton donor substituents, and a monovalent proton A compound having two donor substituents may have a catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, and a substituent 3-hydroxy-2-naphthoic acid which may be present, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, Salts of salicylic acid which may have a substituent, benzyl acid which may have a substituent, or mandelic acid which may have a substituent. A dye comprising the salt of any one of claims 1 and 3 to 5 as an active ingredient. A coloring composition comprising the dye of claim 6.