TWI521022B - Compound - Google Patents

Description

Compound

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

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

As such a dye, for example, a quinacridone dye C.I. Acid Yellow 3 represented by the following formula is widely known.

[Previous Technical Literature] [Non-patent literature]

Non-Patent Document 1: Yokote Masahiro, Shiba Miyazumi, "Synthetic Dyes", First Edition, Nikkan Kogyo Shimbun, April 1978, 128 pages

The above-mentioned compounds previously known cannot sufficiently satisfy the solubility in an organic solvent.

The present invention provides the following [1] to [10].

[1] a compound represented by the formula (1), [In the formula (1), L ¹ represents a single bond, an alkanediyl group having 1 to 8 carbon atoms, -SO ₂ -, -O-, -CO- or -CO-O-, and is contained in the alkanediyl group. The hydrogen atom may also be substituted by a halogen atom, and -CH ₂ - contained in the alkanediyl group may also be substituted by -O- or -CO-; R ¹ and R ² independently of each other represent a hydrogen atom or a carbon number of 1-8. The alkyl group; A ¹ and A ² independently of each other represent a benzene ring which may have a substituent, a naphthalene ring which may have a substituent or a quinoline ring which may have a substituent; m and n independently of each other represent 0 to 5 An integer, wherein m+n is an integer of 1 to 8, and when m+n is an integer of 2 or more, the plurality of -SO ₂ NR ¹ R ² are the same or different from each other].

[2] The compound according to the above [1], wherein A ¹ is a benzene ring which may have a substituent.

[3] As the above-mentioned [1] or a compound [2] of wherein A ¹ is non-substituted benzene ring or a benzene ring having the halo group.

[4] The compound according to any one of the above [1] to [3] wherein A ¹ and A ² are each independently a benzene ring which may have a substituent.

[5] The compound according to any one of the above [1] to [4] wherein A ¹ and A ² are each independently an unsubstituted benzene ring or a benzene ring having a halogen group.

[6] The compound according to any one of the above [1] to [5] wherein R ¹ and R ² are each independently a hydrogen atom or a branched alkyl group having 1 to 8 carbon atoms.

[7] The compound according to any one of the above [1] to [6] wherein L ¹ is a single bond or -SO ₂ -.

[8] The compound according to any one of the above [1] to [7] wherein m+n is an integer of from 1 to 5.

[9] A dye comprising the compound according to any one of the above [1] to [8] as a main component.

[10] A coloring composition comprising the dye according to [9] above.

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

The compound of the present invention is represented by the formula (1) (hereinafter, sometimes referred to as the compound (1)), [In the formula (1), L ¹ represents a single bond, an alkanediyl group having 1 to 8 carbon atoms, -SO ₂ -, -O-, -CO- or -CO-O-, and is contained in the alkanediyl group. The hydrogen atom may also be substituted by a halogen atom, and -CH ₂ - contained in the alkanediyl group may also be substituted by -O- or -CO-; R ¹ and R ² independently of each other represent a hydrogen atom or a carbon number of 1-8. the alkyl group; A ¹ and A ² each independently represent a benzene ring may have a substituent group, the group may have a substituent of the naphthyl ring or group may have a substituent of the quinoline ring; m and n each independently represents 0 to 5 of An integer, wherein m+n is an integer of 1 to 8, and when m+n is an integer of 2 or more, the plurality of -SO ₂ NR ¹ R ² are the same or different from each other].

L ¹ represents a single bond, alkanediyl group having a carbon number of 1 to _{8, -SO 2 -, - O -} , - CO- or -CO-O-. In terms of heat resistance, L ^{1 is} preferably a single bond or -SO ₂ -.

Examples of the alkanediyl group having 1 to 8 carbon atoms include a methylene group, an exoethyl group, a propane-1,3-diyl group, a propionyl-1,2-diyl group, and a propane-2,2-diyl group. Butyl-1,4-diyl, butyl-1,3-diyl, butyl-2,2-diyl, pent-1,5-diyl, pent-2,2-diyl, 2-methylbutyl -3,3-diyl, hex-1,6-diyl, hept-1,7-diyl and octane-1,8-diyl, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the group in which the hydrogen atom contained in the alkanediyl group having 1 to 8 carbon atoms is substituted by a halogen atom may, for example, be 1,1,1,3,3,3-hexafluoropropane-2,2-diyl. 2,2-difluoropropane-1,3-diyl and 2,2-dichloropropane-1,3-diyl and the like.

The group in which -CH ₂ - contained in the alkanediyl group having 1 to 8 carbon atoms is substituted with -O- or -CO- may, for example, be a group represented by the following formula. In the following formula, ^* represents a bonding bond.

R ¹ and R ² independently of each other represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, an n-octyl group, and the like. Linear alkyl; isopropyl, 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 Base, 2-ethylpentyl, 3-ethylpentyl, 1-propylbutyl, 1-(1-methylethyl)butyl, 1-(1-methylethyl)-2-methyl Propyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethyl Hexyl, 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 1,1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl base , 1-ethyl-2-methylpropyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethyl Pentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethyl Pentyl, 1-ethyl-1-methylbutyl, 1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl, 2-ethyl-1-methylbutyl , 2-ethyl-3-methylbutyl, 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-dimethyl Hexyl, 3,4-dimethylhexyl, 3,5-dimethylhexyl, 4,4-dimethylhexyl, 4,5-dimethylhexyl, 1-ethyl-2-methylpentyl , 1-ethyl-3-methylpentyl, 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-B 3-methylpentyl, 3-ethyl-4-methylpentyl, 1-propyl-1-methylbutyl, 1-propyl-2-methylbutyl , 1-propyl-3-methylbutyl, 1-(1-methylethyl)-1-methylbutyl, 1-(1-methylethyl)-2-methylbutyl, 1 a branched alkyl group such as -(1-methylethyl)-3-methylbutyl, 1,1-diethylbutyl or 1,2-diethylbutyl.

Wherein R ¹ and R ² are each independently a branched alkyl group having 3 to 8 carbon atoms, more preferably a branched alkyl group having 6 to 8 carbon atoms, and more preferably a branch having a carbon number of 8 The alkyl group is more preferably 2-ethylhexyl.

Examples of -SO ₂ NR ¹ R ² include an unsubstituted sulfonamide group, an N-1 substituted amine sulfonyl group, and an N,N-2 substituted amine sulfonyl group.

Examples of the N-1 substituted amine sulfonyl group include N-methylaminesulfonyl group, N-ethylaminesulfonyl group, N-propylaminesulfonyl group, and N-isopropylaminesulfonyl group. , N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonyl , N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl)aminesulfonate , N-(2,2-dimethylpropyl)amine sulfonyl, N-(1-methylbutyl)amine sulfonyl, N-(2-methylbutyl)amine sulfonyl, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine sulfonyl , N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1,4-di Methyl amyl sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl)hexylamine sulfonyl and N-(1,1,2,2-tetramethylbutyl)amine sulfonyl and the like.

As the N,N-2 substituted amine sulfonyl group, for example, N,N-dimethylamine sulfonyl group, N,N-ethylmethylamine sulfonyl group, N,N-diethylamine sulfonate Indenyl, N,N-propylmethylaminesulfonyl, N,N-isopropylmethylaminesulfonyl, N,N-tert-butylmethylaminesulfonyl, N,N-butyl Amidoxime, N,N-bis(1-methylpropyl)aminesulfonyl and N,N-heptylmethylaminesulfonyl.

m and n are independent of each other and represent an integer from 0 to 5. Wherein m+n is an integer from 1 to 8, preferably an integer from 1 to 5. Further, it is preferable that m and n are independently 0 or 1 and m+n is 1.

In the case where a plurality of -SO ₂ NR ¹ R ² are present, it is preferred that the groups are the same species.

A ¹ and A ² independently of each other represent a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a quinoline ring which may have a substituent. Examples of the substituents include -R ³ , -OR ³ , -COR ³ , -O-COR ³ , a fluorinated alkyl group having 1 to 8 carbon atoms, a halogen group, a hydroxyl group, a sulfanyl group, a carboxyl group, and a nitro group. , formazan, -NHR ³ and -NR ³ R ^4, and the like. Here, R ³ and R ⁴ represent an alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group include the same groups as those recited above.

Examples of the fluorinated alkyl group having 1 to 8 carbon atoms include a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and the like. Fluorohexyl, perfluoroheptyl and perfluorooctyl.

Examples of -OR ³ 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-ethylhexyloxy group.

Examples of -COR ³ include an ethyl group, a propyl group, a butyl group, a pentamidine group, and a pentamidine group.

Examples of the -O-COR ³ include an ethoxycarbonyl group, a propenyloxy group, a butoxy group, a pentyloxy group, and a p-pentyloxy group.

Examples of -NHR ³ include N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N-pentylamino group and N-octylamino group. Wait.

Examples of -NR ³ R ⁴ include N,N-dimethylamino group, N,N-diethylamino group, N,N-dipropylamino group, and N,N-dibutylamino group. N-butyl-N-methylamino group and N,N-dioctylamino group and the like.

Examples of the halogen group include a fluorine group, a chlorine group, a bromine group, and an iodine group, and a chlorine group is preferred.

In the above, A ^{1 is} preferably a benzene ring which may have a substituent, and A ^{1 is more} preferably an unsubstituted benzene ring or a benzene ring having a halogen group. In this aspect, the halogen group is preferably a chlorine group.

Further, A ¹ and A ^{2 are} preferably a benzene ring which may be independently a substituent, and A ¹ and A ^{2 are more} preferably an unsubstituted benzene ring or a benzene ring having a halogen group. In this aspect, the halogen group is preferably a chlorine group.

Further, it is preferred that A ¹ and A ² are each independently an unsubstituted benzene ring or a benzene ring having a halogen group, and R ¹ and R ² are each independently a hydrogen atom or a branched alkyl group having a carbon number of 8, L ¹ It is a single bond or -SO ₂ -, m and n are independently 0 or 1 and m+n is 1. In this aspect, the halogen group is preferably a chlorine group.

Further preferably, A ¹ and A ² are the same and are an unsubstituted benzene ring or a benzene ring having a halogen group, and R ¹ and R ² are the same and are a hydrogen atom or a branched alkyl group having a carbon number of 8. L ¹ is a single bond or -SO ₂ -, m and n are independently 0 or 1 and m+n is 1. In this aspect, the halogen group is preferably a chlorine group.

As compound (1)

or Examples of the group represented by the following formula (q-1) to formula (q-46) include the following. Among them, preferred are formula (q-1), formula (q-14), formula (q-24), formula (q-26), formula (q-30), formula (q-31), formula (q) -35), a group represented by the formula (q-36) and the formula (q-38), more preferably a formula (q-1), a formula (q-14), a formula (q-26), or a formula (q- 35) and the base represented by the formula (q-38). In the following formula, x represents m or n.

Since the compound (1) is easier to manufacture,

versus It is preferably the same structure.

Examples of the compound (1) include the compound (1-1) to the compound (1-405). Furthermore, Q ¹ means Q ² means

In Table ^1, Q 1 and Q ² column column indicates the type of the above-exemplified group of numbers.

The compound (1) can be produced by introducing a sulfo group into a compound represented by the formula (Z) and then aminating the sulfosulfonium.

[In the formula (Z), L ¹ , A ¹ and A ² represent the same meaning as described above]

The compound represented by the formula (Z) (hereinafter sometimes referred to as "compound (Z)") can be represented by the compound represented by the formula (X), the compound represented by the formula (Y1), and the formula (Y2). The compound shown is produced by reacting in an organic solvent.

[In the formula (X), the formula (Y1) and the formula (Y2), L ¹ , A ¹ and A ² represent the same meanings as described above]

As the organic solvent used for the reaction, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, cyclobutyl hydrazine, N,N-dimethylformamide, N,N- may be mentioned. Dimethylacetamide and a mixed solvent of these. The amount of the organic solvent to be used varies depending on the type of the solvent, and is 3 to 50 parts by mass, preferably 5 to 20 parts by mass, per part by mass of the compound represented by the formula (X).

The total amount of the compound represented by the formula (Y1) and the compound represented by the formula (Y2) is 1 mol, preferably 2 to 8 mol, more preferably 2 to 8 mol, based on the compound represented by the formula (X). 3~5 moles.

The reaction temperature is preferably from 150 to 250 ° C, more preferably from 180 to 220 ° C. The reaction time is preferably from 5 to 72 hours, more preferably from 8 to 24 hours.

After completion of the reaction, the reaction mixture is mixed with a poor solvent of the compound (Z), and the precipitate is collected by filtration, whereby the compound (Z) can be obtained. Examples of the poor solvent include acetonitrile, ethyl acetate, tetrahydrofuran, and diethyl ether.

The amount of the poor solvent to be used is preferably 1 to 50 parts by mass, more preferably 5 to 20 parts by mass, per part by mass of the reaction liquid.

The precipitate obtained by filtration is preferably washed with an alcohol solvent or the like, and then dried. Further, it may be further purified by a known method such as recrystallization as needed. Examples of the alcohol solvent used for washing include methanol, ethanol, and isopropyl alcohol.

Then, the compound (Z) is sulfonated to introduce a sulfo group. The sulfonation can be carried out by a known method, and a method of directly sulfonating the compound (Z) using a sulfonating agent is preferred. By bringing the compound (Z) into contact with the sulfonating agent and When the reaction is carried out, a compound having a sulfo group introduced into the compound (Z) (hereinafter sometimes referred to as "sulfonic acid compound (Z1)") may be produced.

Examples of the sulfonating agent include chlorosulfonic acid, sulfonium chloride, sulfuric acid, fuming sulfuric acid, and sulfur trioxide, and chlorosulfonic acid is preferred. The amount of the sulfonating agent to be used is preferably 1 to 20 parts by mass, more preferably 5 to 10 parts by mass, per part by mass of the compound (Z).

The reaction temperature is preferably from 50 to 150 ° C, more preferably from 70 to 100 ° C. The reaction time is preferably from 2 to 15 hours, more preferably from 4 to 8 hours.

The resulting sulfonic acid compound (Z1) can be extracted by a known method, or can be directly used in the next sulfonylation reaction in the state of the mixture after the sulfonation reaction.

Then, the sulfonic acid compound (Z1) is sulfonated. After the sulfonic acid compound (Z1) has a sulfonyl group which is halogenated to form a sulfonium halide compound (Z2), the sulfonium halide compound (Z2) is reacted with an amine compound, whereby the compound (1) can be obtained.

The sulfonic acid compound (Z1) can be halogenated, for example, using a sulfinium halide compound. Examples of the sulfinium halide compound include sulfinium chloride. The sulfenium halide compound is used in an amount of 1 to 10 moles per mole of the sulfonic acid compound (Z1). However, when water having a large amount of water contained in the sulfonic acid compound (Z1) to be used is carried into the reaction system, it is preferred to further use an excessive amount to decompose water.

The reaction can be carried out in the absence of a solvent or in a solvent. As the solvent, for example, tetrahydrofuran and 1,4-di An ether such as an alkane; a halogenated hydrocarbon such as chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethylene, dichloropropane, chloropentane or 1,2-dibromoethane; a nitrile such as acetonitrile; An amine such as N-methyl-2-pyrrolidone. Among them, preferred are chloroform, acetonitrile and N-methyl-2-pyrrolidone.

The amount of the solvent to be used is preferably from 3 to 10 parts by mass, more preferably from 5 to 8 parts by mass, per part by mass of the sulfonic acid compound (Z1).

The reaction temperature is preferably from 0 to 100 ° C, more preferably from 50 to 80 ° C. The reaction time is from 0.5 to 10 hours, preferably from 1 to 5 hours.

The resulting sulfonium halide compound (Z2) can be extracted by a known method, or can be directly used for the reaction with an amine compound in the state of the reaction mixture.

As a method of extracting the sulfonium halide compound (Z2), the sulfonium halide compound (Z2) can be obtained by mixing the reaction liquid after completion of the reaction with ice water and filtering the precipitate. The amount of the ice water to be used is preferably 3 to 20 parts by mass, more preferably 5 to 12 parts by mass, per part by mass of the reaction mixture. The precipitate obtained by filtration is preferably washed with water or the like to reduce the residue of the sulfonium halide compound.

The reaction of the sulfonium halide compound (Z2) with the amine compound can be carried out by mixing in a solvent. Examples of the solvent used for the reaction include amines such as N-methyl-2-pyrrolidone. This reaction can also be carried out in the presence of a basic catalyst. It is preferred to add an amine compound dropwise after mixing the sulfonium halide compound (Z2) with a solvent.

Examples of the amine compound include n-propylamine, n-butylamine, n-hexylamine, 1,5-dimethylhexylamine, 1,1,3,3-tetramethylbutylamine, 2-ethylhexylamine, and 3 -Amino-1-phenylbutane, isopropoxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, and the like. These may be used singly or in combination of two or more.

The amount of the amine compound used is preferably 3 to 10 moles, more preferably 3 to 7 moles, per mole of the sulfonium halide compound (Z2).

As the basic catalyst, for example, a tertiary amine such as triethylamine, triethanolamine or pyridine is preferable. The amount of the alkaline catalyst used is 1.1 to 2 moles relative to the amine compound 1 mole. The basic catalyst may be added dropwise at the same time as the amine compound, or may be added separately from the amine compound.

The reaction temperature is preferably from 0 to 50 ° C, more preferably from 0 to 30 ° C, still more preferably from 5 to 20 ° C. The reaction time is preferably from 1 to 25 hours.

The compound (1) can be obtained by filtering a precipitate from the reaction liquid after completion of the reaction with the amine compound. An alcohol solvent such as methanol, ethanol or isopropyl alcohol and/or an acidic aqueous solution may be mixed in the reaction liquid to precipitate the product, followed by filtration. The amount of the alcohol solvent to be used is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass, per part by mass of the reaction liquid. As the acidic aqueous solution, an aqueous solution of an acidic substance can be used. The hydrogen ion concentration of the acidic aqueous solution is preferably pH = 0 to 6, more preferably 1 to 5. The acidic substance is not particularly limited, and examples thereof include ammonium chloride, oxalic acid, acetic acid, hydrochloric acid, and sulfuric acid. The amount of the acidic aqueous solution to be used is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass, per part by mass of the reaction liquid.

The compound (1) obtained by filtration is preferably washed with an alcohol solvent or the like. Examples of the alcohol solvent used for washing include methanol, ethanol, and isopropyl alcohol. After washing, drying is preferably carried out.

The compound of the present invention thus obtained is particularly useful as a dye for a color filter of a display device such as a liquid crystal display device because of its high heat resistance.

The coloring composition of the present invention preferably contains the compound of the present invention as a coloring agent (hereinafter sometimes referred to as "coloring agent (A)"), and further contains a resin (B). More preferably, the colored composition of the present invention further comprises at least one selected from the group consisting of a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

The colorant (A) may further contain a pigment and/or a dye (although different from the compound of the present invention) in addition to the compound of the present invention.

As the dye, it can be exemplified as Solvent, Acid, and Basic in the Colour Index (published by The Society of Dyers and Colourists). , reactive, direct, disperse or reduced (Vat) dyes. More specifically, the dye of the following dye index (C.I.) number is mentioned, but it is not limited to these. Among them, an organic solvent-soluble dye is preferred.

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 purple 102; CI solvent green 1, 5; CI acid green 3, 5, 9, 25, 28; CI alkaline green 1; CI reduced green 1 and so on.

As the above pigment, an organic pigment or an inorganic pigment which is generally used for pigment dispersion resist can be mentioned. 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. Or a composite metal oxide. Further, specific examples of the organic pigment and the inorganic pigment include compounds classified as Pigments in the Colour Index (published by The Society of Dyers and Colourists). More specifically, the following dye index (C.I.) number of pigments are mentioned, but it is not limited to these.

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; 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 and the like.

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 which remove the solvent in the coloring composition.

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

These dyes and pigments may be used alone or in combination with the compound of the present invention, or may be used in combination with two or more of the compounds 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, and methacrylic acid/benzyl methacrylate/ Methacrylic 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 from 5,000 to 35,000, more preferably from 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 preferably relative to the solid content of the coloring composition. It is 7 to 65 mass%, more preferably 13 to 60 mass%.

The polymerizable compound (C) is not particularly limited as long as it is a compound which can be polymerized by an active radical generated from the polymerization initiator (D), an acid or the like. 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 the like. Dipentaerythritol hexamethacrylate or the like. These polymerizable compounds may be used singly 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 generator generates active radicals by the action of heat or light. Examples of the living radical generating agent include an alkylphenone compound, a thioxanthone compound, and three Compounds, hydrazine compounds, and the like.

As the above alkylphenone compound, for example, 2-methyl-2- Lolinyl-1-(4-methylsulfanylphenyl)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.

Examples of the above thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthiaxanone, and 2,4-dichloro. Xanthone and 1-chloro-4-propoxythiaxanthone.

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 And 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri Wait.

Examples of the ruthenium compound include an O-acyloxime-based compound, and specific examples thereof include N-benzylideneoxy-1-(4-phenylsulfanylphenyl). Butan-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-acetoxy 1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1- 9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxa Cyclopentylmethyloxy)benzhydryl}-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(2-chlorophenyl)-4,4 can also be used. ',5,5'-Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl hydrazine, diphenylethylenedione, 9,10-phenanthrenequinone , camphorquinone, methyl phenylglyoxylate and titanium titanate compounds.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethylhydrazine. Oxyphenyl dimethyl quinone p-toluene sulfonate, 4-ethoxy phenyl phenyl-methyl-benzyl hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium a sulfonium salt such as fluoroantimonate, diphenylphosphonium p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate; or nitrobenzyl tosylate, benzoin tosylate or the like.

These polymerization initiators 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 in the above range, the sensitivity is high, the exposure time is shortened, and the productivity is improved, which is preferable.

The solvent (E) is not particularly limited as long as it can dissolve the compound of the present invention, and examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols, esters, and amines.

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 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 and 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, and 2-heptanone. 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 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 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.

Since the compound of the present invention exhibits high heat resistance, it is particularly useful as a dye for a color filter of a display device such as a liquid crystal display device.

Further, the coloring composition of the present invention can be used in a known display device including a color filter as a part of its constituent parts (for example, a known liquid crystal display device, an organic EL (Electro Luminescence) device, etc.) Various types of machines related to color images, such as solid-state imaging devices.

[Examples]

Next, the present invention will be more specifically described by way of examples. In the examples, unless otherwise stated, the % or the part of the content or the amount used is a quality standard.

In the following examples, the structure of the compound was analyzed by elemental analysis (VARIO-EL; (manufactured by Elementar Analytical Co., Ltd.) and mass analysis (LC; Model 1200 manufactured by Agilent Technologies, MASS; Agilent) Confirmed by LC/MSD type manufactured by Science and Technology Co., Ltd.).

[Example 1]

After adding 5.26 parts of cyclopentanthene to 7.00 parts of the compound represented by the formula (X-1) (manufactured by Tokyo Chemical Industry Co., Ltd.), the mixture was heated to 180 ° C to be dissolved. After confirming the dissolution, 11.19 parts of quinaldine (Tokyo Chemical Industry Co., Ltd.) was added and refluxed at 200 ° C for 9 hours to carry out a reaction. After completion of the reaction, the reaction solution was poured into 500 parts of acetonitrile and the precipitate was collected by filtration. The obtained precipitate was separately repulped by using 500 parts of ethanol and 500 parts of dimethyl hydrazine each to obtain a yellow solid. The yellow solid was dried under reduced pressure at 60 ° C to obtain 4.5 parts of the compound represented by formula (z-1).

Identification of the compound represented by formula (z-1): (elemental analysis) C70.84 H3.28 N4.75 S5.09

Then, 7.0 parts of the compound represented by the formula (z-1) was added to 67.0 parts of chlorosulfonic acid, and the mixture was stirred at 70 ° C for 4 hours. After stirring, 10.95 parts of sulfinium chloride was added dropwise to the reaction liquid, and the mixture was stirred at 80 ° C for 2 hours, and then cooled to 15 ° C, and further continuously stirred for 14 hours. After completion of the reaction, the mixture was slowly poured into 556 parts of ice water and stirred, followed by filtration. The obtained residue was poured into 200 parts of N-methyl-2-pyrrolidone, and 29.73 parts of 2-ethylhexylamine was added dropwise thereto, and the mixture was stirred at 20 to 30 ° C for 18 hours, and then filtered. Get the residue. The residue was added to 800 parts of 20% acetic acid water and stirred for 2 hours, and then a residue was obtained by filtration. After the residue was added to 400 parts of acetonitrile and stirred for 2 hours, a yellow solid was obtained by filtration. 4.9% of the compound represented by the formula (I-5) was obtained by drying the yellow solid under reduced pressure at 60 ° C for 15 hours.

Identification of the compound represented by formula (I-5) (mass analysis) ionization mode = ESI +: m / z = 780.3 [M] ⁺ Exact Mass: 799.2

Based on the above results, it was confirmed that m+n was 1.

[Embodiment 2]

After adding 5.26 parts of cyclobutyl hydrazine to 7.00 parts of the compound represented by the formula (X-1), the mixture was heated to 180 ° C to be dissolved. After confirming dissolution, 13.88 parts of 8-chloroquinaldine was added and refluxed at 200 ° C for 9 hours. After completion of the reaction, the reaction solution was poured into 500 parts of acetonitrile and the precipitate was collected by filtration. The obtained precipitate was separately repulped by using 500 parts of ethanol and 500 parts of dimethyl hydrazine each to obtain a yellow solid. The yellow solid was dried under reduced pressure at 60 ° C to obtain 8.15 parts of the compound of formula (z-2).

Identification of the compound represented by formula (z-2): (elemental analysis) C63.3 H2.8 N3.8 C110.2 S5.0

Then, 3.0 parts of the compound represented by the formula (z-2) was added to 25.8 parts of chlorosulfonic acid, and the mixture was stirred at 70 ° C for 4 hours. After stirring, 4.21 parts of sulfinium chloride was added dropwise to the reaction liquid, and the mixture was stirred at 80 ° C for 2 hours, and then cooled to 15 ° C or lower, and further continuously stirred for 14 hours. After completion of the reaction, the mixture was slowly poured into 556 parts of ice water and stirred, followed by filtration. The obtained residue was poured into 100 parts of N-methyl-2-pyrrolidone and 2-ethylhexyl was added dropwise thereto. 5.72 parts of the amine was stirred at 20 to 30 ° C for 18 hours, and then the residue was obtained by filtration. After the residue was added to 400 parts of 20% aqueous acetic acid and stirred for 2 hours, a residue was obtained by filtration. After the residue was added to 400 parts of acetonitrile and stirred for 2 hours, a yellow solid was obtained by filtration. 2.9% of the compound represented by the formula (I-20) was obtained by drying the yellow solid under reduced pressure at 60 ° C for 15 hours.

Identification of the compound represented by the formula (I-20) (mass spectrometry) ionization mode = ESI +: m / z = 868.3 [M] + Exact Mass: 867.1

Based on the above results, it was confirmed that m+n was 1.

[Example 3]

After adding 92.65 parts of cyclobutyl hydrazine to 10.0 parts of the compound represented by the formula (X-2) (manufactured by Tokyo Chemical Industry Co., Ltd.), the mixture was heated to 180 ° C to be dissolved. After confirming dissolution, 24.15 parts of quinaldine was added and refluxed at 200 ° C for 9 hours. After completion of the reaction, the reaction solution was poured into 500 parts of acetonitrile and the precipitate was collected by filtration. The obtained precipitate was separately repulped by using 500 parts of ethanol and 500 parts of dimethyl hydrazine each to obtain a yellow solid. The yellow solid was dried at 60 ° C under reduced pressure to obtain 13.5 parts of the compound represented by the formula (z-3).

Identification of the compound represented by formula (z-3): (Elemental analysis) C79.97 H3.68 N5.31

Then, 5.0 parts of the compound represented by the formula (z-3) was added to 53.5 parts of chlorosulfonic acid, and the mixture was stirred at 70 ° C for 4 hours. After stirring, 8.74 parts of sulfite chloride was added dropwise to the reaction liquid, and the mixture was stirred at 80 ° C for 2 hours, and then cooled to 15 ° C, and further continuously stirred for 14 hours. After completion of the reaction, the mixture was slowly poured into 556 parts of ice water and stirred, followed by filtration. The obtained residue was poured into 200 parts of N-methyl-2-pyrrolidone, and 11.87 parts of 2-ethylhexylamine was added dropwise thereto, and the mixture was stirred at 20 to 30 ° C for 18 hours, and then obtained by filtration. Residue. After the residue was added to 800 parts of 20% acetic acid water and stirred for 2 hours, a residue was obtained by filtration. After the residue was added to 400 parts of acetonitrile and stirred for 2 hours, a yellow solid was obtained by filtration. 4.9% of the compound represented by the formula (I-50) was obtained by drying the yellow solid under reduced pressure at 60 ° C for 15 hours.

Identification of the compound represented by formula (I-50) (mass analysis) ionization mode = ESI+: m/z = 736.3 [M] ⁺ Exact Mass: 735.2

Based on the above results, it was confirmed that m+n was 1.

[Example 4]

After adding 64.86 parts of cyclobutyl hydrazine to 7.0 parts of the compound represented by the formula (X-2), the mixture was heated to 180 ° C to be dissolved. After confirming dissolution, 16.90 parts of 8-chloroquinaldine was added and refluxed at 200 ° C for 9 hours. After completion of the reaction, the reaction solution was poured into 500 parts of acetonitrile and the precipitate was collected by filtration. The obtained precipitate was separately repulped by using 500 parts of ethanol and 500 parts of dimethyl hydrazine each to obtain a yellow solid. The yellow solid was dried at 60 ° C under reduced pressure to give 9.0 part of the compound of formula (z-4).

Identification of the compound represented by formula (z-4): (elemental analysis) C68.5 H3.0 N3.6 C110.4

Then, 5.0 parts of the compound represented by the formula (z-4) was added to 47.5 parts of chlorosulfonic acid, and the mixture was stirred at 70 ° C for 4 hours. After stirring, 7.76 parts of sulfite chloride was added dropwise to the reaction liquid, and the mixture was stirred at 80 ° C for 2 hours, and then cooled to 15 ° C, and further continuously stirred for 14 hours. After completion of the reaction, the mixture was slowly poured into 556 parts of ice water and stirred, followed by filtration. The obtained residue was poured into 200 parts of N-methyl-2-pyrrolidone, and 5.27 parts of 2-ethylhexylamine was added dropwise thereto, and the mixture was stirred at 20 to 30 ° C for 18 hours, and then filtered. And get the residue. The residue was added to 800 parts of 20% acetic acid water and stirred for 2 hours, and then a residue was obtained by filtration. After the residue was added to 400 parts of acetonitrile and stirred for 2 hours, a yellow solid was obtained by filtration. 4.9% of the compound represented by the formula (I-65) was obtained by drying the yellow solid under reduced pressure at 60 ° C for 15 hours.

Identification of the compound represented by formula (I-65) (mass analysis) ionization mode = ESI+: m/z = 804.3 [M] ⁺ Exact Mass: 803.2

Based on the above results, it was confirmed that m+n was 1.

[Solubility evaluation]

The compound obtained in Examples 1 to 4 and the compound of Comparative Example 1 were obtained as follows for propylene glycol monomethyl ether (hereinafter abbreviated as PGME), propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA), and cyclohexane. The solubility of ketone (hereinafter abbreviated as CHN) and N-methylpyrrolidone (hereinafter abbreviated as NMP).

0.1 g of the compound was mixed with 1 g of the above solvent in a 50 mL sample tube, and then the sample tube was stoppered, and shaken at 30 ° C for 3 minutes using an ultrasonic vibration machine. Then, after standing at room temperature for 30 minutes, it was filtered and the residue was visually observed. When it was not possible to confirm the insoluble matter, it was judged that the solubility was good, and it was represented by ○ in Table 2, and when the insoluble matter was confirmed, it was judged that the solubility was poor, and it was represented by X in Table 2.

In Table 2, the compound (R-1) was C.I. Acid Yellow 3 (manufactured by Tokyo Chemical Industry Co., Ltd.).

[Example 5] [Preparation of coloring composition]

The following ingredients were mixed to obtain a coloring composition:

[Production of color filter]

The coloring composition obtained above was applied to 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 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.

[Embodiment 6]

A coloring composition and a color filter were obtained in the same manner as in Example 5 except that the compound (I-5) synthesized in Example 1 was replaced with the compound (I-20) synthesized in Example 2.

[Embodiment 7]

A coloring composition and a color filter were obtained in the same manner as in Example 5 except that the compound (I-5) synthesized in Example 1 was replaced with the compound (I-50) synthesized in Example 3.

[Embodiment 8]

A coloring composition and a color filter were obtained in the same manner as in Example 5 except that the compound (I-5) synthesized in Example 1 was replaced with the compound (I-65) synthesized in Example 4.

From the results of Table 2, it is understood that the compound of the present invention exhibits a high solubility for an organic solvent. Further, the colored composition containing the compound can produce a color filter having less impurities and high quality.

[Industrial availability]

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

Claims (9)

a compound represented by the formula (1), [In the formula (1), L ¹ represents a single bond or -SO ₂ -, and the hydrogen atom contained in the alkanediyl group may be substituted by a halogen atom, and the -CH ₂ - contained in the alkanediyl group may also be Substituted by -O- or -CO-; R ¹ and R ² independently of each other represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and A ¹ and A ² independently of each other represent a benzene ring which may have a substituent, or may have a naphthalene ring of a substituent or a quinoline ring which may have a substituent; m and n each independently represent an integer of 0 to 5, wherein m+n is an integer of 1 to 8, and m+n is an integer of 2 or more. In the case, the plurality of -SO ₂ NR ¹ R ² are the same or different from each other]. The compound of claim 1, wherein A ¹ is a benzene ring which may also have a substituent. The compound of claim 1, wherein A ¹ is an unsubstituted benzene ring or a benzene ring having a halogen group. The compound of claim 1, wherein A ¹ and A ² are each independently a benzene ring which may have a substituent. The compound of claim 1, wherein A ¹ and A ² are each independently an unsubstituted benzene ring or a benzene ring having a halogen group. The compound of claim 1, wherein R ¹ and R ² are each independently a hydrogen atom or a branched alkyl group having 1 to 8 carbon atoms. The compound of claim 1, wherein m+n is an integer from 1 to 5. A dye comprising the compound of claim 1 as a main component. A coloring composition comprising the dye of claim 8.