TW201942256A - Complex salt compound, dye composition, coloring agent and coloring method for anodic aluminum oxide, and method for producing said compound - Google Patents

Abstract

The present invention relates to a compound which is represented by general formula (1). (In formula (1), each of R1-R4 moieties independently represents -H, -SO3 -, -NO2 or the like, and adjacent moieties of the R1-R4 moieties may be combined with each other to form a ring; M represents a Cr atom or the like; X represents a non-chromophoric cation; k represents an integer of 1-8; Y represents -O- or the like; and Z represents a group that is represented by one of general formulae (2a)-(2k).) (In general formulae (2a)-(2k), each of R5-R47 moieties independently represents -H, -CN, -COOH, an optionally substituted linear or branched alkyl group having 1-20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6-30 carbon atoms, or the like; each of R48-R51 moieties independently represents -H or -SO3 -; A represents an oxygen atom or the like; *1 represents a bonding hand to be bonded with a nitrogen atom; and *2 represents a bonding hand to be bonded with an oxygen atom).

Description

Staggered salt compound, dye composition, coloring agent and coloring method for anodized aluminum, and method for producing the same

The present invention relates to a staggered salt compound, a dye composition containing the compound, a coloring agent for anodized aluminum containing the dye composition, a method for coloring anodized aluminum using the dye composition, and a method for manufacturing the compound.

Previously, as a method of coloring the surface of aluminum (also including aluminum oxide or aluminum alloy), electricity was applied to the aluminum as an anode in an electrolytic solution containing water and a suitable acid to make the aluminum surface a porous alumina layer. (Oxidized film, commonly referred to as alumina film) treatment (hereinafter referred to as anodizing or anodizing treatment, alumina film treatment, etc.), then use: electrolytic coloring method using inorganic compounds or metal compounds; inorganic dyes, Dyeing methods in which organic dyes (azo dyes, mixed salt compound dyes and metal atoms, acid dyes, direct dyes, etc.) are used as colorants (see Patent Documents 1 to 14).

The use of dyes as colorants has the problem of poor light resistance. In order to improve the light resistance of colored aluminum, various dyes with different salt compounds have been developed, but most of these colors are black or gray (for example, Patent Documents 1 to 6). In order to meet the needs of various colored aluminum in recent years, dyeing methods capable of coping with various colors of dyes have been developed (for example, Patent Documents 7 to 10). In addition, the development of additives for improving light resistance when using organic dyes is also being promoted (for example, refer to Patent Document 8).

On the other hand, a method of coloring anodized aluminum to blue, green, yellow, and red colors by using an electrolytic solution containing an organic acid or an inorganic acid and changing the voltage condition of anodization without using ordinary dyes has also been developed (Patent Documents 11 to 13 and the like), but there are restrictions on the kinds of colors.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 55-60562
[Patent Document 2] Japanese Patent Laid-Open No. 55-97492
[Patent Document 3] Japanese Patent Laid-Open No. 9-302256
[Patent Document 4] Japanese Patent Laid-Open No. 60-235867
[Patent Document 5] Japanese Patent Laid-Open No. 6-93195
[Patent Document 6] Japanese Patent Publication No. 2002-522617
[Patent Document 7] Japanese Patent Publication No. 2013-506053
[Patent Document 8] Japanese Patent Laid-Open No. 2009-91622
[Patent Document 9] Japanese Patent Publication No. 2003-504426
[Patent Document 10] Japanese Patent Laid-Open No. 2000-290524
[Patent Document 11] Japanese Patent Laid-Open No. 59-6397
[Patent Document 12] Japanese Patent Laid-Open No. 10-158890
[Patent Document 13] Japanese Patent Laid-Open No. 2000-96293
[Patent Document 14] Japanese Patent Laid-Open No. 2016-216803

[Problems to be solved by the invention]

In the coloring aluminum market, for example, orange-based dyes are useful because they are light-colored and can impart a golden hue. However, alumina film dyes generally have a tendency to fade more easily than thicker colors. Previous orange-based dyes could not be dyed in light colors. Fully ensure its light resistance. In addition, in terms of color stability (no chromatic aberration, discoloration), it is required to use a single color dye to develop a colorant to a desired color. In view of the foregoing, a monochromatic dye that develops into an orange-based color and a dye for anodized aluminum having high light resistance is desired.

It is an object of one aspect of the present invention to provide a salt compound having a novel structure capable of forming an anodic oxide film having excellent light resistance and an orange-colored color in a single color on the surface of aluminum, aluminum oxide, or aluminum alloy. An object of another aspect of the present invention is to provide a dye composition containing the above-mentioned staggered salt compound, a coloring agent and coloring method for anodized aluminum using the dye composition, and a method for producing the above-mentioned staggered salt compound.
[Technical means to solve the problem]

In order to solve the above-mentioned problems, the inventors have made intensive studies on pigments (dyestuffs) for anodizing aluminum, and as a result, have found that by using a salt compound (azo dye) having a specific structure as a colorant for anodized aluminum, It is possible to form a film colored with a single-color dye to yellow, orange, red, peach, brown, bronze, and other orange-based colors on the anodized aluminum oxide with excellent light resistance. That is, the present invention relates to the following inventions.

[1] A compound represented by the following general formula (1).
[Chemical 1]

[In formula (1),
R ¹ ~ R ⁴ each independently represent _{^{-H, -SO 3 -, -NO 2}} , -NO, -CN, -OH, -COO -, -COOH, -SH,
It may have an amino group having 0 to 20 carbon atoms,
It may have a sulfofluorenyl group having 0 to 20 carbon atoms,
It may have a linear or branched alkyl group having 1 to 20 carbon atoms as a substituent,
Cycloalkyl having 3 to 20 carbon atoms which may have a substituent,
It may have a linear or branched alkoxy group having 1 to 20 carbon atoms in a substituent,
Cycloalkoxy having 3 to 20 carbon atoms which may have a substituent,
It may have a linear or branched alkenyl group having 2 to 20 carbon atoms in a substituent,
May also have a substituent of 1 to 20 carbon atoms,
An aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 30 ring atoms which may also have a substituent,
R ¹ to R ⁴ may also be bonded to each other to form a ring.
M represents a Cr, Fe, Co, Si or Al atom,
X represents a non-chromogenic cation, k represents an integer of 1 to 8,
Y means -O- or -O- (C = O)-,
Z represents a group represented by the following formulae (2a) to (2k)],
[Chemical 2]

[Where,
R ⁵ ~ R ⁴⁷ each independently represent _{^{-H, -SO 3 -, -NO 2}} , -NO, -CN, -OH, -COO -, -COOH, -SH,
It may have an amino group having 0 to 20 carbon atoms,
It may have a sulfofluorenyl group having 0 to 20 carbon atoms,
It may have a linear or branched alkyl group having 1 to 20 carbon atoms as a substituent,
Cycloalkyl having 3 to 20 carbon atoms which may have a substituent,
It may have a linear or branched alkoxy group having 1 to 20 carbon atoms in a substituent,
Cycloalkoxy having 3 to 20 carbon atoms which may have a substituent,
It may have a linear or branched alkenyl group having 2 to 20 carbon atoms in a substituent,
May also have a substituent of 1 to 20 carbon atoms,
An aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 30 ring atoms which may also have a substituent,
R ⁴⁸ ~ R ⁵¹ each independently represent -H, or -SO ₃ ^-,
R ¹⁰ and R ¹¹ , R ¹² to R ¹⁶ , R ¹⁷ to R ²¹ , R ²² to R ²⁶ , R ²⁷ and R ²⁸ , R ²⁹ to R ³⁴ , R ³⁵ to R ³⁹ , R ⁴⁰ to R ⁴⁵ , and R ⁴⁶ and R ⁴⁷ can also be bonded to each other to form a ring,
A represents an oxygen atom or a sulfur atom,
* 1 indicates a bond with a nitrogen atom, * 2 indicates a bond with an oxygen atom]
Compound [2] [1], the general formula wherein (1), R ¹ ~ R ⁴ are independently _{^{-H, -SO 3 -, -NO 2}} ,
It may have an amino group having 0 to 10 carbon atoms,
It may have a linear or branched alkyl group having 1 to 10 carbon atoms,
It may have a linear or branched alkenyl group having 2 to 10 carbon atoms in a substituent, or a fluorenyl group having 1 to 10 carbon atoms in a substituent.
[3] The compound according to [1] or [2], wherein in the general formulae (2a) to (2k),
R ⁵ is a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R ⁶ is -COO ^- , -COOH, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or a fluorenyl group having 1 to 10 carbon atoms which may have a substituent,
R ⁷ or R ⁸ are each independently -H, and may have a linear or branched alkyl group having 1 to 10 carbon atoms or a substituent having 6 to 20 carbon atoms. Aromatic hydrocarbon group,
R ⁹ to R ¹¹ are each independently -H, -CN, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or 6 carbon atoms which may also have a substituent ～ 20 aromatic hydrocarbon group,
R ¹² to R ¹⁶ are each independently -H, and may have a linear or branched alkyl group having 1 to 10 carbon atoms or a substituent having 6 to 20 carbon atoms. Aromatic hydrocarbon group,
R ¹⁷ to R ²¹ are each independently -H, and may have a linear or branched alkyl group having 1 to 10 carbon atoms or a substituent having 6 to 20 carbon atoms. Aromatic hydrocarbon group,
R ²² to R ²⁶ are each independently -H, an amino group having 0 to 20 carbon atoms which may have a substituent, or a linear or branched chain having 1 to 10 carbon atoms which may have a substituent. alkyl,
R ²⁷ and R ²⁸ are each independently -H, and may have a linear or branched alkyl group having 1 to 10 carbon atoms or a substituent having 2 to 20 carbon atoms. Linear or branched alkenyl,
R ²⁹ to R ³⁴ are each independently -H or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
R ³⁵ to R ³⁹ are each independently -H or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
R ⁴⁰ ~ R ⁴² R ⁴⁸ ~ R, and any one or two of the ⁴⁹ is -SO ₃ ^- or -COO ^-, R ⁴⁷ is a substituent may also have a number of carbon atoms of the amino group of 0 to 10, R ⁵⁰ ~ any one of R ⁵⁵ is one or two -SO ₃ ^- or -COO ^-.
[4] The compound according to any one of [1] to [3], wherein Z is a group represented by the above formula (2a), (2b), or (2c).
[5] A dye composition containing the compound according to any one of [1] to [4].
[6] A coloring agent for anodized aluminum, which contains the dye composition according to [5].
[7] A coloring method of anodized aluminum oxide, anodized aluminum oxide, or anodized aluminum alloy, which is characterized by using a dye combination containing 0.02 to 10% by mass of the compound according to any one of [1] to [4] Thing.
[8] a manufacturing method,
It is a method for producing a compound according to any one of [1] to [4], and includes the following general formula (I):
[Chemical 3]

[In formula (I), R ¹ to R ⁴ , Y, and Z have the same meanings as defined above]
A step in which the compound shown is reacted with a compound containing a Cr, Fe, Co, Si or Al atom to obtain a compound represented by the general formula (1).
[8] The production method according to [7], wherein the compound represented by the general formula (I) is prepared by the following formula (II):
[Chemical 4]

[In formula (II), R ¹ to R ⁴ and Y represent the same meanings as defined above]
A compound obtained by diazotizing the compound shown and / or its salt, and a diazo coupling reaction of a coupling component, and the coupling component is a formula (III-a) to (III-k) below :
[Chemical 5]

[In the formula, R ⁵ to R ⁵⁵ and A represent the same meaning as the above definition]
A compound and / or a salt thereof shown in any one of them.
[Effect of the invention]

According to the present invention, it is possible to provide a complex salt compound having a novel structure capable of forming an anodic oxide film having excellent light resistance on the surface of aluminum, aluminum oxide, or aluminum alloy and exhibiting an orange color in a single color. According to the dye composition containing the compound of the present invention, it is possible to obtain a coloring agent for anodized aluminum that can form an orange-colored colored coating film having yellow, orange, red, peach, brown, bronze, and the like having excellent light resistance. In addition, by using this colorant, an anodized aluminum oxide film having excellent light fastness in orange-based colors such as yellow, orange, red, peach, brown, and bronze can be obtained. According to the dye composition containing the compound of the present invention, it is possible to form an anodized aluminum film having excellent heat resistance in addition to light resistance.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various changes can be made within the scope of the gist thereof. A part in the square brackets [] in the compound represented by the general formula (1) is an anion and forms a complex with a non-color-developing cation represented by X in the general formula (1).

The compound of this embodiment is a compound represented by the following general formula (1) (hereinafter also referred to as "compound (1)").
[Chemical 6]

R ¹ ~ R ⁴ each independently represent _{^{-H, -SO 3 -, -NO 2}} , -NO, -CN, -OH, -COO -, -COOH, -SH, also having 0 carbon atom of the substituent group An amine group of -20, a sulfofluorenyl group having 0 to 20 carbon atoms which may have a substituent, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, may have A cycloalkyl group having 3 to 20 carbon atoms as a substituent, a linear or branched alkoxy group having 1 to 20 carbon atoms as a substituent, or 3 to 20 carbon atoms as a substituent A cycloalkoxy group of 20, a linear or branched alkenyl group having 2 to 20 carbon atoms that may have a substituent, a fluorenyl group having 1 to 20 carbon atoms that may have a substituent, or An aromatic hydrocarbon group having 6 to 30 carbon atoms as a substituent or a heterocyclic group having 5 to 30 ring atoms that may have a substituent. R ¹ to R ⁴ may also be formed by bonding adjacent groups to each other. Ring, M represents a Cr, Fe, Co, Si or Al atom, X represents a non-chromic cation, k represents an integer of 1 to 8, Y represents -O- or -O- (C = O)-, and Z represents the following A group represented by the general formulae (2a) to (2k).

Hereinafter, the compound (1) will be specifically described, but the present invention is not limited to these. The anion part may have one kind of structure in the range of the general formula (1), or plural kinds of structures different from each other, and preferably one kind of structure. That is, the plurality of R ¹ to R ⁵⁵ and Y may be the same type or different types, respectively. The non-color-developing cationic portion may be one type or a mixture of plural types, and one type is preferred. In the case where k is 2 to 8, the plurality of Xs existing may be the same kind or different kinds.

In the general formula (1), as the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ⁴ , for example, an unsubstituted amine group (-NH ₂ ) is mentioned. , Mono-substituted amino, di-substituted amino and the like. The number of carbon atoms in the mono-substituted amino group or the di-substituted amino group is, for example, 1 to 20, may be 1 to 10, and may be 2 to 6. The amine group having 0 to 20 carbon atoms which may have a substituent may be an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a heterocyclic ring having 5 to 30 ring atoms through -NH- Base of base. Examples of the mono-substituted amino group include an ethylamino group, an ethylamino group, and a phenylamino group. Examples of the di-substituted amino group include a diethylamino group, a phenylamino group, a diphenylamino group, and an ethylaminophenylamino group. The mono-substituted amino group may be a group represented by -NHCO-R. The substituent R may be, for example, an alkyl group or an aryl group.

In the general formula (1), "a sulfofluorenyl group which may have a substituent having 0 to 20 carbon atoms" represented by R ¹ to R ⁴ means that it has -SO ₂ -R ¹⁰⁰ (or -S (= O ) ₂ -R ¹⁰⁰ ) A sulfofluorenyl group as a substituent R ¹⁰⁰ . The substituent R ¹⁰⁰ may be a group containing a carbon atom or a group containing no carbon atom. When the substituent R ¹⁰⁰ is a group containing a carbon atom, the carbon number of the substituent R ¹⁰⁰ is 1 to 20, may be 1 to 10, and may be 1 to 7. Specific examples of the sulfofluorenyl group which may have a substituent having 0 to 20 carbon atoms include, for example, a sulfonamido group (-S (= O) ₂ -NH ₂ ), a methanesulfonyl group, and a tosylsulfonyl group .

In the general formula (1), the "carbon number 1 to 1" in "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ⁴ 20 linear or branched alkyl group ", specifically, methyl, ethyl, n-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. Linear alkyl group; branched alkyl group such as isopropyl, isobutyl, second butyl, third butyl, isooctyl, and third octyl.

In the general formula (1), R ¹ ~ R as shown in FIG. ⁴ of "may have a substituent group having a carbon number of 3 to 20 atoms of the cycloalkyl group" in the "3 to 20 carbon atoms and the cycloalkyl" Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl.

In the general formula (1), the "number of carbon atoms 1" in "a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ⁴ A linear or branched alkoxy group of -20 ", specifically, methoxy, ethoxy, propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, heptyloxy Linear alkoxy groups such as alkyl, octyloxy, nonyloxy, and decyloxy; isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy, Branched alkoxy such as trioctyloxy.

In the general formula (1), the "cycloalkoxy group having 3 to 20 carbon atoms" in the "cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ⁴ "Specific examples include cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy.

In the general formula (1), the "carbon number 2 to 2" in the "linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ⁴ 20 linear or branched alkenyl group ", specifically, vinyl, allyl, isopropenyl, 2-butenyl, 1-hexenyl, or plural such alkenyl bonds A straight or branched base.

In the general formula (1), the "fluorenyl group having 1 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ^{4 is} a group represented by -C = OR ¹⁰¹ . The substituent R ¹⁰¹ may be a group containing a carbon atom or a group containing no carbon atom. When the substituent R ¹⁰¹ is a group containing a carbon atom, the number of carbon atoms of the substituent R ¹⁰¹ may be, for example, 1 to 20 and may be 1 to 10. The fluorenyl group having 1 to 20 carbon atoms which may have a substituent may be an aromatic hydrocarbon group having the following 6 to 30 carbon atoms or a heterocyclic group having 5 to 30 ring atoms via a fluorenyl group. The base. Examples of the substituent R ¹⁰¹ include -H, -CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH = CH ₂ , and -C ₆ H ₅ (-Ph). Specific examples of the "fluorenyl group having 1 to 20 carbon atoms" in the "fluorenyl group having 1 to 20 carbon atoms which may have a substituent" include, specifically, methylamino, ethylfluorenyl, propionyl, and propylene Fluorenyl, benzamidine and the like.

In the general formula (1), the "aromatic hydrocarbon group having 6 to 30 carbon atoms" in the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent" represented by R ¹ to R ⁴ , Specific examples include phenyl, naphthyl, biphenyl, anthryl, phenanthryl, fluorenyl, bitriphenyl, indenyl, and fluorenyl. The "aromatic hydrocarbon group" in this specification refers to an aromatic hydrocarbon group and a condensed polycyclic aromatic group. Among these, a phenyl group or a naphthyl group is preferred.

In the general formula (1), as the "heterocyclic group having 5 to 30 ring atoms which may have a substituent" represented by R ¹ to R ⁴ , the "heterocyclic group having 5 to 30 ring atoms""Specific examples include pyridyl, pyrimidinyl, triazinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolinyl, naphthyridinyl, indolyl, and benzo Imidazolyl, carbazolyl, carbolinyl, acridinyl, morpholinyl, hydantoinyl, furyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzo Thienyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, and the like.

General formula (1) shown in the R ¹ ~ R ⁴ "substituent group having a carbon number of 0 to 20 atoms of the group", "substituent group having a carbon number of 0 to 20 atoms of sulfo acyl", "having A linear or branched alkyl group having 1 to 20 carbon atoms in a substituent ", a" cycloalkyl group having 3 to 20 carbon atoms in a substituent group ", and" 1 to 20 carbon atoms in a substituent group ""Straight or branched alkoxy", "Cycloalkoxy having 3 to 20 carbon atoms having substituents", "Straight or branched chain alkoxy having 2 to 20 carbon atoms having substituents""Alkenylgroup","fluorenyl group having 1 to 20 carbon atoms having substituents", "aromatic hydrocarbon group having 6 to 30 carbon atoms having substituents" or "ring atom number 5 to 5 having substituents" 30 the heterocyclic group "in the" substituent "specifically include: -SO ₃ ^-, nitro (-NO _2), nitroso (-NO2), cyano (-CN), hydroxyl group (- OH), ^- COO -, carboxyl (-COOH), a thiol group (-SH),
Unsubstituted amino groups; methylamino, dimethylamino, diethylamino, ethylmethylamino, methylpropylamino, di-thirdbutylamino, diphenylamine Radicals such as linear or branched alkyl groups having 1 to 17 carbon atoms or one of aryl groups having 6 to 24 carbon atoms substituted or disubstituted amine groups;
A group having a sulfofluorenyl group (-S (= O) _2- ) such as a sulfonamido (-S (= O) ₂ -NH ₂ ) group, a methanesulfonyl group, a tosylsulfonyl group;
Methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, n-hexyl, isohexyl, heptyl, n-octyl, third octyl, iso Linear or branched alkyl groups having 1 to 17 carbon atoms, such as octyl, nonyl, and decyl;
Cycloalkyl groups having 3 to 17 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl;
Linear or branched alkoxy groups having 1 to 17 carbon atoms such as methoxy, ethoxy, propoxy, third butoxy, n-pentoxy, and n-hexyloxy;
Cycloalkoxy having 3 to 17 carbon atoms such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy;
Vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or such alkenyl bonds A plurality of linear or branched alkenyl groups having 2 to 19 carbon atoms;
Formamyl, ethenyl, propionyl, propenyl, benzyl and the like;
Aromatic hydrocarbon groups having 6 to 24 carbon atoms, such as phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, bitriphenyl, indenyl, and fluorenyl;
Pyridyl, pyrimidinyl, triazinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, pyryl, daphyl, piperidinyl, piperazinyl, quinolinyl, isoquinolinyl, naphthyridinyl , Indolyl, benzimidazolyl, carbazolyl, carbolinyl, acridinyl, morpholinyl, morphinyl, hydantoinyl, furanyl, benzofuranyl, dibenzofuranyl, Pyranyl, coumarin, isobenzofuranyl, Base, oxanthranyl, pyranyl, thienyl, thienyl, benzothienyl, dibenzothienyl, 9-oxothio Hexyl, oxazolyl, benzoxazolyl, morpholinyl, thiazolyl, benzothiazolyl and other heterocyclic groups having 5 to 24 ring atoms;
Cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, (1,3- or 1,4-) cyclohexadienyl, 1,5-cyclooctadienyl Cyclic olefin groups having 3 to 24 carbon atoms and the like. These "substituents" may contain only one or a plurality of them, and when there are a plurality of them, they may be the same or different. These "substituents" may have the above-exemplified substituents. Furthermore, these substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom. Form a ring.

In the general formula (1), R ¹ ~ R ⁴ is preferably _{^{-H, -SO 3 -, -NO 2}} , also having a number of carbon atoms of the substituent group of 0 to 10, the group may have a substituent A straight or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkenyl group having 2 to 10 carbon atoms that may have a substituent, or a carbon that may have a substituent atoms acyl of 1 to 10, more preferably _{^{-H, -SO 3 -, -NO 2}} , methyl, vinyl, or -N (CH _{3) 2.}

In the general formula (1), R ¹ to R ⁴ represent the substituents as described above, but adjacent groups may be bonded to each other through a single bond, a bond through an oxygen atom (-O-), or a bond through a sulfur atom. The bonds (-S-) are bonded to each other to form a ring. For example, R ¹ to R ⁴ may be bonded to each other to form a benzene ring, or R ¹ and R ^{2 may} be bonded to each other to form a benzene ring.

In the general formula (1), "M" represents a chromium atom (Cr), an iron atom (Fe), a cobalt atom (Co), a silicon atom (Si), or an aluminum atom (Al), preferably a Cr atom or a Co atom , More preferably a Cr atom.

In the general formula (1), "X" is a non-color-developing cation, and specific examples thereof include hydrogen ion (H ⁺ ), lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), potassium ion (K ⁺ ), and the like. Alkali metal ions, cations containing organic compounds, etc. Among these, an alkali metal ion is more preferable, and K ⁺ or Na ^{+ is more} preferable.

k represents the number of non-color-developing cations "X", and represents an integer of 1 to 8, preferably an integer of 3 to 7.

In the general formula (1), "Y" means "-O-" or "-O- (C = O)-", and in the case of "-O- (C = O)-", it is preferably Bonding is performed like "M" and "MO- (C = O)-".

In the general formula (1), "Z" is a divalent group represented by the following general formulae (2a) to (2k).
[Chemical 7]

Wherein, R ⁵ ~ R ⁴⁷ each independently represent _{^{-H, -SO 3 -, -NO 2}} , -NO, -CN, -OH, -COO -, -COOH, -SH, 0 to 20 carbon atoms, the Amine group, sulfofluorenyl group having 0 to 20 carbon atoms, linear or branched alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, and 1 to 20 carbon atoms Straight or branched alkoxy group, cycloalkoxy group with 3 to 20 carbon atoms, straight or branched chain alkenyl group with 2 to 20 carbon atoms, 1 to 20 carbon atom Group, aromatic hydrocarbon group having 6 to 30 carbon atoms, or heterocyclic group having 5 to 30 ring atoms, amine group, sulfonyl group, alkyl group, cycloalkyl group, alkoxy group in R ¹ to R ⁴⁷ , Cycloalkoxy, alkenyl, fluorenyl, aromatic hydrocarbon, and heterocyclic group may each have a substituent independently or not.

R ¹⁰ and R ¹¹ , R ¹² to R ¹⁶ , R ¹⁷ to R ²¹ , R ²² to R ²⁶ , R ²⁷ and R ²⁸ , R ²⁹ to R ³⁴ , R ³⁵ to R ³⁹ , R ⁴⁰ to R ⁴⁵ , and R ⁴⁶ and R ⁴⁷ may be bonded to each other to form a ring.

R ⁵ to R ⁴⁷ may be each independently a base exemplified in R ¹ to R ⁴ .

R ⁴⁸ ~ R ⁵¹ each independently represent -H, or -SO ₃ ^-. A represents an oxygen atom or a sulfur atom. In the formula, * 1 represents a bond with a nitrogen atom, and * 2 represents a bond with an oxygen atom.

In the formula (2a), R ⁶ is preferably -COO ^-, -COOH, may also have a linear or branched alkyl group having a carbon number of the substituent group of 1 to 10 atoms, or the group may have a substituent The fluorenyl group having 1 to 10 carbon atoms is more preferably -COO-, -COOH or methyl. In the formula (2a), R ^{5 is} preferably a linear or branched alkyl group having 1 to 10 carbon atoms that may have a substituent, or 6 to 20 carbon atoms that may also have a substituent. Aromatic hydrocarbon group. The base represented by the formula (2a) may be, for example, a base represented by the following formula (2a ').
[Chemical 8]

In the formula (2a '), R ^5a to R ^5e have the same meanings as defined in R ⁵ to R ⁴⁷ . R ^5a to R ^5e may be bonded to each other to form a ring. R ^5a ~ R ^5e is preferably any one or two of _{^{-SO 3 -, -NO 2, -SO}} 2 NH 2, or may have a substituent group of carbon atoms, a straight chain or branched chain of 1 to 10 Of alkyl.

In the formula (2b), R ⁷ or R ^{8 is} preferably each independently -H, and may have a linear or branched alkyl group having 1 to 10 carbon atoms or may have a substituent, or may have In the aromatic hydrocarbon group having 6 to 20 carbon atoms of the substituent, R ⁷ and R ^{8 are more} preferably each independently -H, methyl, or phenyl.

In the formula (2c), R ⁹ to R ¹¹ are each preferably a linear or branched alkyl group having 1 to 10 carbon atoms, each independently being -H, -CN, or optionally having a substituent, or The aromatic hydrocarbon group having 6 to 20 carbon atoms may have a substituent, more preferably R ⁹ is ethyl, R ¹⁰ is -CN, and R ¹¹ is methyl.

In the formula (2d), R ¹² to R ^{16 are} preferably each independently -H, and may have a linear or branched alkyl group having 1 to 10 carbon atoms, or may have a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms as a substituent.

In the formula (2e), R ¹⁷ to R ^{21 are} preferably each independently -H, and may have a linear or branched alkyl group having 1 to 10 carbon atoms, or may have a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms as a substituent.

In the formula (2f), R ²² to R ^{26 are} preferably each independently -H, an amino group having 0 to 20 carbon atoms that may have a substituent, or 1 to carbon atoms that may also have a substituent. A straight or branched alkyl group of 10.

In the formula (2g), R ²⁷ and R ^{28 are} preferably each independently -H, and may have a linear or branched alkyl group having 1 to 10 carbon atoms, or may have a substituent. A linear or branched alkenyl group having 2 to 20 carbon atoms in the substituent. R ³¹ and R ³² may be bonded to form a ring. In the case of forming a ring, a 6-membered ring is preferred.

In the formula (2h), R ²⁹ to R ³⁴ are each preferably a linear or branched alkyl group having 1 to 10 carbon atoms, each independently being -H or a substituent, and more preferably all Is -H.

In formula (2i), R ³⁵ to R ³⁹ are each preferably -H or a linear or branched alkyl group having 1 to 10 carbon atoms, which may have a substituent, and more preferably- H or methyl.

In the formula (2j), preferably any one of R ⁴⁰ ~ R ⁴⁵ is in the two or -SO ₃ ^- or -COO ^-, more preferably R ⁴⁵ is -SO ₃ ^-. R ^{47 is} preferably an amine group having 0 to 10 carbon atoms which may have a substituent, and more preferably -NH ₂ .

In the formula (2k), preferably any one of R ⁴⁶ ~ R ⁵¹ is in the two or -SO ₃ ^- or -COO ^-, more preferably R ⁴⁹ is -SO ₃ ^-. R ⁵¹ may be -H.

The compound represented by the general formula (1) includes all stereoisomers which may be generated, and any of the isomers can be preferably used as the compound of the present invention. For example, when the compound represented by the following general formula (1-a) exists with respect to the compound of the general formula (1), the compound of the present invention includes the general formula (1) and the general formula (1-a) The compound may be a mixture of two or more kinds selected from these stereoisomers.

[Chemical 9]

Specific examples of the compound of the present invention represented by the general formula (1) will be shown in the following formulas, but the present invention is not limited to these. In addition, in the exemplified compounds, the entire charge of the anion portion in the square brackets [] of the general formula (1) is described, and a part of the hydrogen atom is omitted in the structural formula.

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21]

[Chemical 22]

[Chemical 23]

[Chemical 24]

[Chemical 25]

[Chemical 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chem 34]

[Chemical 35]

[Chemical 36]

[Chemical 37]

[Chemical 38]

[Chemical 39]

[Chemical 40]

[Chemical 41]

[Chemical 42]

[Chemical 43]

[Chemical 44]

[Chemical 45]

[Chemical 46]

[Chemical 47]

[Chemical 48]

[Chemical 49]

[Chemical 50]

[Chemical 51]

[Chemical 52]

The compound (1) may be a compound represented by any one of the formulae (3-1) to (13-4), and from the viewpoint of further excellent light resistance and the viewpoint of further excellent heat resistance, it may be a formula The compound represented by any one of (3-1) to (5-1) may be represented by formula (3-17), (3-24), (4-1), or (5-1) Of compounds.

An example of a method for producing a compound represented by the general formula (1) is shown below, but it is not limited to this method. Specifically, first, by making the following general formula (II):
[Chem 53]

[In formula (II), R ¹ to R ⁴ and Y have the same meanings as defined above]
The aromatic amine derivative and / or its salt shown and having an appropriate substituent are reacted in an acid aqueous solution such as hydrochloric acid and sulfuric acid with a basic aqueous solution prepared using sodium nitrite and the like at an appropriate temperature to obtain the following general formula. Formula (IV):
[Chemical 54]

[In formula (IV), R ¹ to R ⁴ and Y have the same meanings as defined above]
The compound shown and / or its salt (diazo component).

[Z-OH] or [Z-OH] or [Z-OH] is obtained by dissolving a compound represented by the formula "Z-OH" or "Z = O" (details will be described later) in an aqueous solution such as sodium hydroxide and reacting Z = O] Salt of compound (Coupling component). It is also possible to use "Z-OH" or "Z = O" directly as an even component.

Next, by reacting the diazo component with the coupling component (diazo coupling reaction), a compound represented by the following general formula and / or a salt thereof is obtained as an azo dye.
[Chem 55]

[In the formula, R ¹ to R ⁴ , Y, and Z have the same meanings as defined above].

Then, the reaction solution containing the above-mentioned azo dye and the aqueous solution containing the compound containing the atom represented by M are prepared and reacted by making the atom (M): azo dye = 1: 2, and the salt is then mixed. By chemical conversion and salting out, the compound (1) can be produced in the form of a 1: 2 type complex salt compound. The compound containing an atom represented by M is a compound containing Cr, Fe, Co, Si, or Al atoms, and may be used alone or in combination of two or more kinds. Specific examples of the compound containing an atom represented by M include, for example, chromium acetate.

As "Z-OH" or "Z = O", specifically, it may be any one of the compounds represented by the following general formulae (III-a) to (III-k).
[Chemical 56]

[In the formula, R ⁵ to R ⁵¹ and A have the same meanings as defined above].

The method for producing a compound represented by the general formula (1) in this embodiment includes reacting a compound represented by the general formula (I) with a compound containing a Cr, Fe, Co, Si, or Al atom to obtain the general formula (1). ) For the compound shown.

The compound represented by the general formula (I) is one obtained by diazotizing a diazonium compound obtained by diazotizing the compound represented by the above formula (II) and / or a salt thereof with a diazo coupling reaction of a coupling component, and The coupling component may be a compound and / or a salt thereof represented by any one of the general formulae (III-a) to (III-k).

Compound (1) can be purified by known methods such as: purification by column chromatography; adsorption purification by silica gel, activated carbon, activated clay, etc .; recrystallization and crystallization by solvent. Compound identification and physical property evaluation can use UV-Vis, thermogravimetry-differential thermal analysis (TG-DTA), gas chromatography (GC), nuclear magnetic resonance analysis (NMR) analysis, etc. And proceed.

The compound (1) can be used as a component of a dye composition. Even if the compound (1) is used alone, aluminum, fibers, and the like can be colored. That is, the compound (1) can be preferably used as a pigment compound for coloring aluminum, fibers, and the like by using a single monochrome dye alone. The compound (1) may be used in combination of two or more kinds to obtain a plurality of colors by color mixing. The dye composition may be mixed with other ingredients for optimal dyeing (coloring using a dye). Specific examples include liquids (solvents) such as water, alcohols, and solvents; and additives such as surfactants. The solvent is preferably water. The compound (1) may be used in combination with other dyes as a component of a dye composition. Other compounds, pigments, and dyes other than the pigment-based compound (1), specifically, ruthenium complexes, coumarin-based pigments, anthocyanins-based pigments, merocyanine-based pigments, and rhodocyanine-based compounds Pigment, phthalocyanine pigment, porphyrin pigment, Department of pigments and so on. In the case where the compound (1) is used in combination with other components, the use amount of the other components with respect to the compound (1) is preferably 10 to 200% by mass, and more preferably 20 to 100% by mass.

The dye composition of this embodiment can be used as a coloring agent for anodized aluminum. When compound (1) is used as a coloring agent such as anodized aluminum, the concentration of compound (1) in the dye composition containing compound (1) in the coloring (dyeing) method is relative to the total amount of the dye composition, It is preferably 0.02 to 10% by mass, and more preferably 0.05 to 1% by mass.

Here, the anodized aluminum refers to aluminum in which an electrolytically treated aluminum surface is treated to form an oxide layer having pores in an electrolytic solution such as an acid aqueous solution. The coloring agent for anodized aluminum refers to a coloring (staining) by which the compound (1) can be adsorbed into the pores by using a dye composition containing the compound (1) on the aluminum surface having the pores. Generally, in order to improve the durability and light resistance of the colored aluminum surface, a sealing process for blocking the pores is performed after the coloring.

Examples of aluminum in the anodized aluminum include aluminum, aluminum oxide, aluminum alloys with other metals, and the like, and metals or metal compounds containing aluminum.

As a method for coloring aluminum using a coloring agent for anodized aluminum, a method known as a method for dyeing an aluminum oxide film can be used. For example, the methods described in Japanese Industrial Standards (JIS H 8601: 1999 "Anodized Coatings of Aluminum and Aluminum Alloys"), Patent Documents 1 to 3, and 8 can be used. The coloring method of aluminum is not particularly limited, and an example is shown below.

First, an aluminum plate is degreased with an acid aqueous solution such as sulfuric acid, oxalic acid, chromic acid, and sulfonic acid, and washed with water. Next, the degreased aluminum plate is used as an anode, and an acidic aqueous solution is used as an electrolyte for electrolysis. On the surface of the aluminum anode, an anodic oxide film (alumina film) having a large number of pores is formed (anodized), and then Washed. Then, after surface adjustment, water washing, and the like are appropriately performed, it is immersed in an aqueous solution of a coloring agent for anodized aluminum containing a dye composition containing the compound of the present invention, and the dye is adsorbed (dyed, electrolytically colored) into the pores, and aluminum is used. The oxide hydrate and the like can seal the pores on the surface to form a sealing substance, whereby coloring can be performed.
When the dye composition of the present invention is used in combination of two or more kinds, or when the dye composition of the present invention is used in combination with other dyes, a mixed solution of all the dyes to be used may be prepared and anodized aluminum may be dipped therein, Alternatively, each pigment solution can be separately prepared and sequentially immersed in each solution.

The electrolysis conditions during coloring can be either direct current electrolysis or alternating current electrolysis, preferably direct current electrolysis. The current density is preferably 0.1 to 10 A / dm ² , and more preferably 0.5 to 3 A / dm ² . The energization time is preferably from 10 seconds to 60 minutes. The thickness of the anodized film is preferably 2 to 20 μm.

The processing temperature of each of the above steps is preferably an appropriate temperature, and the temperature during anodization is preferably 0 to 80 ° C. The temperature during dyeing is preferably from 10 ° C to 70 ° C. Other processing temperatures are preferably 10 to 80 ° C.

The dye composition of this embodiment can also be used similarly to an anodic oxide using a metal other than aluminum. For example, magnesium, zinc, titanium, zirconium, etc. can also be used for non-metals such as conductive plastics as long as they can adsorb dyes to anodic pores.

The coloring agent for anodized aluminum in this embodiment can be evaluated by measuring hue, light resistance, heat resistance, and the like with respect to the characteristics of a sample colored with aluminum. The hue can be visually evaluated for hue or uniformity, and can also be measured in the form of density (K / Sd), hue (L ^* , a ^* , b ^* ), and color difference (ΔE ^* ) using a color difference meter.

According to the coloring agent for anodized aluminum according to this embodiment, yellow, orange, red, peach, brown, bronze, these light colors (light peaches, etc.), or different shades such as dark colors can be displayed. According to the coloring agent for anodized aluminum according to this embodiment, it is also possible to display a color mixture (yellow-red, orange, red, purple, green, yellow-green, dark blue, black, gray) by combining the above-mentioned compound with other pigments. , Brown, gold, bronze and other intermediate colors). The intermediate color is preferably black or gray.

The light resistance test of colored aluminum using the coloring agent for anodized aluminum oxide of this embodiment can also use a test machine that simulates sunlight including ultraviolet light, etc., to irradiate the sample with light for a fixed time, and use a color difference meter to measure the test. The change of hue of colored aluminum before and after was evaluated. Judgment of light resistance can also be based on the hue of tinted aluminum according to the method specified in Japanese Industrial Standards (Gray for Discoloration and Discoloration, JIS L 0804).

The heat resistance test of colored aluminum using the coloring agent for anodized alumina according to this embodiment may be, for example, heating in a thermostat or hot-air dryer in a temperature range of 50 to 300 ° C for 30 minutes to 50 hours, etc. as appropriate. The method of evaluating the change in hue before and after the test in the same manner as the light resistance test, such as the method of fixing time.

The colored aluminum using the coloring agent for anodized aluminum according to this embodiment is used for various aluminum plate materials, aluminum exteriors, and the like.
[Example]

Hereinafter, the present invention will be specifically described by way of examples, but it is not limited to the following examples.

[Synthesis Example 1: Synthesis of Compound (3-1)]
(Preparation of diazo component liquid)
In a reaction vessel, 8.7 g of 2-amino-4-methylphenol, 120 mL of water, and 9.0 g of 98% sulfuric acid were placed. While the obtained reaction solution was stirred at 0 ° C, 4.9 g of a 40% by mass sodium nitrite aqueous solution was added dropwise, and then a reaction was performed for 2 hours to obtain a diazo component liquid.

(Preparation of Coupled Liquid)
In a reaction vessel, put 20.1 g of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one, 150 mL of water, and 6.4 g of a 48% by mass sodium hydroxide aqueous solution. The mixture was stirred at 10 ° C for 2 hours to obtain a coupling liquid.

(Diazo coupling)
A diazo component liquid was put into the coupled coupling liquid while stirring, and stirred for 18 hours to perform a diazo coupling reaction. The completion of the reaction was confirmed by shallow layer chromatography (TLC). The purity of the product was confirmed by high-speed liquid chromatography (HPLC) and the retention time peak positions and areas obtained by observing typical azo dyes.

(Wrong salting)
The reaction solution after the coupling was filtered, and 200 mL of solids and water collected by filtration were placed in the reaction container to disperse the solids in water. 3.5 g of chromium acetate was added to the dispersion, and the mixture was stirred at 95 ° C for 10 hours. The completion of the reaction was confirmed by TLC. The reaction solution was cooled to 25 ° C., and 20 g of common salt was added to perform salting out. Thereafter, the reaction solution was filtered. The solid collected by filtration was dried under reduced pressure, and a compound (compound (3-1)) represented by the formula (3-1) was obtained as a solid powder (32.1 g, yield: 100%).

[Synthesis Example 2: Synthesis of Compound (3-7)]
(Preparation of diazo component liquid)
In a reaction vessel, 9.8 g of 2-amino-4-nitrophenol, 180 mL of water, and 9.3 g of 35% hydrochloric acid were placed. While the obtained reaction solution was stirred at 0 ° C, 10.8 g of a 40% by weight sodium nitrite aqueous solution was added dropwise, and a reaction was performed for 2 hours to obtain a diazo component liquid.

(Preparation of Coupled Liquid)
In a reaction container, put 16.5 g of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one, 180 mL of water, and 12.6 mL of a 48% by mass sodium hydroxide aqueous solution. The mixture was stirred at 10 ° C for 2 hours to obtain a coupling liquid.

(Diazo coupling)
A diazo component liquid was put into the coupled coupling liquid while stirring, and stirred for 18 hours to perform a diazo coupling reaction. The completion of the reaction was confirmed by shallow layer chromatography (TLC). The purity of the product was confirmed by high-speed liquid chromatography (HPLC) and the retention time peak positions and areas obtained by observing typical azo dyes.

(Wrong salting)
The reaction solution after the coupling was filtered, and 200 mL of solids and water collected by filtration were placed in the reaction container to disperse the solids in water. 7.3 g of chromium acetate was added to the dispersion, and the mixture was stirred at 95 ° C for 10 hours. The completion of the reaction was confirmed by TLC. The reaction solution was cooled to 25 ° C., and 20 g of common salt was added to perform salting out. Thereafter, the reaction solution was filtered. The solid collected by filtration was dried under reduced pressure, and the compound represented by the above formula (3-7) was obtained as a solid powder (30.0 g, yield: 98.9%).

[Synthesis Example 3: Synthesis of Compound (3-2)]
In the preparation of the diazo component liquid, 3-amino-4-hydroxybenzenesulfonic acid was used instead of 2-amino-4-methylphenol. In the preparation of the coupling liquid, 3-methyl-1- ( In addition to 4-sulfophenyl) -5-pyrazolinone, instead of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one, it was carried out in a synthetic manner. Compound (3-2) was obtained in the same manner as in Example 1.

[Synthesis Example 4: Synthesis of Compound (3-3)]
In the preparation of diazo component liquid, 2-amino-4-nitrophenol is used instead of 2-amino-4-methylphenol. In the preparation of coupling liquid, 3-carboxy-1- (4- Sodium sulfophenyl) -5-pyrazolinone instead of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one, and sodium acetate was added to the complex salt Compound (3-3) was obtained in the same manner as in Synthesis Example 1 except that salting out was performed in place of common salt.

[Synthesis Example 5: Synthesis of Compounds (3-4) and (3-5)]
In the preparation of the diazo component liquid, 3-amino-4-hydroxybenzenesulfonic acid or 3-amino-2-hydroxy-5-nitrobenzenesulfonic acid is used instead of 2-amino-4-methylphenol, In the preparation of the coupling liquid, 3-methyl-1- (3'-sulfonamidophenyl) -5-pyrazolinone was used instead of 3-methyl-1- (4-sulfophenyl)- Except for 2-pyrazolin-5-one, compound (3-4) or (3-5) was obtained in the same manner as in Synthesis Example 1.

[Synthesis Example 6: Synthesis of Compound (3-6)]
In the preparation of diazo component liquid, 3-amino-2-hydroxy-5-nitrobenzenesulfonic acid is used instead of 2-amino-4-methylphenol. In the preparation of coupling liquid, 3-carboxyl group is used. In addition to sodium-1- (4-sulfophenyl) -5-pyrazolinone instead of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one, Compound (3-6) was obtained in the same manner as in Synthesis Example 1.

[Synthesis Example 7: Synthesis of Compound (3-17)]
In the preparation of diazo component liquid, 2-amino-4-nitrophenol is used instead of 2-amino-4-methylphenol. In the preparation of coupling liquid, 3-carboxy-1- (4- In addition to sodium sulfophenyl) -5-pyrazolinone instead of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one, the same procedure as in Synthesis Example 1 Compound (3-17) was obtained in the same manner.

[Synthesis Example 8: Synthesis of Compound (3-24)]
In the preparation of the diazo component liquid, 1-amino-2-naphthol-4-sulfonic acid is used instead of 2-amino-4-methylphenol, and in the preparation of the coupling liquid, 1,3-dimethyl A compound was obtained in the same manner as in Synthesis Example 1 except that methyl-5-pyrazolinone was used instead of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one. (3-24).

[Synthesis Example 9: Synthesis of Compound (4-1)]
In the preparation of the diazo component liquid, 3-amino-4-hydroxybenzenesulfonic acid is used instead of 2-amino-4-methylphenol. In the preparation of the coupling liquid, barbituric acid is used instead of 3-methyl A compound (4-1) was obtained in the same manner as in Synthesis Example 1 except for the exception that the compound was 1- (4-sulfophenyl) -2-pyrazolin-5-one.

[Synthesis Example 10: Synthesis of Compounds (4-2) to (4-4)]
In the preparation of a diazo component liquid, 3-amino-4-hydroxybenzenesulfonic acid or nitramine (3-amino-2-hydroxy-5-nitrobenzenesulfonic acid) is used instead of 2-amino-4 -Methylphenol, used in the preparation of coupling liquid, using barbituric acid or 1,3-dimethylbarbituric acid instead of 3-methyl-1- (4-sulfophenyl) -2-pyridine Except for oxazolin-5-one, compounds (4-2) to (4-4) were obtained in the same manner as in Synthesis Example 1.

[Synthesis Example 11: Synthesis of Compound (5-1)]
In the preparation of the diazo component liquid, 3-amino-4-hydroxybenzenesulfonic acid is used instead of 2-amino-4-methylphenol. In the preparation of the coupling liquid, 3-cyano-1-ethyl is used. 6-hydroxy-4-methyl-2-pyridone instead of 3-methyl-1- (4-sulfophenyl) -2-pyrazolin-5-one Compound (5-1) was obtained in the same manner as in Example 1.

＜ Evaluation of hue and light resistance ＞
[Example 1]
Anodizing was performed on an aluminum substrate in the following procedure to produce colored aluminum. Furthermore, in the steps of anodizing and dyeing, two dyeing conditions are set which change the treatment time and the concentration of the dye compound.
In a (defatted) container, mix a degreasing agent (TOP ADD-100, manufactured by Okuno Pharmaceutical Industry Co., Ltd.) 150 mL, 70 mL of 98% sulfuric acid, and 1000 mL of water to prepare a degreasing solution, and cut it into a dye of an appropriate size. The aluminum substrate was immersed therein, and degreased at 60 ° C for 3 minutes, and then washed with water.
(Anodic oxidation) Use 180% sulfuric acid to prepare 180 g / L electrolyte, connect the aluminum substrate to the electrode of the electrolytic device, and immerse it in the electrolyte tank at a temperature of 20 ± 1 ℃ and a current density of 1.0 A / dm ² Anodizing was performed under the conditions of the energization time to obtain an anodized film having the following thickness. After oxidation, washing with water was performed.
Dyeing condition (1): 15 minutes after anodizing. Film thickness: 5 μm
Dyeing conditions (2): Anodized film thickness for 45 minutes after application of electricity: 15 μm
(Surface adjustment) A surface adjustment solution (manufactured by Okuno Pharmaceutical Industry Co., Ltd., TAC SORMAL 121) and water was used to prepare a surface adjustment solution having a concentration of 50 mL / L, and the aluminum substrate was immersed therein at 45 ° C for 1 minute. After immersion, the aluminum substrate was washed with water.
(Dyeing) Using the compound (A-1) obtained in Synthesis Example 1 as a dye, a dyeing aqueous solution containing a dye having the following concentration was prepared as the dye composition of the present invention, and dipped for the following dyeing time, all in Dyeing was performed at a temperature of 55 ° C. After dyeing, the aluminum substrate was washed with water.
Dyeing condition (1): Pigment concentration of 0.1% by weight Dyeing time: 30 seconds Dyeing condition (2): Pigment concentration of 0.2% by weight Dyeing time: 5 minutes
(Sealing) A 40 mL / L sealing solution was prepared using a sealing agent (TOP Seal H-298, manufactured by Okano Pharmaceutical Industry Co., Ltd.) and water, and sealing was performed at about 90 ° C for 15 minutes. After the sealing process, drying is performed with warm air.

(Hue evaluation) The hue of the compound (3-1) was evaluated visually using a tinted aluminum plate. The evaluation results are shown in Table 1.

(Light resistance test) The light resistance test was performed with the following method about the colored aluminum plate coloring using the compound (3-1). Using a xenon attenuation meter / ATLAS Ci3000 + Xenon Weather Ometer (manufactured by Atlas), the irradiance: 300-400 nm, 60 W / m ² , temperature in the test tank: 38 ° C, humidity: 50%, black panel (BP) temperature: The colored aluminum plate was irradiated at 63 ° C. for 50 hours, and the obtained results were visually judged by the number of gray scales (fastness for discoloration and fade, JIS L 0804). The number of stages is the highest at level 5 and the lowest at level 1. The higher the level, the stronger the color and the hue before irradiation. In the evaluation method of the present invention, the determination result of the number of levels is divided into three levels, and the evaluation is performed according to the following determination criteria. The results are summarized in Table 1.
Gray scale judgment criterion: Correspondence between the number of levels and the evaluation (A, B, C) in the present invention
Levels 5 to 4: A (especially good light resistance)
Level 3: B (normal level of light resistance)
Below level 2: C (low light resistance)

[Example 9 to Example 15]
A colored aluminum plate was produced in the same manner as in Example 1 except that the compounds shown in Table 2 were used instead of the compound (3-1) as the dye, and the hue and light resistance were evaluated. The measurement results are collectively shown in Table 2.

[Comparative Example 1 to Comparative Example 5]
As a pigment, instead of the compound (3-1), acid red 182, 183, 362, and TAC Orange LH (301), which is a known orange-based alumina film dye that can be used in a single color and does not belong to the present invention, as shown in the following formula: (Manufactured by Okano Pharmaceutical Industry Co., Ltd.) and TAC Orange CH (302) (manufactured by Okano Pharmaceutical Industry Co., Ltd.) configured by blending multiple dyes. The hue and light resistance were evaluated in the same manner as in Example 1, and the results were summarized. Shown in Table 2.

[Chemical 57]

[Table 1]

According to the results in Table 2, by using an anodized aluminum colorant containing the dye composition containing the compound of the present invention, it is possible to form yellow, orange, red, and other orange-based films having high light resistance on aluminum. On the other hand, those obtained using the pigment of the comparative example had poor light resistance.

＜ Evaluation of heat resistance ＞
(Heat resistance test)
With respect to the colored aluminum plate (Example 9) which was colored under the dyeing condition (2) of the above example using the compound (3-17), a heat resistance test was performed by the following method. Using a constant temperature dryer (manufactured by AS ONE Co., Ltd., model: 87L EOP-450V), the samples were heated under the following exposure conditions.
Dryer temperature and heating time: 200 ° C-5 hours, 250 ° C-3 hours The method for evaluating the heat resistance of the present invention is to measure the color difference of colored aluminum samples before and after heating by using the following color difference meter and follow the following criteria Visual evaluation. The results are shown in Table 2.
Device: Color Difference Meter (Konica Minolta Spectrophotometer, Model: CM-3700A)
Color difference: ΔE ^* _ab (L ^* a ^* b ^* , CIE 1976)
And ΔE ^* ₀₀ (CIE DE2000)
Viewing angle: 10 °
Criteria for determining heat resistance:
A: Good heat resistance (no discoloration or discoloration)
B: Normal level heat resistance (no discoloration but slight discoloration)
C: Low heat resistance (fading and discoloration)

A heat resistance test was performed in the same manner as in Example 9 except that (5-1) was used instead of compound (3-17). The results are summarized in Table 2.

[Comparative Examples 1 to 3]
The heat resistance test was performed in the same manner as in Example 9 except that the previous orange-based pigment, namely, acid red 182, 183, or 362 of the above formula was used instead of compound (3-17). The results are summarized in Table 2.

[Table 2]

According to the results in Table 2, by using an anodized aluminum colorant containing the dye composition containing the compound of the present invention, an orange-based film having high heat resistance can be formed on aluminum. The heat resistance of the film using the pigment of the example was not inferior to that of the previous orange pigment.
[Industrial availability]

According to the dye composition containing the compound of the present invention, it is possible to obtain a coloring agent for anodized aluminum having excellent light resistance and capable of forming an orange-based colored film in a single color. In addition, by using this colorant, an anodized aluminum film excellent in light resistance when colored in a single color to be orange is obtained. The colored film obtained by using the dye composition containing the compound of the present invention is also excellent in heat resistance.

Claims (9)

A compound represented by the following general formula (1), [Chem. 1] [Formula (1), R ¹ ~ R ⁴ each independently represent _{^{-H, -SO 3 -, -NO 2}} , -NO, -CN, -OH, -COO -, -COOH, -SH, also having Amino group having 0 to 20 carbon atoms as a substituent, sulfofluorenyl group having 0 to 20 carbon atoms as a substituent, linear or branched chain having 1 to 20 carbon atoms as a substituent An alkyl group, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, or a substituent A cycloalkoxy group having 3 to 20 carbon atoms in the group, a linear or branched alkenyl group having 2 to 20 carbon atoms that may have a substituent, and 1 to 20 carbon atoms that may have a substituent A fluorenyl group, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 30 ring atoms which may also have a substituent, and R ¹ to R ⁴ may also be adjacent Radicals are bonded to each other to form a ring, M represents Cr, Fe, Co, Si or Al atom, X represents a non-chromic cation, k represents an integer of 1 to 8, and Y represents -O- or -O- (C = O )-, Z represents a group represented by the following general formulae (2a) to (2k)], [Chem 2 ] [Wherein, R ⁵ ~ R ⁴⁷ each independently represent _{^{-H, -SO 3 -, -NO 2}} , -NO, -CN, -OH, -COO -, -COOH, -SH, it may have a substituent group of An amine group having 0 to 20 carbon atoms, a sulfofluorenyl group having 0 to 20 carbon atoms that may have a substituent, and a linear or branched alkyl group having 1 to 20 carbon atoms that may have a substituent A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, a carbon which may also have a substituent A cycloalkoxy group having 3 to 20 atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms that may have a substituent, and a fluorenyl group having 1 to 20 carbon atoms that may have a substituent , An aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 30 ring atoms which may also have a substituent, R ⁴⁸ to R ⁴⁷ each independently represent -H, or -SO ₃ ^-, R ¹⁰ and ^{R 11, R 12 ~ R 16} , R 17 ~ R 21, R 22 ~ R 26, R 27 and ^{R 28, R 29 ~ R 34} , R 35 ~ R 39, R 40 ~ R ^45, R ^46, and R ⁴⁷ and also adjacent the groups bonded to each other Form a ring, A represents an oxygen atom or a sulfur atom, * represents a bond to the nitrogen atom of the junction bond, * 2 represents a bond bonded to an oxygen atom of]. The compound of the requested item 1, wherein in the above general formula (1), R ¹ ~ R ⁴ are independently _{^{-H, -SO 3 -, -NO 2}} , may also have substituent groups of carbon atoms from 0 to 10 An amine group, a linear or branched alkyl group having 1 to 10 carbon atoms that may have a substituent, or a linear or branched chain olefin having 2 to 10 carbon atoms that may have a substituent Or a fluorenyl group having 1 to 10 carbon atoms which may have a substituent. For example, the compound of claim 1 or 2, wherein in the general formulae (2a) to (2k), R ⁵ is a linear or branched alkyl group having 1 to 10 carbon atoms, which may have a substituent, may also have carbon atoms or a substituent of the aromatic hydrocarbon group having 6 to 20, R ⁶ is -COO ^-, -COOH, also having an alkoxy substituent having a carbon number of 1 to 10 atoms of straight-chain or branched-chain of Or a fluorenyl group having 1 to 10 carbon atoms which may have a substituent, and R ⁷ or R ⁸ are each independently -H, and may be a straight or branched chain having 1 to 10 carbon atoms which may have a substituent. Alkyl groups or aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent, and R ⁹ to R ¹¹ are each independently -H, -CN, and may have 1 to 10 carbon atoms having a substituent. A linear or branched alkyl group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R ¹⁶ to R ²⁰ are each independently -H and may have a carbon atom which may have a substituent A linear or branched alkyl group having 1 to 10 or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R ²¹ to R ²⁵ are each independently -H and may have a substituent. Carbon number of base 1 ～ 10 A linear or branched alkyl group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R ²⁶ to R ³⁰ are each independently -H and may have a carbon atom which may have a substituent 0 to 20 amine groups, or 1 to 10 carbon atoms, which may have substituents, linear or branched alkyl groups, R ³¹ and R ³² are each independently -H, and may have a substituent Linear or branched alkyl groups having 1 to 10 carbon atoms, or linear or branched alkenyl groups having 2 to 20 carbon atoms that may have a substituent, R ³³ to R ³⁸ respectively Independently -H or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ³⁹ to R ⁴³ are each independently -H or a carbon atom which may also have a substituent number 1 ~ 10 linear or branched chain of the alkyl group, R ⁴⁴ ~ R ⁴⁶ R ⁴⁸ ~ R, and any one or two of the ⁴⁹ is -SO ₃ ^- or -COO ^-, R ⁴⁷ is also having the carbon atoms, a substituted amino group of 0 to 10, any one of R ⁵⁰ ~ R ⁵⁵ in one or two of the -SO ₃ ^- or -COO ^-. The compound according to any one of claims 1 to 3, wherein Z is a base represented by the above formula (2a), (2b) or (2c). A dye composition containing the compound according to any one of claims 1 to 4. A coloring agent for anodized aluminum, which contains the dye composition according to claim 5. A coloring method of anodized aluminum oxide, anodized aluminum oxide, or anodized aluminum alloy, characterized in that a dye composition containing 0.02 to 10% by mass of the compound according to any one of claims 1 to 4 is used. A manufacturing method, which is a method for manufacturing a compound according to any one of claims 1 to 4, and further comprising the following general formula (I): [In the formula (III), R ¹ to R ⁴ , Y, and Z have the same meanings as defined above] The compound shown is reacted with a compound containing a Cr, Fe, Co, Si, or Al atom to obtain the general formula ( 1) Step of the compound shown. The method according to claim 8, wherein the compound represented by the general formula (I) is obtained by the following formula (II): [In the formula (II), R ¹ to R ⁴ and Y represent the same meaning as the above definition] The diazo compound obtained by diazotizing the compound shown in the formula and / or its salt and the diazo coupling reaction of the coupling component The obtained ones, and the aforementioned coupling units are the following general formulae (III-a) to (III-k): [化 5] [In the formula, R ⁵ to R ⁵⁵ and A represent the same meanings as defined above] and / or a salt thereof.