TWI582176B - Salt for dye - Google Patents

Description

Dye salt

This invention relates to a salt useful as a dye.

Dyes are used, for example, in the fields of fiber materials, liquid crystal display devices, ink jets, and recording materials.

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

There is a case where the solubility of the above-mentioned compound which is previously known to an organic solvent is not necessarily sufficiently satisfactory.

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

[1] a salt of a salt represented by the formula (1) and a phosphonium cation derived from a dye capable of forming a salt with the anion,

In the formula (1), Z ₁ and Z ₂ each independently represent a group having two substituents from which a proton-donating substituent is released from a proton.

[2] The salt according to [1], wherein the above cerium cation is a cation derived from a cyanine dye, a cation derived from a triarylmethane dye, derived from A cation of a dye or a cation derived from an anthraquinone dye.

[3] The salt according to [1] or [2], wherein Z ₁ and Z ₂ are each independently a group represented by the following formulas (a-1) to (a-10),

(wherein R ₂₁ and R ₂₂ each independently represent a hydrogen atom, a substituted alkyl group having 1 to 6 carbon atoms, a substituted cycloalkyl group having 3 to 7 carbon atoms or a substituted phenyl group; R ₂₃ to R ₉₂ each independently represent 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 amine group or a nitrate base).

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

[5] The salt according to any one of [1] to [4] wherein the base having two substituents derived from a proton-donating substituent releasing a proton has two monovalent protons a compound in which two proton-donating substituents respectively release a proton, and a compound having two monovalent proton-donating substituents is a catechol which may have a substituent, and may have a substituent 2,3-dihydroxynaphthalene, 2,2'-biphenol which may have a substituent, 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, a binaphthol which may have a substituent, a salicylic acid which may have a substituent, a diphenyl glycolic acid which may have a substituent or a mandelic acid which may have a substituent .

[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 an organic solvent.

The salt of the present invention is a salt of an anion represented by the formula (1) and a phosphonium cation derived from a dye which forms a salt with the anion.

[In the formula (1), Z ₁ and Z ₂ each independently represent a group having two substituents derived from a monovalent proton-donating substituent releasing a proton]

The salt of the present invention has the same charge as the + charge.

Examples of the dye capable of forming a salt with the anion include a cyanine dye, an anthraquinone dye, and a triarylmethane dye. Dyes, phthalocyanine dyes, diarylmethane dyes, acridine dyes, hydrazine Dye, thiophene dye, Dyes, nitrogen methine dyes, azo dyes, etc. Among them, preferred are cyanine dyes, triarylmethane dyes, Dyes and anthraquinone dyes. Such salts of the present invention exhibit color properties that can be used as dyes by the inclusion of dye-derived cations.

Examples of the phosphonium cation include an ammonium cation derived from the above dye, an oxonium cation, a phosphonium cation, a phosphonium cation, and the like.

Hereinafter, the cation constituting the salt of the present invention will be specifically exemplified by the dye which is the source.

Examples of the cation derived from the cyanine dye include a cation having a cyanine skeleton represented by the formula (1-1) to the formula (1-42). Further, in the formula, "n-Pr" means n-propyl group, "n-Bu" means n-butyl group, and "s-Bu" means a second butyl group.

Examples of the cyanine dye include salts of the cation represented by the formula (1-1) to the formula (1-42) and the counter anion. Examples of the counter anion include halide ions (e.g., Cl ^- , Br ^- , I ^- ), perchlorate anions, chlorate anions, thiocyanate anions, phosphorus hexafluoride anions, antimony hexafluoride anions, tetrafluoride. Boron anion, C ₆ H ₅ SO ₃ ^- , CH ₃ -C ₆ H ₄ SO ₃ ^- , CF ₃ SO ₃ ^-, and the like.

Examples of the dye which provides a cation derived from a triarylmethane dye include CI basic red 9, CI basic violet 1, CI basic violet 2, CI basic violet 3, CI basic violet 4, and CI basic violet 13 , CI alkaline violet 14, CI alkaline violet 23, CI alkaline blue 1, CI alkaline blue 5, CI alkaline blue 7, CI alkaline blue 8, CI alkaline blue 11, CI alkaline blue 15, CI Basic Blue 18, CI Basic Blue 20, CI Basic Blue 21, CI Basic Blue 24, CI Basic Blue 26, CI Alkaline Green 1, CI Alkaline Green 4, etc., and are respectively of the following formula (g- 1) The dye represented by ~(g-7). Further, a dye which can be used as such precursors, for example, C.I. Solvent Blue 5 (which can be a precursor of C.I. Basic Blue 7), and the like can be also mentioned.

Source of offering Dye cation dye, ie The dye has a molecule The general name for the dye of the skeleton. Preferably in the The skeleton has at least one substitutable amine group, more preferably two substitutable amine groups. It is preferred that the cation contained in the salt of the present invention is a cation having a structure in which a nitrogen atom of a substituted amine group is positively charged, and more preferably an iminium cation.

As this Examples of the dye include an Eosin dye, a Fluorescein dye, a Rhodamine dye, a Pyronine dye, and a red basic dye. Further, as described in Synlett, 2010, No. 1, p. 89-92, A Rhodamine-based dye or a red-basic dye (Rosamine)-based dye in which an oxygen atom of a skeleton is substituted with a sulfur atom, a selenium atom or a ruthenium atom.

The dye usually has an inorganic anion such as Cl ^- or PF ₆ ^- or an acidic group such as a carboxylate group (-COO ^- ) or a sulfonate group (-SO ₃ ^- ) in the molecule. In the case of the former, Dyes are so-called basic dyes, derived from The cation of the dye is usually self The dye removes some or all, preferably all, of the cations of the inorganic anion. In the latter case, Dyes are called internal salts, derived from The cation of the dye is usually a cation of a structure in which a part or all (preferably all) of the acidic groups of the internal salt are neutralized. Here, as the acidic group, for example, a group in which a carboxylate group (-COO ^- ) is neutralized is a carboxyl group (-COOH) or a salt thereof (-COONa or the like), and a sulfonate group (-SO ₃ ^- ) is And the group formed is a sulfo group (-SO ₃ H) or a salt thereof (-SO ₃ Na, etc.).

As Specific examples of the basic dye in the dye include CI basic red 1, CI basic red 2, CI basic red 3, CI basic red 4, basic red 8, basic red 11, and CI alkaline purple. 10. CI Basic Violet 11, CI Basic Violet 25, and dyes represented by the following formulas (h-1) to (h-86), respectively.

As Specific examples of the internal salt in the dye include CI medium red 27 and dyes represented by the following formulas (h-100) to (h-122).

Examples of the dye which provides a cation derived from an anthraquinone dye include C.I. Basic Blue 22, C.I. Basic Blue 35, C.I. Basic Blue 45, C.I. Basic Blue 47 and the like.

[In the formula (1), Z ₁ and Z ₂ each independently represent a group having two substituents derived from a monovalent proton-donating substituent releasing a proton]

The substituent of the anion having two substituents derived from a monovalent proton-donating substituent releasing a proton from two of the proton-donating substituents of a compound having two monovalent proton-donating substituents protons are released from the base, in the formula _{(1), Z 1, Z} 2 via the release of two protons bonded to bond each bonded to the boron atom. Examples of the monovalent proton-donating substituent include a carboxyl group and a hydroxyl group.

Examples of Z ₁ and Z ₂ include groups represented by the following formulas (a1) to (a10).

(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 3 to 7 cycloalkyl group which may be substituted or a substituted phenyl group, R ₂₃ to R ₉₂ each independently represent 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 amine group or a nitro group. )

Preferred are the groups represented by the formula (a-1), the formula (a-5), the formula (a-6) and the formula (a-8), and more preferably the formula (a-1) and the formula (a-). 8) The base represented, and more preferably the base represented by the formula (a-1). In terms of ease of manufacture, Z ₁ and Z ₂ are preferably the same. Further, it is preferred that Z ₁ and Z ₂ in the formula (1) are bonded to a boron atom to form a 5-membered ring, a 6-membered ring or a 7-membered ring including the boron atom.

As the compound having two monovalent proton-donating substituents, preferred are catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, and 2,2'- which may have a substituent. Biphenol, 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, may have a substituent Binaphthol, a salicylic acid which may have a substituent, a diphenyl glycolic acid which may have a substituent or a mandelic acid which may have a substituent.

Examples of the salicylic acid which may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, and 3-chlorosalicylic acid. , 4-bromosalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-t-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-dihydroxybenzoic acid), 6-hydroxysalicylic acid (alias: 2,6 -dihydroxybenzoic acid) and the like.

As the above-described diphenyl glycolic acid which may have a substituent, for example,

Wait.

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

Wait.

Specific examples of the group having two substituents derived from a monovalent proton-donating substituent releasing a proton may be exemplified by salicylic acid.

In general, two of the proton-donating substituents in each of the compounds having two monovalent proton-donating substituents are proton-free.

Examples of the anion represented by the formula (1) include an anion (BC-1) to an anion (BC-28).

Among them, as the anion represented by the formula (1), anion (BC-1), anion (BC-2), anion (BC-3), anion (BC-25), anion (BC-26), The anion (BC-27) is more preferably an anion (BC-1) or an anion (BC-25), and further preferably an anion (BC-1). When it is such an anion, the salt of the present invention tends to be excellent in solubility in an organic solvent.

Examples of the salt of the present invention include a salt (I-1) to a salt (I-90).

The salt of the present invention can be produced by mixing a dye with an alkali metal salt of an anion represented by the formula (1) in a solvent. Examples of the alkali metal include lithium, sodium, potassium, and the like.

Examples of the solvent to be used in the mixing include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylammonium, acetonitrile, and acetic acid B. Ester, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, two Alkane, water, chloroform, etc.

Among them, preferred are N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylhydrazine, methanol, ethanol, isopropanol and water. . When these solvents are present, the solubility of the dye and the alkali metal salt of the anion represented by the formula (1) tends to be high.

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

Mixing the dye with an alkali metal salt of an anion represented by formula (1) to dissolve both This may be carried out in the above solvent or may be carried out without being dissolved. However, the salt of the present invention can be obtained in a higher yield by using a solvent which dissolves both and dissolving both.

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

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

When the solvent used for the mixing is a solvent compatible with water, ion-exchanged water is added to the solution, and the mixture is further stirred for 1 to 3 hours. Thereafter, the precipitate is obtained by filtration to obtain the salt of the present invention. It can also be washed with ion exchange water as needed.

When the solvent used for the mixing is a solvent which is incompatible with water, ion-exchanged water is added to the solution, and the mixture is further stirred for 1 to 3 hours. Thereafter, an organic layer is obtained by liquid separation, and a solution containing the salt of the present invention can be obtained. It can also be washed with ion exchange water as needed. The solvent of the present invention can be obtained by removing the solvent from the solution containing the salt of the present invention.

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

The dyes can be used by commercially available ones. For example, you can also use the "Theory to Make Dye Chemistry" by Hiroshi Hiroshi, Jebsen-do, 396~402, 357~366, 369~377 and 235~241 pages; Songju Masahiro Supervisor "Synthesis of Functional Pigments" And Applied Technology, CMC Publishing, 89-96 pages; Synlett, 2010, No. 1, p. 89-92, J. Organic Chemistry, 2008, Vol. 73, 8711-8718, etc. .

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

The salt of the present invention thus obtained can be used as a dye. Further, since the salt of the present invention has high solubility in an organic solvent, it is particularly useful as a display device such as a liquid crystal display device. The dye used in the color filter.

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

The colored composition of the present invention preferably contains the dye of the present invention as a colorant (hereinafter sometimes referred to as "colorant (A)"), and further contains a resin (B). More preferably, the coloring composition of the present invention further comprises a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

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

As a dye different from the dye of the present invention, a Colour Index (published by The Society of Dyers and Colourists) can be cited as a solvent (Solvent), an acidity (Acid), a basicity (Basic), and an active (reactive). ), Direct, Disperse, or Vat dyes. More specifically, the dye of the following color index (C.I.) number is mentioned, but it is not limited to these.

CI Solvent Yellow 25, 79, 81, 82, 83, 89; CI Acid Yellow 7, 23, 25, 42, 65, 76; CI Reactive Yellow 2, 76, 116; CI Direct Yellow 4, 28, 44, 86, 132; CI disperse yellow 54, 76; CI solvent orange 41, 54, 56, 99; CI acid orange 56, 74, 95, 108, 149, 162; CI active orange 16; CI direct orange 26; CI solvent red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218; CI acid red 73, 91, 92, 97, 138, 151, 211, 274, 289; CI acid purple 102; CI solvent green 1, 5; C.I. Acid Green 3, 5, 9, 25, 28; C.I. Basic Green 1; C.I. Reduction Green 1 and the like.

As the pigment, an organic pigment or an inorganic pigment which is generally used for pigment dispersion photoresist can be cited. Examples of the inorganic pigment include a metal compound such as a metal oxide or a metal salt, and specific examples thereof include oxidation of a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc or ruthenium. Or composite metal oxide. Further, specific examples of the organic pigment and the inorganic pigment include a compound classified as a pigment in a Colour Index (published by The Society of Dyers and Colourists). More specifically, the following pigment index (C.I.) number of pigments may be mentioned, but it is not limited thereto.

CI 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; CI Pigment oranges 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168 , 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; CI Pigment Green 7, 10 , 15, 25, 36, 47 and 58 and so on.

The content of the colorant (A) is preferably from 5 to 60% by mass based on the solid content of the coloring composition. Here, the solid content component means the total of the components other than the solvent in the coloring composition.

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

The dyes and pigments different from the dye of the present invention may be used alone or in combination with the dye of the present invention, or may be used in combination with the dye of the present invention.

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

Specific examples of the resin (B) include methacrylic acid-benzyl methacrylate copolymer, methacrylic acid-benzyl methacrylate-styrene copolymer, and methacrylic acid-benzyl methacrylate-methyl. Acrylic acid Ester copolymer, methacrylic acid-styrene-benzyl methacrylate-N-phenyl maleimide copolymer, methacrylic acid-styrene-glycidyl methacrylate copolymer, and the like.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 5,000 to 35,000, more preferably 6,000 to 30,000.

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

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, based on the solid content of the coloring composition.

The polymerizable compound (C) is not particularly limited as long as it is a compound which can be polymerized by an active radical, an acid or the like which is produced from the polymerization initiator (D). For example, a compound having a polymerizable ethylenically unsaturated bond or the like can be given.

The polymerizable compound (C) is preferably a polymerizable compound having three or more polymerizable groups. Examples of the polymerizable compound having three or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, and dipentaerythritol. Hexamethyl acrylate and the like. The above-mentioned polymerizable compound (C) may be used alone or in combination of two or more.

The content of the polymerizable compound (C) is preferably 5 to 65% by mass, and more preferably 10 to 60% by mass based on the solid content of the coloring composition.

Examples of the polymerization initiator (D) include a living radical generator, an acid generator, and the like. The living radical generating agent generates active radicals by the action of heat or light. Examples of the living radical generating agent include an alkylphenone compound and 9-oxosulfuric acid. Compound, three Compounds, hydrazine compounds, and the like.

As the above alkylphenone compound, for example, 2-methyl-2- Lolinyl-1-(4-methylsulfonylphenyl)propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin dimethyl ketal, 2 -Hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.

As the above 9-oxygen sulfur Examples of the compound include 2-isopropyl 9-oxosulfuric acid. 4-isopropyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 1-chloro-4-propoxy 9-oxosulfur Wait.

As the above three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

Examples of the ruthenium compound include an O-fluorenyl fluorene-based compound, and specific examples thereof include N-benzylideneoxy-1-(4-phenylsulfonylphenyl)butan-1-one- 2-imine, N-benzylideneoxy-1-(4-phenylsulfonylphenyl)octane-1-one-2-imine, N-ethyloxy-1-[9-B -6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-{ 2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzimidyl}-9H-indazol-3-yl]ethane-1- Imine and the like.

Further, as the living radical generating agent, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or 2,2'-bis(o-chlorophenyl)-4,4',5 can be used. , 5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzoin, 9,10-phenanthrenequinone, camphorquinone, benzene Methyl glyoxylate, titanium titanate compound, and the like.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylhydrazine hexafluoroantimonate, and 4-ethyloxyphenylphenyl p-toluenesulfonate. Methyl hydrazine, 4-ethenyloxyphenyl-methyl-benzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenylphosphonium p-toluenesulfonate And sulfonium salts such as diphenylphosphonium hexafluoroantimonate, or nitrobenzyl sulfonates, benzoin tosylate salts, and the like.

These 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, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator is within the above range, it is preferable because the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

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

Examples of the ethers include tetrahydrofuran, tetrahydropyran, and 1,4-two. Alkane, 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl 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, diethylene glycol single Butyl ether acetate and the like.

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

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, and 4-hydroxy-4-methyl-2. - Pentanone, cyclopentanone, cyclohexanone, and the like.

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

Examples of the above esters include ethyl acetate, n-butyl acetate, and isobutyl acetate. Ester, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, Butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3 -ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy- Ethyl 2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, 3-methoxybutyl acetate, 3-methyl acetate -3-methoxybutyl ester, γ-butyrolactone, and the like.

Examples of the above guanamines 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 from 70 to 95% by mass, more preferably from 75 to 90% by mass, based on the coloring composition.

The colored composition of the present invention may optionally contain various additives such as a surfactant, a filler, other polymer compound, adhesion promoter, antioxidant, ultraviolet absorber, light stabilizer, chain transfer agent, and the like.

The salt of the present invention can be used as a dye. Since the molar absorption coefficient is high and it exhibits high solubility to an organic solvent, it is particularly useful as a dye used for a color filter of a display device such as a liquid crystal display device.

Further, the coloring composition containing the salt of the present invention can be used in a known manner in a display device including a color filter as a part of its constituent parts (for example, a known liquid crystal display device, organic EL (Electroluminescence)) Various devices related to color images, such as devices and solid-state imaging devices.

Example

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

Synthesis Example 1 of an alkali metal salt of an 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 the mixture was stirred at 60 °C. Furthermore, a solution obtained by dissolving 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.) in 67 parts of methanol was added at 60 degrees. Stir under 7 hours. After the mixture was cooled to room temperature, a precipitate was obtained by suction filtration, and washed with 70 parts of acetone to obtain 5.62 parts of a compound represented by the formula (BC-26-Li).

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

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

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

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

Synthesis Example 4 of an alkali metal salt of an 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 the mixture was stirred at room temperature. Further, 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 the mixture was stirred at 100 ° C for 1 hour. After the mixture was cooled to room temperature, a precipitate was obtained by suction filtration, and washed with 50 parts of cold ion-exchanged water to obtain 5.90 parts of a compound represented by the formula (BC-3-Li).

Synthesis Example 5 of an alkali metal salt of an anion represented by the formula (1)

50 parts of methanol was added to 2.00 parts of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and dissolved. Further, 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 degrees. Stir for 5 hours. After the mixture was cooled to room temperature, a precipitate was obtained by suction filtration, and washed with 15 parts of methanol to obtain 6.78 parts of a compound represented by formula (BC-2-Na).

Synthesis Example 6 of an alkali metal salt of an anion represented by the formula (1)

50 parts of methanol was added to 2.00 parts of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and dissolved. Further, 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 the mixture was stirred at 65 ° C for 8.5 hours. After the mixture was cooled to room temperature, a precipitate was obtained by suction filtration, and washed with 237 parts of ion-exchanged water to obtain 10.90 parts of a compound represented by the formula (BC-1-Na).

Example 1

A solution of 2.00 parts of the compound represented by (h-1) dissolved in 10 parts of N-methylpyrrolidone was added at room temperature, and 1.26 parts of the compound represented by the formula (BC-26-Li) was added. Dissolve A solution of 19 parts of N-methylpyrrolidone was stirred for 8 hours. To the mixed solution, 116 parts of ion-exchanged water was added, and the mixture was further stirred for 4 hours. Thereafter, precipitates were taken by suction filtration, and washed with 144 parts of ion-exchanged water to obtain 2.07 parts of the salt represented by the formula (I-83).

Example 2

The compound represented by the formula (BC-25-Na) was added to a solution obtained by dissolving 2.00 parts of the compound represented by (h-1) in 10 parts of N-methylpyrrolidone at room temperature. The solution was dissolved in 5.7 parts of N-methylpyrrolidone and stirred for 6 hours. To the mixed solution, 63 parts of ion-exchanged water was added, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 64 parts of ion-exchanged water to obtain 2.65 parts of the salt represented by the formula (I-65).

Example 3

The compound represented by the formula (BC-3-Li) was added to a solution obtained by dissolving 2.00 parts of the compound represented by (h-1) in 10 parts of N-methylpyrrolidone at room temperature. The solution was dissolved in 6.7 parts of N-methylpyrrolidone and stirred for 7 hours. 67 parts of ion-exchange water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 67 parts of ion-exchanged water to obtain 2.76 parts of the salt represented by the formula (I-82).

Example 4

The compound represented by the formula (BC-2-Na) was added to a solution obtained by dissolving 2.00 parts of the compound represented by (h-1) in 10 parts of N-methylpyrrolidone at room temperature. The solution was dissolved in 5.3 parts of N-methylpyrrolidone and stirred for 7 hours. 61 parts of ion-exchange water was added to this mixture, and it stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 65 parts of ion-exchanged water to obtain 2.44 parts of a salt represented by the formula (I-48).

Example 5

2.00 parts of the compound represented by (h-1) was dissolved in N-methylpyrrolidone at room temperature A solution prepared by dissolving 1.11 parts of the compound represented by the formula (BC-1-Na) in 5.5 parts of N-methylpyrrolidone was added to the solution prepared in 10 parts, and the mixture was stirred for 7 hours. To the mixture, 124 parts of ion-exchanged water was added, and the mixture was further stirred for 1 hour. Thereafter, precipitates were taken by suction filtration, and washed with 124 parts of ion-exchanged water to obtain 1.02 parts of a salt represented by the formula (I-31).

Example 6

The compound represented by the formula (BC-27-Na) was added to a solution obtained by dissolving 2.00 parts of the compound represented by (h-1) in 10 parts of N-methylpyrrolidone at room temperature. The solution was dissolved in 5.5 parts of N-methylpyrrolidone and stirred for 7 hours. 62 parts of ion-exchange water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 42 parts of ion-exchanged water to obtain 2.89 parts of the salt represented by the formula (I-84).

Example 7

2.00 parts of C.I. Basic Violet 11 (Aizen Cathilon Brilliant Pink CD-BH, manufactured by Hodogaya Chemical Industry Co., Ltd.) was dissolved in 10 parts of N-methylpyrrolidone at room temperature. A solution obtained by dissolving 1.38 parts of the compound represented by the formula (BC-2-Na) in 6.9 parts of N-methylpyrrolidone was added to the resulting solution, followed by stirring for 7 hours. To the mixture, 68 parts of ion-exchanged water was added, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 145 parts of ion-exchanged water to obtain 2.83 parts of the salt represented by the formula (I-18).

Example 8

Adding 2.00 parts of CI Basic Violet 11 (Aizen Cathilon Brilliant Pink CD-BH, manufactured by Hodogaya Chemical Industry Co., Ltd.) to a solution of 10 parts of N-methylpyrrolidone at room temperature, and adding A solution of 1.33 parts of the compound represented by the formula (BC-25-Na) dissolved in 6.7 parts of N-methylpyrrolidone was stirred and stirred for 7 hours. 67 parts of ion-exchange water was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 50 parts of ion-exchanged water to obtain 2.50 parts of the salt represented by the formula (I-28).

Example 9

To the 4.00 part of the compound represented by the formula (XA-1), 28 parts of N-methylpyrrolidone was added, and the mixture was stirred at room temperature. Further, 6.85 parts of dibutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the temperature was raised to 65 degrees, and stirred for 1.5 hours. After the mixture was cooled to room temperature, 388 parts of 10% hydrochloric acid was added while maintaining the temperature at 25 degrees or less, and the mixture was further stirred for 1 hour. By pumping The precipitate was collected by suction filtration, and washed with 388 parts of ion-exchanged water to obtain 3.01 part of the compound represented by the formula (h-120).

The compound represented by the formula (BC-1-Na) is added to a solution obtained by dissolving 1.00 part of the compound represented by the formula (h-120) in 5 parts of N-methylpyrrolidone at room temperature. The mixture was warmed to 60 degrees and stirred for 9 hours. The mixture was cooled to room temperature, and 20 parts of 10% saline was added thereto, followed by stirring for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 19 parts of ion-exchanged water to obtain 1.38 parts of the salt represented by the formula (I-45).

Example 10

10.0 parts of the compound represented by the formula (XA-1) and 40 parts of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, and diethylamine was added dropwise to the mixture (Tokyo Chemical Industry Co., Ltd.) Manufactured in 7.2 parts, heated to 65 ° C and stirred for 3 hours. After cooling the reaction solution to room temperature, it was poured into 280 parts of 0.5% saline. Obtaining the obtained precipitate by suction filtration residue to leave 200 parts of the sub-exchanged water was washed and dried to obtain 8.0 parts of the compound represented by the formula (h-100). The yield was 68%.

Identification of compounds represented by formula (h-100)

(mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 479.3 exact mass: 478.2

The compound represented by the formula (BC-1-Na) is added to a solution obtained by dissolving 1.00 part of the compound represented by the formula (h-100) in 5 parts of N-methylpyrrolidone at room temperature. The mixture was warmed to 60 degrees and stirred for 9 hours. The mixture was cooled to room temperature, and 20 parts of 10% saline was added thereto, followed by stirring for 1 hour. Thereafter, precipitates were obtained by suction filtration, and washed with 19 parts of ion-exchanged water to obtain 1.30 parts of the salt represented by the formula (I-43).

Example 11

The compound represented by the formula (BC-18-Na) is added to a solution obtained by dissolving 4.07 parts of the compound represented by the formula (h-1) in 20 parts of N-methylpyrrolidone at room temperature. Stir for 6 hours. 20 parts of 10% saline was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, precipitates were taken by suction filtration, and washed with 19 parts of ion-exchanged water to obtain 6.29 parts of the salt represented by the formula (I-88).

Example 12

To a solution obtained by dissolving 3.94 parts of CI Basic Violet 11 in 20 parts of N-methylpyrrolidone at room temperature, 3.16 parts of the compound represented by the formula (BC-18-Na) was added, and stirred for 6 hours. . 20 parts of 10% saline was added to the mixture, and the mixture was further stirred for 1 hour. Thereafter, precipitates were taken by suction filtration, and washed with 19 parts of ion-exchanged water to obtain 6.34 parts of the salt represented by the formula (I-89).

Example 13

The solution prepared by dissolving CI alkaline red 14.0 parts in 20 parts of N-methylpyrrolidone was heated to 60 degrees, and 2.90 parts of CI solvent yellow 21 was added and dissolved in 14.5 parts of N-methylpyrrolidone. The resulting solution was warmed to 60 degrees and stirred for 3 hours.

2.44 parts of the compound represented by the formula (BC-18-Na) was added to the mixture, and the mixture was further stirred at 60 °C for 8 hours. The mixture was cooled to room temperature, and 138 parts of ion-exchanged water was added, followed by stirring for 1 hour. Thereafter, the precipitate is obtained by suction filtration to ion-exchange water. 213 parts were washed to obtain a mixed salt of a salt represented by the formula (I-90) and a salt of CI basic red 1 represented by the formula (IA-1) and an anion salt of CI solvent yellow 21 (hereinafter, It is 7.47 parts of a mixed salt (I-90-IA-1).

[Measurement of absorbance]

0.35 g of the salt was dissolved in a solvent and the volume was set to 250 cm ³ , and 2 cm ^{3 of the} salt was diluted with a solvent to be 100 cm ³ , and adjusted to a solution having a concentration of 0.028 g/L. For this solution, the maximum absorption wavelength (λ _max ) and the maximum absorption wavelength (λ _max ) were measured using an ultraviolet visible spectrophotometer (V-650DS, manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). The absorbance underneath. The solvent to be used together with the results is shown in Table 4. DMF (dimethylformamide) is an abbreviation for N,N-dimethylformamide.

[Evaluation of Solubility]

The compound obtained in each of Examples 1 to 12, the compound represented by the formula (h-1), the formula (h-120), and the formula (h-100), and the CI basic violet 11 were obtained as follows. Propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA (propylene glycol monomethyl ether acetate)), propylene glycol monomethyl ether (hereinafter abbreviated as PGME (propylene glycol monomethyl ether)), ethyl lactate (hereinafter abbreviated as EL (ethyl lactate) The solubility of).

Further, with respect to the mixed salt I-90-IA-1 and CI basic red 1 obtained in Example 13, N,N-dimethylformamide (hereinafter abbreviated as DMF) and two were obtained in the following manner. The solubility of acetol (hereinafter abbreviated as DAA (diacetone alcohol)).

The compound and the above solvent were mixed in a 50 mL test tube at the following ratio, after which the tube was stoppered and shaken at 30 ° C for 3 minutes by means of an ultrasonic oscillator. After allowing to stand at room temperature for 30 minutes, filtration was carried out to visually observe the residue. When the insoluble matter as the residue could not be confirmed, the solubility was judged to be good, and when the insoluble matter was confirmed, the solubility was judged to be poor. Table 5 shows the maximum concentration at which the solubility is judged to be good. The results are shown in Tables 5 and 6. × means 1% and is bad.

Example 14 [Preparation of coloring composition]

mixing:

A coloring composition is obtained.

[Production of color filter]

The coloring composition obtained above was applied onto the glass by a spin coating method, and the volatile component was volatilized. After cooling, light irradiation was performed using a patterned quartz glass mask and an exposure machine. After the light irradiation, development was carried out with an aqueous potassium hydroxide solution, and the mixture was heated to 200 ° C in an oven 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-31) synthesized in Example 5 was used instead of the compound (I-43) synthesized in Example 10.

From the results of Tables 5 and 6, it was found that the salt of the example showed a higher solubility for the organic solvent. Further, the colored composition containing the salt is less likely to generate foreign matter, and a high-quality color filter can be produced.

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

Claims (4)

a salt of the anion represented by the formula (1) and a phosphonium cation derived from a dye capable of forming a salt with the anion, the sulfonium cation being a cation derived from a triarylmethane dye, derived from a cation of a dye or a cation derived from an anthraquinone dye, [In the formula (1), Z ₁ and Z ₂ are each independently a group represented by the formula (a-1), (a-5), (a-6) or (a-8), (wherein R ₂₃ to R ₂₆ , R ₄₁ to R ₅₂ and R ₆₁ to R ₆₈ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a carbon number of 1; ~4 haloalkyl, halogen atom, hydroxyl group, amine group or nitro group). The salt of claim 1, wherein the base having two substituents derived from the monovalent proton-donating substituent releases protons from the two proton-donating compounds having two monovalent proton-donating substituents a group in which a substituent exudes a proton, and a compound having two monovalent proton-donating substituents is a catechol which may have a substituent, a 2,3-dihydroxynaphthalene which may have a substituent, may have a substitution 2,2'-biphenol, 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthalene which may have a substituent Formic acid, binaphthol which may have a substituent, salicylic acid which may have a substituent, diphenyl glycolic acid which may have a substituent or may have a substituent The bitter almond acid. A dye comprising the salt of claim 1 as an active ingredient. A coloring composition comprising the dye of claim 3.