TWI499645B - Pyridone compounds - Google Patents

Description

Pyridone compound

The present invention relates to a compound useful as a dye.

The dye is used, for example, for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, inkjet, and the like.

For example, a compound represented by the following formula is disclosed in Example 1 of Patent Document 1.

[Patent Document 1] Japanese Patent Laid-Open 2004-2630

The molar absorption coefficient of the previous compound and the solubility in an organic solvent may not be sufficient to meet the demand.

The present invention provides the following [1] to [6].

[1] A compound represented by the formula (I):

[In the formula (I), X ¹ and X ² each independently represent -O-CO- or -CO-O-, L ¹ and L ² represent an alkanediyl group having 1 to 8 carbon atoms, and R ¹ represents a hydrogen atom, Methyl or ethyl, R ² represents a hydrogen atom, a cyano group or an amine carbenyl group, R ³ represents an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group, and R ⁴ to R ⁷ independently represent a hydrogen atom and carbon. An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a hydroxyl group, a cyano group or a nitro group, and at least one of them represents a nitro group].

[2] The compound according to [1] above, wherein X ¹ is *-O-CO- (* represents a bonding position with L ¹ ).

[3] The compound of [1] or [2] above, wherein R ⁵ or R ⁶ is a nitro group.

[4] The compound according to any one of the above [1] to [3] wherein R ² is a cyano group.

[5] A dye comprising the compound according to any one of the above [1] to [4] as an active ingredient.

[6] A colored resin composition containing the dye, resin and solvent of the above [5].

The present invention is a compound represented by the formula (I) (hereinafter, sometimes referred to as a compound (I)). Also included in the compounds of the invention are their tautomers.

[In the formula (I), X ¹ and X ² each independently represent -O-CO- or -CO-O-, L ¹ and L ² represent an alkanediyl group having 1 to 8 carbon atoms, and R ¹ represents a hydrogen atom, Methyl or ethyl, R ² represents a hydrogen atom, a cyano group or an amine carbenyl group, R ³ represents an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group, and R ⁴ to R ⁷ independently represent a hydrogen atom and carbon. An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a hydroxyl group, a cyano group or a nitro group, and at least one of them represents a nitro group].

X ^{1 is} preferably *-O-CO- (* indicates a bonding position with L ¹ ). When X ¹ is *-O-CO-, the production of the compound (I) tends to be easy.

L ¹ and L ² are an alkanediyl group having 1 to 8 carbon atoms, preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms.

Examples of the alkanediyl group having 1 to 8 carbon atoms include a methylene group, an ethyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a butane-1,4-diyl group. Butane-1,3-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl Wait.

R ¹ is a hydrogen atom, a methyl group or an ethyl group.

-L ¹ -X ¹ -L ² -X ² -R ^{1 is} preferably a group having two ester bonds or a group having one ester bond and one carboxyl group. When it has the base mentioned above, the solubility in an organic solvent tends to improve.

As ^{-L 1 -X 1 -L 2 -X 2} -R 1, for example, include a group represented by the formula (f-1) ~ formula (f-26) of.

Wherein, the group represented by the formula (f-4), the group represented by the formula (f-5), the group represented by the formula (f-20), the group represented by the formula (f-25), and the formula (f- 26) The base indicated is easy to obtain raw materials, and thus is preferable.

R ² is a hydrogen atom, a cyano group or an amine mercapto group. Among them, a cyano group is preferred in terms of easy availability of raw materials.

R ³ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom.

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

Examples of the alkyl group having 1 to 4 carbon atoms which are substituted by a halogen atom include a trifluoromethyl group and a pentafluoroethyl group.

As R ³ , a methyl group or a trifluoromethyl group is preferred, and a methyl group is particularly preferred.

R ⁴ to R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a hydroxyl group, a cyano group or a nitro group. And at least one of them is a nitro group.

When the compound (I) has a nitro group, the spectral density tends to be high.

Among them, it is preferred that R ⁵ or R ⁶ is a nitro group, and more preferably R ⁵ is a nitro group. If the nitro group is present at these positions, the spectral density tends to be higher.

Examples of the alkyl group having 1 to 8 carbon atoms include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group; Propyl, isobutyl, t-butyl, isopentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl , 2-ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl , 3-ethylpentyl, 1-propylbutyl, 1-(1-methylethyl)butyl, 1-(1-methylethyl)-2-methylpropyl, 1-methyl Heptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl , 3-ethylhexyl, 4-ethylhexyl, 1-n-propylpentyl, 2-propylpentyl, 1-(1-methylethyl)pentyl, 1-butylbutyl, 1- Butyl-2-methylbutyl, 1-butyl-3-methylbutyl, 1-(1,1-dimethylethyl)butylbutyl, tert-butyl, 1,1-di Methylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethyl- 2- Propyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,2-dimethyl Pentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl, 1-ethyl-1 -methylbutyl, 1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl, 2-ethyl-1-methylbutyl, 2-ethyl-3-methyl Butyl, 1,1-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2 ,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 3,3-dimethylhexyl, 3,4-dimethyl Hexyl, 3,5-dimethylhexyl, 4,4-dimethylhexyl, 4,5-dimethylhexyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methyl Pentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 2-ethyl-2-methylpentyl, 2-ethyl-3-methylpentyl , 2-ethyl-4-methylpentyl, 3-ethyl-1-methylpentyl, 3-ethyl-2-methylpentyl, 3-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 1-propyl-1-methylbutyl, 1-propyl-2-methylbutyl, 1-propyl-3- Butyl, 1-(1-methylethyl)-1-methylbutyl, 1-(1-methylethyl)-2-methylbutyl, 1-(1-methylethyl) a branched alkyl group such as -3-methylbutyl group, 1,1-diethylbutyl group or 1,2-diethylbutyl group.

Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and a 2-ethyl group. Hexyloxy group and the like.

Examples of the alkoxyalkyl group having 2 to 8 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, and a 1-ethyl group. Oxypropyl, 2-ethoxypropyl, 1-ethoxy-1-methylethyl, 1-methyl-2-ethoxyethyl, 1-(1-methylethoxy) Propyl, 2-(1-methylethoxy)propyl, 1-(1-methylethoxy)-1-methylethyl, 2-(1-methylethoxy)-1- Methyl ethyl, 3-ethoxypropyl and the like.

Examples of the compound represented by the formula (I) include the compound (I-1) to the compound (I-111). Y ¹ represents -L ¹ -X ¹ -L ² -X ² -R ¹ . In Table 1, the Y ¹ column describes the number of the formula of the above-exemplified base.

Among them, preferred are the compound (I-1), the compound (I-2), the compound (I-46), the compound (I-68) and the compound (I-90).

These compounds have a tendency to have high solubility in organic solvents.

A method of producing the compound (I) will be described.

The azo compound can be produced by coupling a diazonium salt and a pyridone compound diazo by the method described in Japanese Patent Publication No. Hei 7-88633.

The diazonium salt represented by the formula (a2) can be obtained, for example, by diazotizing an amine represented by the formula (a1) with nitrous acid, nitrite or nitrite.

[In the formula (a1) and the formula (a2), R ⁴ to R ⁷ represent the same meanings as those in the formula (I). A ¹ represents an inorganic or organic anion].

Examples of the inorganic anion include a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, and a hypochlorite ion.

Examples of the organic anion include CH ₃ COO ⁻ , C ₆ H ₅ COO ⁻ and the like.

Preferred are chloride ions, bromide ions, CH ₃ COO ^- and the like.

Production of a compound (I) wherein X ¹ is *-O-CO- (* represents a bond to L ¹ ), that is, a compound represented by the formula (Ia) (hereinafter sometimes referred to as "compound (Ia)") The method is explained.

In the formula (Ia), R ¹ to R ⁷ , L ¹ , L ² and X ² represent the same meanings as those in the formula (I).

By diazo coupling of a diazonium salt represented by the formula (a2) and a compound represented by the formula (b1) in an aqueous solvent, a compound represented by the formula (II-a) can be produced (hereinafter sometimes referred to as "a compound" (II-a)"). The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

In the formulae (b1) and (II-a), R ² to R ⁷ and L ¹ represent the same meanings as those in the formula (I).

Then, the compound (I-a) can be obtained by reacting the compound (II-a) with a compound represented by the formula (b2) (hereinafter sometimes referred to as "compound (b2)") in the presence of an organic solvent. The reaction temperature is preferably from 30 ° C to 180 ° C, more preferably from 50 ° C to 120 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 1 hour to 4 hours.

In the formula (b2), R ¹ , L ² and X ² represent the same meanings as those in the formula (I). Z ¹ represents a chlorine atom or a bromine atom].

Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, and butanol; and nitrohydrocarbons such as nitrobenzene. The solvent is a ketone solvent such as methyl isobutyl ketone or a guanamine solvent such as 1-methyl-2-pyrrolidone.

The amount of the compound (b2) to be used is usually 1 mol or more and 8 mol or less per mol of the compound (II-a), preferably 1 mol or more and 4 mol or less.

Then, the compound (I) wherein X ¹ is *-CO-O- (* represents a bond to L ¹ ), that is, the compound represented by the formula (Ib) (hereinafter sometimes referred to as "compound (Ib)") The manufacturing method will be described.

In the formula (Ib), R ¹ to R ⁷ , L ¹ , L ² and X ² represent the same meanings as those in the formula (I).

In the same manner as described above, a compound represented by the formula (II-b) can be produced by coupling a diazonium salt represented by the formula (a2) with a compound represented by the formula (b3) in an aqueous solvent. It is called "compound (II-b)"). The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 1 hour to 4 hours. Examples of the aqueous solvent include the same solvents as those enumerated above.

In the formulae (b3) and (II-b), R ² to R ⁷ and L ¹ represent the same meanings as those in the formula (I).

Then, the compound (I-b) can be obtained by reacting the compound (II-b) with a compound represented by the formula (b4) (hereinafter sometimes referred to as "compound (b4)") in the presence of an organic solvent. The reaction temperature is preferably from 30 ° C to 180 ° C, more preferably from 50 ° C to 120 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 1 hour to 4 hours.

R ¹ -X ² -L ² -OH (b4)

In the formula (b4), R ¹ , X ² and L ² represent the same meanings as those in the formula (I).

The organic solvent used herein may, for example, be the same solvent as the one used in the reaction of the compound (II-a) and the compound (b2).

The amount of the compound (b4) to be used is usually 1 mol or more and 8 mol or less, more preferably 1 mol or more and 4 mol or less, based on the compound (II-b).

In the reaction, in order to carry out the reaction smoothly, it is more preferable to add an acidic catalyst. Examples of the acidic catalyst include inorganic acids such as sulfuric acid and hydrochloric acid.

The amount of the catalyst used is arbitrary, and it is preferably 0.01 mol or more and 4 mol or less, more preferably 0.8 to 2 mol, based on 1 mol of the compound (b4).

The method of obtaining the target compound, that is, the compound (I) (that is, the compound (I-a) or the compound (I-b)), from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferred to mix the reaction mixture with an acid (e.g., acetic acid or the like) and water, and the precipitated crystals are collected by filtration. It is preferred that the above acid is prepared by previously preparing an aqueous acid solution, and then adding the reaction mixture to the above aqueous solution. The temperature at the time of adding the reaction mixture is usually 10 ° C or more and 50 ° C or less, preferably 20 ° C or more and 50 ° C or less, more preferably 20 ° C or more and 30 ° C or less. Further, it is preferred to add the reaction mixture to an aqueous acid solution and then stir at the same temperature for about 0.5 to 2 hours. The crystals to be filtered are preferably washed by water or the like, followed by drying. Further, it may be further purified by a known method such as recrystallization, as needed.

The compound (I) thus obtained is useful as a dye. Further, since the compound (I) has a high molar absorption coefficient and a high solubility in 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.

The dye of the present invention is a dye containing the compound (I) of the present invention as an active ingredient. The colored resin composition of the present invention contains the dye of the present invention as a colorant (hereinafter sometimes referred to as "colorant (A)"), and further contains a resin (B) and a solvent (E). The colored resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).

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 the dye different from the dye of the present invention, a Colour Index (published by The Society of Dyers and Colourists) can be classified into a solvent (Solvent), an acid (Acid), and an alkaline ( Basic), reactive, direct, disperse or reduced (Vat) dyes. More specifically, a dye of the color index (C.I.) number as described below may be 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 reactive 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 Violet 102; CI Solvent Green 1, 5; CI Acid Green 3, 5, 9, 25, 28; CI Alkaline Green 1; CI Reducing Green 1 and the like.

As the pigment, an organic pigment or an inorganic pigment which is usually used in a pigment dispersion resist 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 oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Composite metal oxide.

Further, examples of the organic pigment and the inorganic pigment include a compound classified into a pigment (Pigment) in a Colour Index (published by The Society of Dyers and Colourists). More specifically, a color index (C.I.) numbered pigment as described below may be mentioned, but 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.

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

The content of the colorant (A) is preferably from 5 to 60% by mass based on the solid content of the colored resin composition. Here, the solid content component means a total component other than the solvent in the colored resin 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 of two or more kinds of the dyes of the present invention.

The resin (B) is not particularly limited, and any resin can be used. The resin (B) is preferably an alkali-soluble resin, more preferably a resin containing a structural unit derived from (meth)acrylic acid. Here, (meth)acrylic acid 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, methacrylic acid/benzyl methacrylate/methacrylic acid. different 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, more preferably from 60 to 135.

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

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

The polymerizable compound (C) is preferably a photopolymerizable compound having three or more polymerizable groups. Examples of the photopolymerizable compound having a polymerizable group of 3 or more include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, and the like. Dipentaerythritol hexamethacrylate or the like. The photopolymerizable compound (C) may be used alone or in combination of two or more.

The content of the polymerizable compound (C) is usually preferably from 5 to 65% by mass, more preferably from 10 to 60% by mass, based on the solid content of the colored resin 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 alkylphenol compound, for example, 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)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 For the compound, for example, 2-isopropyl-9-oxysulfide 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 ruthenium compound, and specific examples thereof include N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one- 2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-ethyloxy-1-[9-ethyl -6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2 -methyl-4-(3,3-dimethyl-2,4-dioxolanylmethyloxy)benzylidenyl}-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' may be used. 5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzoin, 9,10-phenanthrenequinone, camphorquinone, Methyl phenylglyoxylate, a titanocene compound, and the like.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenyloxyphenyldimethylate. Base p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, An anthracene salt such as phenylhydrazine p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate or a nitrobenzyl tosylate or a benzoin tosylate.

The above polymerization initiators (D) may be used singly 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, high sensitivity is obtained, exposure time is shortened, and productivity is improved, which is preferable.

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

Examples of the above 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 ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol single Ethyl acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acid esters, etc.

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

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl ester, butyl butyrate, alkyl ester, methyl lactate, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy acetic acid Methyl ester, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate Ethyl acetate, ethyl 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 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 singly or in combination of two or more.

The content of the solvent (E) in the colored resin composition is preferably from 70 to 95% by mass, more preferably from 75 to 90% by mass, based on the amount of the colored resin composition.

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

The compounds of the invention are useful as dyes. Since the compound of the present invention has a high molar absorption coefficient and exhibits excellent solubility in 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 colored resin composition containing the compound of the present invention can be used in a known manner for 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

The invention will now be described in more detail by way of examples.

In the examples and comparative examples, the % and the parts indicating the content or the amount used are based on mass unless otherwise specified.

In the following examples, the structure of the compound was confirmed by NMR (Nuclear Magnetic Resonance) (JMM-ECA-500, manufactured by JEOL Ltd.).

[Example 1]

After adding 80 parts of water to 18.2 parts of 5-nitro-o-amine benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 part of sodium hydroxide was added and dissolved. Under ice cooling, 19.7 parts of a 35% aqueous sodium nitrite solution was added, followed by a small amount of 26.2 parts of 35% hydrochloric acid, and stirred for 2 hours to dissolve, thereby obtaining a suspension containing a diazonium salt.

On the other hand, 26.0 parts of ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.8 parts of methyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2-aminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) 24.4 parts were mixed and stirred at 95 ° C for 24 hours. After cooling the reaction solution to room temperature, it was added to a mixture of 304 parts of water and 35 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue obtained by suction filtration, and then dried to obtain 20.4 parts of a compound represented by the formula (c-1).

Then, 20.4 parts of the compound represented by the formula (c-1) was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. Therein, the above suspension containing a diazonium salt was added dropwise using a pump for 15 minutes. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, whereby a yellow suspension was obtained. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 38.7 parts of the compound of the formula (d-1).

Then, 30.1 parts of the compound represented by the formula (e-1) was added to 38.7 parts of the compound represented by the formula (d-1), and the mixture was stirred at 70 ° C for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, it was added to water to obtain 42.35 parts of the compound represented by the formula (I-1). The structure was confirmed by ¹ H-NMR.

Identification of Compound (I-1)

¹ H-NMR: 2.50 (4H, m), 2.98 (3H, s), 3.52 (3H, s), 4.10 (2H, t), 4.22 (2H, t), 8.14 (1H, d), 8.44 (1H) , m), 8.70 (1H, d).

0.35 g of the compound represented by the formula (I-1) obtained was dissolved in dimethylformamide and the volume was adjusted to 250 cm ³ , and 2 cm ^{3 was} diluted by ethyl lactate and the volume was adjusted to 100. Cm ³ (concentration: 0.028 g/L), an absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V-650DS, manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). The compound has a yellow color of λmax = 435 nm and a molar absorption coefficient of up to 60,000.

[Embodiment 2]

25.7 parts of the compound represented by the formula (e-2) was added to 30.1 parts of the compound represented by the formula (d-1), and the mixture was stirred at 70 ° C for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, it was added to water to obtain 37.0 parts of the compound represented by the formula (I-46). The structure was confirmed by ¹ H-NMR.

Identification of Compound (I-46)

¹ H-NMR: 1.10 (3H, t), 2.49 (2H, t), 2.49 (2H, t), 2.56 (3H, s), 3.96 (2H, q), 4.10 (2H, t), 4.23 (2H) , t), 8.16 (1H, d), 8.46 (1H, dd), 8.70 (1H, d), 14.50 (1H, bs), 15.56 (1H, s).

0.10 g of the compound represented by the formula (I-46) obtained was dissolved in dimethylformamide and the volume was adjusted to 250 cm ³ , and 2 cm ^{3 was} diluted by ethyl lactate and the volume was adjusted to 100. Cm ³ (concentration: 0.0080 g/L), an absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V-650DS, manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). The compound has a yellow color of λmax = 438 nm and a molar absorption coefficient of up to 50,000.

[Comparative Example 1]

In Example 1, 2-aminoterephthalic acid was used instead of 5-nitro-o-amine benzoic acid, and compound (c-2) represented by the following structural formula was used instead of (c-1) described above. The compound was synthesized in the same manner as in Example 1 to obtain a compound represented by the formula (i).

0.35 g of the obtained compound represented by the formula (i) was dissolved in dimethylformamide and the volume was adjusted to 250 cm ³ , and 2 cm ^{3 was} diluted by ethyl lactate to adjust the volume to 100 cm ³ ( Concentration: 0.028 g/L), an absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V-650DS, manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). The compound has a λmax = 440 nm and a molar absorption coefficient of only 42,000.

<Evaluation of Solubility>

The compound obtained in Example 1, Example 2, and Comparative Example 1 was obtained in the following manner in propylene glycol monomethyl ether (hereinafter abbreviated as PGME), ethyl lactate (hereinafter abbreviated as EL), and N-methylpyrrolidone. Solubility in (hereinafter referred to as NMP).

The compound was mixed with the above solvent in a 50 mL sample tube, and then the sample tube was stoppered and shaken at 30 ° C for 3 minutes by an ultrasonic vibration machine. Then, it was allowed to stand at room temperature for 30 minutes, and then filtered, and the residue was visually observed. When the insoluble matter could not be confirmed, it was judged that the solubility was good, and it was indicated as ○ in Table 2, and when the insoluble matter was confirmed, the solubility was judged to be inferior in Table 2 and indicated as × in Table 2.

0.5% compound 0.01 g, solvent 2 g

1% compound 0.01 g, solvent 1 g

3% compound 0.03 g, solvent 1 g

Example 3 [Preparation of Colored Photosensitive Resin Composition]

(A) Colorant: Compound (I-1): Compound synthesized in Example 1 20 parts

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

(C-1) Polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 30 parts

(D-1) Photopolymerization initiator: benzoin dimethyl ketal (Irgacure 651, manufactured by Chiba‧ Japan) 15 parts

(E-1) Solvent: propylene glycol monomethyl ether 680 parts

The above components are mixed to obtain a colored resin composition.

[Production of color filter]

The colored resin composition obtained above was applied onto the glass by spin coating to volatilize the volatile component. After cooling, light irradiation was performed using a patterned quartz glass mask and an exposure machine. After the light irradiation, development was carried out using an aqueous potassium hydroxide solution, and the mixture was heated to 200 ° C in an oven to obtain a color filter.

Example 4

A colored resin composition and a color filter were obtained in the same manner as in Example 3 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-46) synthesized in Example 2.

From the results of Table 2, it is understood that the compound of the present invention exhibits a high solubility to an organic solvent. The colored resin composition containing the compound has less generation of impurities, and a high-quality color filter can be produced.

Industrial availability

Since the moth of the compound of the present invention has a high light absorption coefficient and is excellent in solubility in 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 colored resin composition containing the compound of the present invention can be used in a known manner for a display device including a color filter as a part of a constituent member (for example, a known liquid crystal display device, an organic EL device, etc.), and a solid-state imaging device. And so on in various machines related to coloring images.

Claims (6)

a compound represented by formula (I), [In the formula (I), X ¹ and X ² each independently represent -O-CO- or -CO-O-, L ¹ and L ² represent an alkanediyl group having 1 to 8 carbon atoms, and R ¹ represents a hydrogen atom, Methyl or ethyl, R ² represents a hydrogen atom, a cyano group or an amine carbenyl group, R ³ represents an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group, and R ⁴ to R ⁷ independently represent a hydrogen atom or a nitrate Base, and at least one of them represents a nitro group]. The compound of claim 1, wherein X ¹ is *-O-CO-, and [* represents a bonding position with L ¹ ]. The compound of claim 1 or 2, wherein R ⁵ or R ⁶ is a nitro group. The compound of claim 1, wherein R ² is cyano. A dye comprising the compound of claim 1 as an active ingredient. A colored resin composition containing the dye, resin and solvent of claim 5.