JP2021055095A - Xanthene-based coloring pigment, dye composition, coloring agent and coloring method for anodized aluminum, and method for producing the coloring pigment - Google Patents

Abstract

To provide a xanthene-based coloring pigment capable of forming an anodic oxide film, the surface of aluminum, aluminum oxide or aluminum alloy of which does not contain heavy metals such as chromium and that exhibits a monochroic and purplish color.SOLUTION: A xanthene-based coloring pigment is expressed by the following general formula (1). [In the formula (1), R1 and R2 are each independently an optionally substituted 6-30C naphthyl group or an optionally substituted 6-30C phenyl group, provided that at least one of R1 and R2 is the optionally substituted 6-30C naphthyl group].SELECTED DRAWING: None

Description

The present invention relates to xanthene dyes and dye compositions suitable for colorants for anodized aluminum. The present invention also relates to a method for coloring aluminum anodized aluminum using the dye and dye composition, and a method for producing the dye.

Conventionally, as a method of coloring the surface of aluminum (including its oxide or alloy), aluminum is energized (anodized) as an anode in an electrolytic solution containing water and an appropriate acid, and a porous aluminum oxide film (anodic oxide) is applied to the surface. After forming an alumite film), a method of coloring the surface using an organic dye (or an organic dye) as a colorant is used (Patent Documents 1 to 5).

In order to meet the demand for a wide variety of colored aluminum products in recent years, a coloring method (Patent Document 4) capable of dealing with dyes of various colors has been developed. For example, a purple xanthene dye is known as a colorant for aluminum anodized aluminum (Patent Documents 4 and 5, etc.), but the hue and light resistance are insufficient, and a single dye does not require color mixing. A dye having good light resistance is required.

Chromium-containing dyes for alumite films (Patent Documents 1 to 3 and the like) have excellent light resistance and heat resistance and have been used for general purposes. However, in recent years, they do not contain heavy metals such as chromium from the environmental point of view. , Dyes having various hues are required.

Japanese Unexamined Patent Publication No. 9-302256 Japanese Unexamined Patent Publication No. 60-235867 Special Table 2002-522617 Japanese Unexamined Patent Publication No. 63-312998 Special Table 2013-506053

Dyes that do not contain chromium and have a desired hue are limited, and it is useful to develop a dye having a novel structure having a desired hue.

The problem to be solved by the present invention is a novel xanthene capable of forming a monochromatic, purple-based anodized film on the surface of aluminum, aluminum oxide or aluminum alloy, which does not contain heavy metals such as chromium. It is an object of the present invention to provide a dye system, a dye composition containing the dye, a colorant and a coloring method for anodized aluminum composed of the dye composition, and a method for producing the dye.

In order to solve the above problems, the inventors have diligently studied a dye (dye) for aluminum anodic oxidation, and as a result, by using a xanthene dye having a specific structure as a colorant for aluminum anodic oxide, on aluminum anodic oxide. In addition, it was found that an anodic oxide film having a monochromatic and purple color can be formed. That is, the present invention is composed of the following contents.

1. 1. A xanthene dye represented by the following general formula (1).

[In equation (1), R ¹ and R ² are independent of each other.
A naphthyl group having 6 to 30 carbon atoms, which may have a substituent,
Alternatively, it represents a phenyl group having 6 to 30 carbon atoms which may have a substituent.
However, at least one of ^{R 1} and R ^{2 is}
It is a naphthyl group having 6 to 30 carbon atoms which may have a substituent. ]

2. ^{A xanthene-based dye in which R 1} or R ² is any one of the monovalent groups represented by the following general formulas (2) to (4) in the general formula (1).

[In formulas (2) to (4), R ^{3 to} R ²¹ are independently of -H, -OH, -COOM, -NO ₂ , -NO, -CN, -SO ₃ M, -SH, respectively.
An amino group having 0 to 20 carbon atoms, which may have a substituent,
A sulfonyl 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,
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 cycloalkoxy group having 3 to 20 carbon atoms, which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
It represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent.
M represents a hydrogen atom or an alkali metal atom. ]

3. 3. In the general formula (2) or ^(3), R 3 ^{to R 16} are each independently, -H, -SO ₃ H or xanthene dye is the _-SO 3 Na.

4. In the general formula (4), R ^{17 to} R ²¹ may independently have —H, a linear or branched alkyl group having 1 to 10 carbon atoms, or a substituent. A xanthene dye that is an amino group with 0 to 10 atoms.

5. A dye composition containing the xanthene dye.

6. A colorant for anodized aluminum containing the dye composition.

7. A method for coloring aluminum anodized aluminum, anodized aluminum oxide, or an anodized aluminum alloy, which comprises using a dye composition containing 0.02 to 10% by mass of the xanthene-based dye.

8. A method for producing xanthene dyes,
A manufacturing method characterized in that only step 1 is performed, or step 2 is performed after step 1.
Step 1: With the compound represented by the following formula (5),
Reacting the compound represented by the following general formula (2a) or (3a).
Step 2: The intermediate obtained in Step 1 and
The compound represented by the following general formula (2a), (3a) or (4a) is reacted.

[In the formulas (2a), (3a) or (4a), R ^{3 to} R ²¹ have the same meaning as the definitions of the general formulas (2) to (4). ]

INDUSTRIAL APPLICABILITY According to the present invention, a novel xanthene dye, which is capable of forming an anodic oxide film which does not contain heavy metals such as chromium and exhibits a monochromatic and purple color on the surface of aluminum, aluminum oxide or aluminum alloy, can be obtained. It is possible to provide a dye composition contained therein, a colorant and a coloring method for anodized aluminum composed of the dye composition, and a method for producing the dye.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof. Hereinafter, the xanthene-based dye represented by the general formula (1) will be specifically described, but the present invention is not limited thereto.

The xanthene dye according to the present invention is represented by the following general formula (1). In the general formula (1), R ¹ and R ² are independently "a naphthyl group having 6 to 30 carbon atoms which may have a substituent" or "a carbon atom which may have a substituent". It represents "phenyl group of number 6 to 30". However, ^{at least one of R 1} and R ² is a "naphthyl group having 6 to 30 carbon atoms which may have a substituent". Specifically, when R ¹ is "a phenyl group having 6 to 30 carbon atoms which may ^{have a substituent", R 2} is "the number of carbon atoms which may have a substituent". 6 to 30 naphthyl groups ". Further, when R ² is "a phenyl group ^{having 6 to 30 carbon atoms which may have a substituent", R 1} is "a phenyl group having 6 to 30 carbon atoms which may have a substituent". It is a naphthyl group of. Further, ^{both R 1} and R ² may be "naphthyl groups having 6 to 30 carbon atoms which may have a substituent".

In the general formula (1), the "number of carbon atoms" in the "naphthyl group having 6 to 30 carbon atoms which may have a substituent" is, for example, 10 to 30, 10 to 25, 10 to 20, 10 It may be ~ 18, 10-15, or 10-12, and may be 10. In the general formula (1), the "number of carbon atoms" in the "phenyl group having 6 to 30 carbon atoms which may have a substituent" is, for example, 6 to 25, 6 to 20 or 6 to 18. You can.

In the general formula (1), "a naphthyl group having 6 to 30 carbon atoms which may have a substituent" or "a phenyl group having 6 to 30 carbon atoms which may have a substituent" in " Specifically, as a "substituent",
Hydroxy group (-OH), -COOM (M is an alkali metal atom such as lithium atom (Li), sodium atom (Na), potassium atom (K)), carboxyl group (-COOH), nitro group (-NO ₂ ) , Nitroso group (-NO), cyano group (-CN), -SO ₃ M (M is an alkali metal atom such as lithium atom (Li), sodium atom (Na), potassium atom (K)), sulfonic acid group _(-SO 3 H), thiol group (-SH),
An unsubstituted amino group; a monosubstituted amino group in which a group having 0 to 20 carbon atoms is bonded via -NH-; a disubstituted amino group in which a group having 0 to 20 carbon atoms is bonded via -N <;
Group having - sulfonamide _{(-S (= O) 2 -NH} 2) group, mesyl group, a sulfonyl group such as tosyl group _{(-S (= O) 2)} ;
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, n-hexyl group, isohexyl group, heptyl group, n-octyl group, t- Linear or branched alkyl groups such as octyl group, isooctyl group, nonyl group, decyl group;
Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group;
Linear or branched alkoxy groups such as methoxy group, ethoxy group, propoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group;
Cycloalkoxy groups such as cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group;
Vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, or linear chain in which a plurality of alkenyl groups thereof are bonded. Or a branched alkenyl group;
Acyl groups such as formyl group, acetyl group, propionyl group, acryryl group, benzoyl group;
Aromatic hydrocarbon groups such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, triphenylenyl group, indenyl group, fluorenyl group;
Pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, pyrazinyl group, pyridadinyl group, piperidinyl group, piperazinyl group, quinolyl group, isoquinolyl group, naphthyldinyl group, indolyl group, benzoimidazolyl group, carbazonyl group. , Carbolinyl group, acridinyl group, phenanthrolinyl group, phenanthridinyl group, hydantoin group, flanyl group, benzofuranyl group, dibenzofuranyl group, pyranyl group, cummarinyl group, isobenzofuranyl group, xanthenyl group, oxanthrenyl group , Pyranonyl group, thienyl group, thiopyranyl group, benzothienyl group, dibenzothienyl group, thioxanthenyl group, oxazolyl group, benzoxazolyl group, morpholinyl group, thiazolyl group, benzothiazolyl group and other heterocyclic groups;
Cyclic olefin groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, (1,3- or 1,4-) cyclohexadienyl group, 1,5-cyclooctadienyl group; etc. Can be given.
Only one of these "substituents" may be contained, a plurality of these "substituents" may be contained, and when a plurality of these "substituents" are contained, they may be the same or different from each other. Moreover, these "substituents" may have the above-exemplified substituents. When the "substituent" contains a carbon atom, the carbon atom is included in the above "number of carbon atoms 6 to 30".

In the xanthene dye represented by the general formula (1), R ¹ or R ² is preferably a monovalent group of any one represented by the following general formulas (2) to (4). The monovalent group represented by the general formula (2) ^{is a naphthyl group having a group represented by R 3 to} R ⁹ , and the monovalent group represented by the general formula (3) is represented by R ^{10 to} R ¹⁶ . The naphthyl group having a group represented, the monovalent group represented by the general formula (4) ^{is a phenyl group having a group represented by R 17 to} R ²¹ , and the broken line portion represents a connecting portion. ..

In the general formula ^{(2) ~ (4),} R 3 ~R 21 are each _{^{independently, -H, -OH, -COO -,}} -COOM, -NO 2, -NO, -CN, -SO 3 M, -SH,
An amino group having 0 to 20 carbon atoms, which may have a substituent,
A sulfonyl 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,
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 cycloalkoxy group having 3 to 20 carbon atoms, which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
It is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent.
Here, M represents an alkali metal atom such as a hydrogen atom (H); a lithium atom (Li), a sodium atom (Na), and a potassium atom (K), and M may be a hydrogen atom or a sodium atom. preferable. When R ^{3 to} R ²¹ contain a carbon atom, the carbon atom is a "naphthyl group having 6 to 30 carbon atoms which may have a substituent" or a "substituent" in the general formula (1). Is included in "6 to 30 carbon atoms" in "a phenyl group having 6 to 30 carbon atoms which may have."

In the general formulas (2) to (4), the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by ^{R 3 to} R ^{21 is an unsubstituted amino group (-NH).} ₂ ), mono-substituted amino groups, di-substituted amino groups and the like. The number of carbon atoms in the mono- or di-substituted amino group is, for example, 1 to 20, may be 1 to 10, and may be 2 to 6. The amino group having 0 to 20 carbon atoms which may have a substituent is an aromatic hydrocarbon group having 6 to 20 carbon atoms and 1 carbon atom, which will be described later, via -NH- or -N <. It may be a group to which an acyl group of ~ 20 and a heterocyclic group having 2 to 20 carbon atoms are bonded. Examples of the monosubstituted amino group include an ethylamino group, an acetylamino group, and a phenylamino group. Examples of the disubstituted amino group include a dialkylamino group having 2 to 20 carbon atoms such as a dimethylamino group, a diethylamino group and a dibutylamino group; a diphenylamino group and an acetylphenylamino group.

In the general formula (2) to ^(4), "Good sulfonyl group which may have a substituent group having a carbon number of 0 to 20" represented by R 3 ^{to R 21} _are, -SO ^{2 -R 100} (or means ^{_{-S (= O) 2 -R 100}} ) in what a sulfonyl group having a substituent ^{R 100} represented. R ¹⁰⁰ may be a group containing a carbon atom or a group not containing a carbon atom. When R ¹⁰⁰ is a carbon-containing group, the ^{number of carbon atoms of R 100} is 1 to 20, may be 1 to 10, and may be 1 to 7. Examples of the sulfonyl group which may have a substituent having 0 to 20 carbon atoms include a sulfonamide group (-S (= O) _2- NH ₂ ), a mesyl group and a tosyl group.

In the general formulas (2) to (4), "carbon" in "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 3 to} R ^21. Specific examples of the "linear or branched alkyl group having 1 to 20 atoms" include a methyl group, an ethyl group, an n-propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Linear alkyl groups such as groups and decyl groups; branched alkyl groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group and t-octyl group can be mentioned.

In the general formulas (2) to (4), "a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent" represented by ^{R 3 to} R ^{21 has "a cycloalkyl group having 3 to 20 carbon atoms".} Specific examples of the "cycloalkyl group" include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group and the like.

In the general formulas (2) to (4), "carbon" in "a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 3 to} R ^21. Specific examples of the "linear or branched alkoxy group having 1 to 20 atoms" include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, and a heptyl. Linear alkoxy groups such as oxy group, octyloxy group, nonyloxy group and decyloxy group; isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group, t-octyloxy group and the like. A branched alkoxy group can be mentioned.

In the general formulas (2) to (4), "a cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent" represented by ^{R 3 to} R ^{21 has "a cycloalkoxy group having 3 to 20 carbon atoms".} Specific examples of the "cycloalkoxy group" include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group and the like.

In the general formulas (2) to (4), "carbon" in "a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent" represented by ^{R 3 to} R ^21. Specific examples of the "linear or branched alkenyl group having 2 to 20 atoms" include a vinyl group, an allyl group, an isopropenyl group, a 2-butenyl group, a 1-hexenyl group, or an alkenyl group thereof. Examples thereof include a plurality of bonded linear or branched groups.

In the general formulas (2) to (4), the "acyl group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 3 to} R ^{21 is-(C = O) -R.} It is a group represented by ^101. Substituent R ¹⁰¹ may be a group containing a carbon atom or a group not containing a 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. Examples of the substituent R ¹⁰¹ include -H, -CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH = CH ₂ , -C ₆ H ₅ (phenyl group) and the like. Specific examples of the "acyl group having 1 to 20 carbon atoms" in the "acyl group having 1 to 20 carbon atoms which may have a substituent" include a formyl group, an acetyl group, a propionyl group, and an acryryl group. , Benoxyl group and the like.

In the general formulas (2) to (4), the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent" represented by ^{R 3 to} R ^{21 has "6 to 6 carbon atoms".} Specific examples of the "30 aromatic hydrocarbon groups" include a phenyl group, a benzoyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, an indenyl group, a fluorenyl group and the like. It may be via a group or an amino group. Here, the "aromatic hydrocarbon group" in the present invention represents an aromatic hydrocarbon group and a condensed polycyclic aromatic group, and among these, a phenyl group or a naphthyl group is preferable.

In the general formulas (2) to (4), "a heterocyclic group having 2 to 20 carbon atoms which may have a substituent" represented by ^{R 3 to} R ^{21 has "a heterocyclic group having 2 to 20 carbon atoms".} Specific examples of the "heterocyclic group" include pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyldinyl group, indolyl group, benzoimidazolyl group and carbazonyl group. Carbolinyl group, acridinyl group, phenanthrolinyl group, hydantin group, flanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl The group etc. can be mentioned.

Represented ^{by R 3 to R 21} in the general formulas (2) to (4),
"Amino group having 0 to 20 carbon atoms having a substituent",
"Sulfonyl group having 0 to 20 carbon atoms having a substituent",
"Linear or branched alkyl group having 1 to 20 carbon atoms having a substituent",
"Cycloalkyl group having 3 to 20 carbon atoms having a substituent",
"Linear or branched alkoxy group having 1 to 20 carbon atoms having a substituent",
"Cycloalkoxy group having 3 to 20 carbon atoms having a substituent",
"Linear or branched alkenyl group having 2 to 20 carbon atoms having a substituent",
"Acyl group having 1 to 20 carbon atoms having a substituent",
The "substituent" in "aromatic hydrocarbon group having 6 to 20 carbon atoms having a substituent" or "heterocyclic group having 2 to 20 carbon atoms having a substituent"
The above-mentioned "naphthyl group having 6 to 30 carbon atoms which may have a substituent" or "phenyl group having 6 to 30 carbon atoms which may have a substituent" in the general formula (1). The same as those mentioned as "substituents" in. Only one of these "substituents" may be contained, a plurality of these "substituents" may be contained, and when a plurality of these "substituents" are contained, they may be the same or different from each other. Moreover, these "substituents" may have the above-exemplified substituents. When the "substituent" contains a carbon atom, the carbon atom is the above-mentioned "carbon atom number 0 to 20", "carbon atom number 1 to 20", "carbon atom number 2 to 20", "carbon atom number 2 to 20". It is included in "Equation 3 to 20" and "Number of carbon atoms 6 to 20". Further, 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 to form a ring.

In the general formula (2) or ^(3), R 3 ^{to R 16} are each independently, -H, it is preferably -SO ₃ H or _-SO 3 Na.

At least one of R ³ to R ⁹ may be a -SO ₃ M, ^{R 5} may be a -SO ₃ M. At least one of R ¹⁰ to R ¹⁶ may be a -SO ₃ ^{M, R 12} or ^{R 13} may be a -SO ₃ M.

In the general formula (4), R ^{17 to} R ²¹ each independently have —H, a linear or branched alkyl group having 1 to 10 carbon atoms, or a carbon atom which may have a substituent. It is preferably several to 10 amino groups.

The compound which is the xanthene dye of the present invention represented by the general formula (1) (hereinafter, also simply referred to as dye (1)) includes all possible stereoisomers and tautomers. Specific examples of the dye (1) are shown in the following formulas, but the present invention is not limited thereto. In the structural formula, some hydrogen atoms are omitted.

An example of the method for producing the xanthene dye (dye (1)) of the present invention represented by the general formula (1) is shown below, but the method is not limited to this method. Specifically, the production method of the present invention
A method for producing the dye (1) by performing only the following "step 1", or
This is a method for producing the dye (1) by performing the following "step 2" after the "step 1".
Step 1: With the compound represented by the following formula (5),
Reacting the compound represented by the following general formula (2a) or (3a).
Step 2: The intermediate obtained in Step 1 and
The compound represented by the following general formula (2a), (3a) or (4a) is reacted.

[In the formulas (2a), (3a) or (4a), R ^{3 to} R ²¹ have the same meaning as the definitions of the general formulas (2) to (4). ]

Hereinafter, "step 1" will be described. The starting material (5) (3,6-dichloro-9- (2-sulfonatophenyl) xanthylium) and the corresponding group (R ^{3) represented by the general formula (2a) or (3a).} and naphthylamine derivatives having to R ^16), any solvent which dissolves these materials, by reacting with conditions such as appropriate temperature and reaction time, xanthene dyes for the purpose, or the intermediates thereof Obtainable.
The solvent is not particularly limited, but specifically, esters such as ethyl acetate and -n-butyl acetate; diethyl ether, propylene glycol monomethyl ether (PGME), ethylene glycol monoethyl ether (ethyl cellosolve). Ethers such as; ether esters such as propylene glycol monomethyl ether acetate (PGMEA); ketones such as acetone and cyclohexanone; alcohols such as methanol, ethanol and 2-propanol; diacetone alcohol (DAA) and the like; benzene and toluene , Aromatic hydrocarbons such as xylene; amides such as N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP); dimethylsulfoxide (DMSO) and the like. These solvents may be used alone or in combination of two or more. Of these, N-methylpyrrolidone is preferable.

Hereinafter, "step 2" will be described. After performing the above-mentioned "step 1", a naphthylamine derivative having ^{the obtained intermediate and a corresponding group (R 3 to} R ¹⁶ ) represented by the general formula (2a), (3a) or (4a). By reacting a compound or ^{an aniline derivative compound having a corresponding group (R 17 to} R ²¹ ) in an arbitrary solvent that dissolves these raw materials under conditions such as an appropriate temperature and reaction time, the object is achieved. Xanthene-based dyes can be obtained. As the solvent, the same solvent as those mentioned in step 1 can be used, and among these, N-methylpyrrolidone is preferable.

In step 1 or step 2, which is a method for producing the dye (1), the charged molar ratio of the formula (5) as a starting material to the general formulas (2a), (3a) or (4a) is the formula. (5) The general formula (2a), (3a) or (4a) is preferably 2 to 20 times the molar equivalent with respect to 1 mol.

The dye (1) can be purified by a known method such as purification by column chromatography; adsorption purification with silica gel, activated carbon, activated clay, etc .; recrystallization with a solvent, various crystallization methods using an acid, or the like. ..

The identification and physical property evaluation of the dye (1) of the present invention, its intermediate, or various products obtained in the above step 1 or step 2 are performed by ultraviolet-visible absorption spectrum analysis (UV-Vis), thermal weight measurement-difference. Thermal analysis (TG-DTA), gas chromatography analysis (GC), thin layer chromatography analysis (TLC), gas chromatography-mass spectrometry (GC / MS), nuclear magnetic resonance spectroscopy (NMR) analysis, etc. can be performed. it can.

The xanthene dye (dye (1)) represented by the general formula (1) in the present invention does not contain heavy metals such as chromium on the surface of aluminum, aluminum oxide or aluminum alloy, and is monochromatic and purple. It is possible to form an anodized film exhibiting the above. Further, the dye (1) can have sufficient heat resistance and / or light resistance. Therefore, the dye (1) can be used as a component of the dye composition. The dye (1) can also be used alone to color aluminum, aluminum oxide, fibers and the like. That is, the dye (1) can be suitably used as a dye compound for coloring aluminum, aluminum oxide, fibers, etc. by using one kind of monochromatic dye alone. Two or more dyes (1) may be used in combination in order to obtain various colors by mixing colors. The dye composition may be mixed with other components for optimum dyeing (coloring with a dye). Specific examples thereof include liquids (solvents) such as water, alcohol and solvents; additives such as surfactants; and the like. Water is preferable as the solvent. The dye (1) may be used as a component of the dye composition in combination with other dyes. Other dyes are compounds other than dye (1), pigments, dyes, etc., and specifically, ruthenium complex, coumarin dye, cyanine dye, merocyanine dye, rodacianin dye, phthalocyanine dye, porphyrin. Examples include system pigments and other xanthene pigments. When the dye (1) and other components are used in combination, the amount of the other components used with respect to the dye (1) is preferably 10 to 200% by mass, more preferably 20 to 100% by mass. .. The aluminum oxide is a composition obtained by oxidizing aluminum and mainly containing aluminum and oxygen, and the composition ratio may be arbitrary, and the aluminum oxide is contained, and the crystal system may be single crystal, polycrystalline or amorphous. It may be present or a mixture thereof.

The dye composition of the present invention can be applied as a colorant for anodized aluminum. The dye composition described above can also be used as a colorant used in an anodized aluminum alloy. That is, as one embodiment of the present invention, use (application) of a xanthene dye represented by the general formula (1) for coloring aluminum anodized aluminum or an aluminum alloy anodized aluminum or a dye composition containing the dye. Is provided. Further, as an embodiment of the present invention, a xanthene dye represented by the general formula (1) for producing a colorant for aluminum anodized aluminum or an aluminum alloy anodized alloy, or a dye composition containing the dye. Use is provided.

When the dye (1) is used as a colorant such as aluminum anodized aluminum, the concentration of the dye (1) in the dye composition containing the dye (1) is based on the total amount of the dye composition in the coloring (dyeing) method. It is preferably 0.02 to 10% by mass, and more preferably 0.05 to 3% by mass. The lower the concentration of the dye (1), the lighter the color can be colored, and the higher the concentration, the more neutral to the dark color can be colored.

Here, the anodized aluminum means aluminum that has been subjected to a treatment for forming an oxide layer having pores on the surface of the electrolyzed aluminum in an electrolytic solution such as an acid aqueous solution. The colorant for anodized aluminum means one that can be colored (dyed) by adsorbing the dye (1) in the pores on the aluminum surface having the pores. Usually, in order to improve the durability and light resistance of the colored aluminum surface, a pore-sealing treatment for closing the pores is performed after coloring.

Examples of aluminum in anodized aluminum include aluminum-containing metals or metal compounds such as aluminum, aluminum oxide, and aluminum alloys with other metals.

Here, the anodized aluminum alloy means an alloy in which the surface of the aluminum alloy is anodized. The aluminum alloy in the anodized aluminum alloy means an alloy containing aluminum as a main component, and means an alloy with a metal such as copper, manganese, silicon, magnesium, zinc, and nickel. The composition ratio of aluminum and other metals is not particularly limited.

As a method for coloring aluminum using a colorant for anodized aluminum, a method known as an alumite dyeing method can be used. For example, the method described in Japanese Industrial Standards (JIS H 8601: 1999 “Aluminum and Aluminum Alloy Anodized Film”), Patent Document 1 and the like can be used. The method for coloring aluminum is not particularly limited, but an example is shown below.

First, the aluminum plate is degreased and washed with an aqueous acid solution such as sulfuric acid, oxalic acid, chromic acid, and sulfonic acid. Next, the degreased aluminum plate is used as an anode and electrolyzed using an acid aqueous solution as an electrolytic solution to form an anodized film (anodized film) forming many pores on the surface of the aluminum anode (anodized). ), Wash with water. Subsequently, after appropriately performing surface adjustment, washing with water, etc., the dye is immersed in an aqueous solution of a colorant for aluminum anoxide containing a dye composition containing the compound of the present invention, and the dye is adsorbed (dyed, dyed) in the pores. It can be colored by electrolyzing) and sealing the pores on the surface with aluminum oxide hydrate or the like to form a sealing substance.
When two or more kinds of dye compositions of the present invention are used in combination, or when the dye composition of the present invention is used in combination with other dyes, even if a mixed solution of all the dyes to be used is prepared and aluminum anodized aluminum is immersed. Well, each dye solution may be prepared separately and aluminum anodized may be immersed in each solution in sequence.

The electrolysis conditions at the time of coloring of the present invention may be DC electrolysis or AC electrolysis, and DC electrolysis is preferable. The current density is preferably from ^{0.1~10A / dm 2, 0.5~3A / dm} 2 is more preferable. The energizing time is preferably 10 seconds to 60 minutes. The thickness of the anodized film is preferably 2 to 20 μm. As for these anodizing conditions, the longer the energization time is and the thicker the anodizing film is, the darker the color is. Therefore, by adjusting these conditions, light to neutral to dark colors can be adjusted.

The treatment temperature of each of the above steps is preferably a suitable temperature, and the temperature at the time of anodizing is preferably 0 to 80 ° C. The temperature at the time of dyeing is preferably 10 ° C to 70 ° C. Other treatment temperatures are preferably 10 to 80 ° C.

The dye composition in the present embodiment can also be used for anodized oxides using a metal other than aluminum. For example, magnesium, zinc, titanium, zirconium, etc., which can adsorb dyes in anodized pores, can be applied to non-metals such as conductive plastics.

The colorant for aluminum anodic oxide of the present embodiment can be evaluated by measuring the characteristics of a sample colored in aluminum by measuring hue, light resistance, heat resistance, and the like. Hue can be visually evaluated for hue and uniformity, and can be measured as density (K / Sd), hue (L ^* , a ^* , b ^* ) and color difference (ΔE ^* ) with a color difference meter. Good.

The color that can be represented by using the colorant for aluminum anodide of the present embodiment can represent a purple color such as purple, bluish purple, and reddish purple. It is possible to represent different shades such as these light colors (light purple, etc.) and dark colors (dark purple, etc.). The colorant for anodized aluminum of the present embodiment can also represent a mixed color (intermediate color) by using the above-mentioned compound in combination with another dye.

In the light resistance test of aluminum colored with the colorant for aluminum anoxide of the present embodiment, the sample is irradiated with light for a certain period of time using a testing machine that imitates sunlight including ultraviolet light, and before and after the test. This may be done by measuring the change in the hue of the colored aluminum. Specifically, even if it is evaluated by ^{the color difference ΔE *} _ab (or ΔE ^* ) before and after the light irradiation test obtained by measuring the tint with ^{the CIE L *} a ^* b ^* color system using a color difference meter or the like. Good. In the determination of light resistance, the hue of colored aluminum may be visually determined for dyeing fastness using a gray scale according to a method defined by Japanese Industrial Standards (JIS L 0804 "Gray scale for discoloration and fading"). ..

The heat resistance test of aluminum colored with the colorant for aluminum anoxide of the present embodiment is suitable, for example, in a thermostat in a temperature range of 50 to 300 ° C. or in a hot air dryer for 30 minutes to 50 hours. Similar to the light resistance test, there is a method of evaluating the change in hue before and after the test, such as a method of heating for a certain period of time.

The colored aluminum using the colorant for anodized aluminum of the present embodiment is used for a wide variety of aluminum plate materials and products using an aluminum exterior.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples. In the examples, the maximum absorption wavelength (λmax) (nm) measured by ultraviolet-visible absorption spectrum analysis (UV-Vis) of an aqueous solution of a compound (dye) is shown.

[Synthesis Example 1] Synthesis of dye (1-1) In a reaction vessel, 3,6-dichloro-9- (2-sulfonatophenyl) xanthylium (or dichlorosulfofluorane, product name: DCSF, Taiyo Fine Chemical Co., Ltd.) ) 40 g, 73.2 g of 5-amino-2-naphthalene sulfonic acid, and 240 mL of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 140 ° C. for 20 hours. The reaction solution was solvent-removed at 120 ° C.-reduced pressure and concentrated. 300 mL of 30% hydrochloric acid was added to the residue, the mixture was stirred at room temperature for 30 minutes, the precipitated solid was collected by filtration and dried to obtain the desired pigment (1-1) as a black-purple powder (36.8 g) (λmax:). 539 nm).

[Synthesis Example 2] Synthesis of dye (1-2) 8.5 g of DCSF, 22.5 g of 6-amino-2-naphthalene sulfonic acid and 40 mL of NMP were placed in a reaction vessel, and the mixture was stirred at 160 ° C. for 21 hours. The reaction mixture was allowed to cool to 30 ° C. or lower, 50 mL of acetonitrile was added, the mixture was stirred for 30 minutes, and the precipitated solid was filtered. After adding 60 mL of 17.5% hydrochloric acid and stirring at room temperature for 30 minutes, the precipitated crystals were filtered and dried to obtain the desired dye (1-2) as a black-purple powder (18.1 g) (. λmax: 567 nm).

[Synthesis Example 3] Synthesis of dye (1-3) 8.0 g of DCSF, 9.7 g of 7-amino-2-naphthalene sulfonic acid and 30 mL of NMP were placed in a reaction vessel, and the mixture was stirred at 60 ° C. for 3 hours. The reaction mixture was allowed to cool to 30 ° C. or lower, and the precipitated solid was filtered and dried to obtain 6.6 g of an intermediate. Subsequently, 5.0 g of the intermediate, 6.8 g of 2-amino-5- (diethylamino) toluene, and 20 mL of NMP were placed in another reaction vessel, and the mixture was stirred at 120 ° C. for 4 hours. The reaction mixture was placed in 200 mL of 5% hydrochloric acid and stirred at room temperature for 30 minutes. The precipitated solid is collected by filtration, placed in 50 mL of water, neutralized by adding a 48% aqueous sodium hydroxide solution, dried under reduced pressure at 80 ° C. for 24 hours or more, and the target pigment (1-3) is a black-purple powder. (5.5 g) (λmax: 552 nm).

[Synthesis Example 4] Synthesis of dye (1-4) 6.9 g of DCSF, 9.09 g of 6-amino-1-naphthol-3-sulfonic acid and 50 mL of NMP were placed in a reaction vessel and stirred at 140 ° C. for 21 hours. did. The reaction solution was placed in 200 mL of water, and 100 mL of 35% hydrochloric acid was further added to precipitate the dye. The solid was taken out by filtration, and after drying, the desired dye (1-4) was obtained as a bluish-purple powder (14.3 g) (λmax: 563 nm).

[Example 1]
<Making colored aluminum>
Colored aluminum was produced by anodizing the aluminum substrate in the following procedure. The treatment time and dye compound concentration were set in the steps of anodizing and dyeing.
(Solvent degreasing) A mixture of 150 mL of a degreasing agent (Top ADD-100, manufactured by Okuno Pharmaceutical Industry Co., Ltd.), 70 mL of 98% sulfuric acid, and 1000 mL of water was prepared as a degreasing solution, and aluminum for dyeing was cut to an appropriate size. The substrate was immersed, degreased at 60 ° C. for 3 minutes, and then washed with water.
(Anodizing) 180 g / L electrolytic solution was prepared using 98% sulfuric acid, an aluminum substrate was connected to the electrodes of the electrolytic device, immersed in an electrolytic solution tank, and the temperature was 19 to 21 ° C., and the current density was 1.0 A /. Anodization ^{was performed under the condition of energization time of dm 2} or less to obtain an anodized film having the following thickness. After oxidation, it was washed with water.
Anodizing conditions: 15 minutes of energization Anodized film thickness: 5 μm
(Surface adjustment) A surface adjustment solution having a concentration of 50 mL / L was prepared using a surface conditioner (TAC Somar 121 manufactured by Okuno Pharmaceutical Industry Co., Ltd.) and water, and the aluminum substrate was immersed at 45 ° C. for 1 minute. After the immersion, the aluminum substrate was washed with water.
(Dyeing) Using the dye (1-1) obtained in Synthesis Example 1, a dyeing aqueous solution containing each of the following concentrations of dye was prepared as the dye composition of the present invention, and immersed in the dyeing time below. Both were dyed at a temperature (building bath temperature) of 55 ° C. After dyeing, the aluminum substrate was washed with water.
Dyeing conditions: Dye concentration 2.0% by weight Dyeing time: 30 seconds (sealing) 40 mL / L sealing liquid was prepared using a sealing agent (Top Seal H-298, manufactured by Okuno Pharmaceutical Industry Co., Ltd.) and water. Then, the hole was sealed at about 90 ° C. for 15 minutes. After the sealing treatment, it was dried with warm air.

<Evaluation of hue>
The hue of the colored aluminum plate colored with the dye (1-1) is visually evaluated and evaluated by the ^{CIE L *} a ^* b ^* color system with a color difference meter (device name: Konica Minolta spectroscopic color difference meter model: CM-3700A). did. The results of the evaluated hues are shown in Table 1.

[Examples 2 to 4]
A colored aluminum plate was prepared in the same manner as in Example 1 except that the dye (1-2), (1-3), or (1-4) was used instead of the dye (1-1). And the hue was evaluated. The results are summarized in Table 1.

[Reference Example 1 to Reference Example 4]
Instead of the dye (1-1), the following dye represented by the following formula, which does not belong to the present invention (the maximum absorption wavelength (λmax) (nm) of the aqueous solution is also shown):
(D-1) C.I. I. Acid Red 289 (λmax: 526nm),
(D-2) C.I. I. Acid Violet 102 (λmax: 533 nm),
(D-3) C.I. I. Acid Violet 9 (λmax: 529 nm),
(D-4) C.I. I. Acid Red 92 (λmax: 538nm)
Table 1 summarizes the results of producing colored aluminum under the same production conditions as in Example 1 and evaluating the hue.

[Example 5]
<Evaluation of light resistance>
The colored aluminum plate colored with the dye (1-3) was subjected to a light resistance test by the following method. Using a xenon fade meter / ATLAS Ci3000 + Xenon Weather Ometer (manufactured by Atlas), irradiance: 300-400 nm, 60 W / m ² , test tank temperature: 38 ° C, humidity: 50%, black panel (BP) temperature: 63 When a colored aluminum plate was irradiated for 50 hours, 100 hours, and 200 hours under the condition of ° C., the hue and the color difference ΔE ^* before and after light irradiation were measured with a color difference meter, and the dyeing fastness was determined by the gray scale grade. The light resistance was judged by visual judgment (JIS L 0804 "gray scale for discoloration and fading"). As for the series, the fifth series is the highest, the first grade is the lowest, and the higher the series, the darker the color (the ^{smaller the color difference ΔE *} ) and the more the hue before irradiation is maintained. In the evaluation method of the present invention, the judgment result of the series is divided into three stages, evaluated according to the following judgment criteria, and the results are shown in Table 2.
Grayscale criteria: Correspondence between series and evaluation in the present invention Grades 5 to 4: A (especially good light resistance)
Grade 3: B (normal level of light resistance)
Level 2 or lower: C (low light resistance)

[Reference Examples 5 to 7]
Table 2 summarizes the results of evaluating the light resistance of the colored aluminum produced by using the dyes (D-2) to (D-4) instead of the dyes (1-3) in the same manner as in Example 4. Shown.

From the results in Tables 1 and 2, by using an anodized aluminum colorant composed of a dye composition containing the dye of the present invention, a purple-based light resistance comparable to that of conventional products can be obtained on aluminum. It was possible to form a film to have.

(Heat resistance test)
[Examples 6 to 8]
For the dyes (1-1), (1-2) and (1-4), in Example 1 above, the anodized film thickness and dyeing time were set to light color (7 μm for 30 seconds), neutral color (11 μm for 2 minutes), and so on. A heat resistance test was carried out by the following method on an aluminum plate colored in the same manner as in Example 1 except that it was dyed under three conditions of dark color (15 μm for 5 minutes). The sample was heated under the following exposure conditions using a constant temperature dryer (manufactured by AS ONE Corporation, model: 87L EOP-450V).
Dryer temperature and heating time: 200 ° C-5 hours or 250 ° C-3 hours The heat resistance evaluation method of the present invention measures the color difference of a colored aluminum sample before and after heating with the following color difference meter and visually. , Evaluated according to the following criteria. The results are shown in Table 2.
Equipment: Color difference meter (Spectroscopic color difference meter manufactured by Konica Minolta Co., Ltd., Model: CM-3700A)
Color difference calculation formula: ΔE ^* _ab (L ^* a ^* b ^* , CIE 1976)
And ΔE ^* ₀₀ (CIE DE2000)
Viewing angle: 10 °
Heat resistance criterion: The ^{smaller the color difference E *} _{ab, the} better the heat resistance.
A: Good heat resistance ΔE ^* ≤ 2.0
B: Normal level heat resistance 2.0 <ΔE ^* ≦ 5.0
C: Low heat resistance ΔE ^* > 5.0

[Reference Example 8 to Reference Example 11]
Table 3 summarizes the results of evaluating the heat resistance of the samples colored in the same manner for the compounds (D-1) to (D-4) of Reference Examples 1 to 2 in the same manner as in Examples 6 to 9. Shown.

From the results in Table 3, by using an anodized aluminum colorant composed of a dye composition containing the compound of the present invention, purple, bluish purple, bluish purple, and bluish films were formed on aluminum, and heat resistance was obtained. It was possible to form a highly acidic film. It has heat resistance comparable to that of conventional purple to blue xanthene dyes of the same color.

According to the dye composition containing a xanthene-based dye according to the present invention, it can be used for various materials as a colorant having excellent light resistance and heat resistance and not containing heavy metals such as chromium. In particular, it is possible to obtain a colorant for anodized aluminum that forms a single-colored purple-based colored film. Further, by using the colorant, it is possible to obtain an anodized aluminum film having excellent light resistance and heat resistance, which is colored in a single color and purple.

Claims (8)

A xanthene dye represented by the following general formula (1).

[In equation (1), R ¹ and R ² are independent of each other.
A naphthyl group having 6 to 30 carbon atoms which may have a substituent, or
Represents a phenyl group having 6 to 30 carbon atoms which may have a substituent.
However, at least one of ^{R 1} and R ^{2 is}
It is a naphthyl group having 6 to 30 carbon atoms which may have a substituent. ] The xanthene-based dye according to claim 1, wherein in the general formula (1), R ¹ or R ² is any one of the monovalent groups represented by the following general formulas (2) to (4).

[In formulas (2) to (4), R ^{3 to} R ²¹ are independently of -H, -OH, -COOM, -NO ₂ , -NO, -CN, -SO ₃ M, -SH, respectively.
An amino group having 0 to 20 carbon atoms, which may have a substituent,
A sulfonyl 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,
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 cycloalkoxy group having 3 to 20 carbon atoms, which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
It represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent.
M represents a hydrogen atom or an alkali metal atom. ] In the general formula (2) or ^(3), R 3 ^{to R 16} are each independently, -H, a -SO ₃ H or _-SO 3 Na, xanthene dyes described in claim 2. In the general formula (4), R ^{17 to} R ²¹ may independently have —H, a linear or branched alkyl group having 1 to 10 carbon atoms, or a substituent. The xanthene dye according to claim 2 or 3, which is an amino group having 0 to 10 atoms. A dye composition containing the xanthene-based dye according to any one of claims 1 to 4. A colorant for anodized aluminum containing the dye composition according to claim 5. Aluminum anodic oxide, aluminum anodic oxide, or anodic oxidation, which comprises using a dye composition containing 0.02 to 10% by mass of the xanthene-based dye according to any one of claims 1 to 4. How to color aluminum alloy. A method for producing xanthene dyes,
A manufacturing method characterized in that only step 1 is performed, or step 2 is performed after step 1.
Step 1: With the compound represented by the following formula (5),
Reacting the compound represented by the following general formula (2a) or (3a).
Step 2: The intermediate obtained in Step 1 and
Reacting the compounds represented by the following general formulas (2a), (3a) or (4a).

[In the formulas (2a), (3a) or (4a), R ^{3 to} R ²¹ have the same meaning as the definitions of the general formulas (2) to (4). ]