Xanthene-based pigment, dye composition, coloring agent and coloring method for anodic aluminum oxide, and method for producing said pigment

Abstract

(Problem) To provide a novel xanthenic pigment capable of forming an anodic oxide film on the surface of aluminum, aluminum oxide, or aluminum alloy that does not contain heavy metals such as chromium and also exhibits a single purple color. (Solution) A xanthenic pigment represented by the following general formula (1). [In Formula (1), R1 and R2 each independently represent a naphthyl group having 6 to 30 carbon atoms that may have substituents, or a phenyl group having 6 to 30 carbon atoms that may have substituents. Provided, at least one of R1 and R2 is a naphthyl group having 6 to 30 carbon atoms that may have substituents.]

Description

Technology Field

[0001] The present invention relates to a xanthenic pigment and dye composition suitable for use as a coloring agent for anodic aluminum oxide. Furthermore, the invention relates to a method for coloring anodic aluminum oxide using the pigment and dye composition, and a method for manufacturing the pigment. Background Technology

[0002] Conventionally, as a method for coloring the surface of aluminum (including its oxide or alloy), a method is used in which aluminum is used as an anode and an electric current is applied (anodic oxidation) in an electrolyte containing water and a suitable acid, and a porous aluminum oxide film (alumite film) is formed on the surface, and then an organic pigment (or organic dye) is used as a coloring agent to color the surface (Patent Documents 1 to 5).

[0003] In order to meet the recent demand for a wide variety of colored aluminum products, a coloring method capable of handling various colored dyes (Patent Document 4) is being developed. For example, purple xanthenic pigments are known as coloring agents for anodic aluminum (Patent Documents 4, 5, etc.), but their color and lightfastness are insufficient, and there is a demand for a single pigment that has good lightfastness without requiring mixing.

[0004] In addition, chromium-containing dyes for anodizing films (Patent Documents 1 to 3, etc.) have been widely used because they have excellent lightfastness and heat resistance, but recently, there is a demand for dyes with various colors that do not contain heavy metals such as chromium for environmental reasons. Prior art literature

[0005] Japanese Published Patent Application No. Hei 9-302256, Japanese Published Patent Application No. Sho 60-235867, Japanese Published Patent Application No. 2002-522617, Japanese Published Patent Application No. Sho 63-312998, Japanese Published Patent Application No. 2013-506053 The problem to be solved

[0006] Pigments that do not contain chromium and have a desired color are limited, and the development of pigments with novel structures that have a desired color is useful.

[0007] The problem to be solved by the present invention is to provide a novel xanthenic pigment capable of forming an anodic oxide film on the surface of aluminum, aluminum oxide, or aluminum alloy that does not contain heavy metals such as chromium and exhibits a single purple color, a dye composition containing said pigment, a coloring agent for anodic aluminum composed of said dye composition, a coloring method, and a method for manufacturing said pigment. means of solving the problem

[0008] In order to solve the above problem, the inventors carefully examined pigments (dyes) for aluminum anodic oxidation and discovered that by using a xanthenic pigment having a specific structure as a coloring agent for anodic aluminum, it is possible to form an anodic oxidation film on anodic aluminum that exhibits a single color in the purple color family. That is, the present invention is composed of the following contents.

[0009] 1. A xanthenic pigment represented by the following general formula (1).

[0010] [Chemical Formula 1]

[0011]

[0012] [In Equation (1), R 1 and R 2 Each independently,

[0013] Naphthyl groups having 6 to 30 carbon atoms that may have substituents,

[0014] Alternatively, it represents a phenyl group having 6 to 30 carbon atoms that may have substituents.

[0015] However, R 1 and R 2 At least one of them is,

[0016] It is a naphthyl group having 6 to 30 carbon atoms that may have substituents.

[0017] 2. In the above general formula (1), R 1 or R 2 A xanthenic pigment of any one type represented by the following general formulas (2) to (4).

[0018] [Chemical Formula 2]

[0019]

[0020] [Chemical Formula 3]

[0021]

[0022] [Chemical Formula 4]

[0023]

[0024] [Among equations (2) to (4), R 3 ~ R 21 -H, -OH, -COOM, -NO2, -NO, -CN, -SO3M, -SH, each independently

[0025] Amino groups having 0 to 20 carbon atoms that may have substituents,

[0026] A sulfonyl group having 0 to 20 carbon atoms that may have substituents,

[0027] A straight-chain or branched alkyl group having 1 to 20 carbon atoms that may have substituents,

[0028] A cycloalkyl group having 3 to 20 carbon atoms that may have substituents,

[0029] A straight-chain or branched alkoxy group having 1 to 20 carbon atoms that may have substituents,

[0030] A cycloalkoxy group having 3 to 20 carbon atoms that may have substituents,

[0031] A straight-chain or branched alkenyl group having 2 to 20 carbon atoms that may have substituents,

[0032] An acyl group having 1 to 20 carbon atoms that may have substituents,

[0033] An aromatic hydrocarbon group having 6 to 20 carbon atoms that may have substituents, or

[0034] It represents a complex ring with 2 to 20 carbon atoms that may have substituents.

[0035] M represents a hydrogen atom or an alkali metal atom.

[0036] 3. In the above general formula (2) or (3), R 3 ~ R 16 These are xanthenic pigments that are, independently, -H, -SO3H, or -SO3Na.

[0037] 4. In the above general formula (4), R 17 ~ R 21 A xanthenic pigment having, respectively, -H, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or an amino group having 0 to 10 carbon atoms that may have a substituent.

[0038] 5. A dye composition containing the above xanthenic pigment.

[0039] 6. A coloring agent for anodic aluminum containing the above dye composition.

[0040] 7. A method for coloring anodized aluminum, anodized aluminum oxide, or anodized aluminum alloy, characterized by using a dye composition containing 0.02 to 10 mass% of the above xanthenic pigment.

[0041] 8. A method for manufacturing xanthenic pigments,

[0042] A manufacturing method characterized by performing only Process 1, or performing Process 2 after Process 1.

[0043] Process 1: A compound represented by the following formula (5), and

[0044] Reacting a compound represented by the following general formula (2a) or (3a).

[0045] Process 2: The intermediate obtained in Process 1 above, and,

[0046] Reacting a compound represented by the following general formulas (2a), (3a), or (4a).

[0047] [Chemical Formula 5]

[0048]

[0049] [Chemical Formula 6]

[0050]

[0051] [Chemical Formula 7]

[0052]

[0053] [Chemical Formula 8]

[0054]

[0055] [Equation (2a), (3a) or (4a), R 3 ~ R 21 [It has the same significance as the definitions of the above general formulas (2) to (4).] Effects of the invention

[0056] The present invention provides a novel xanthenic pigment capable of forming an anodic oxide film on the surface of aluminum, aluminum oxide, or aluminum alloy that does not contain heavy metals such as chromium and exhibits a single purple color, a dye composition containing the pigment, a coloring agent for anodic aluminum comprising the dye composition, a coloring method, and a method for manufacturing the pigment. Specific details for implementing the invention

[0057] The embodiments of the present invention will be described in detail below. Furthermore, the present invention is not limited to the embodiments described below and can be implemented with various modifications within the scope of its gist. The xanthenic pigment represented by the above general formula (1) will be described in detail below, but the present invention is not limited to these.

[0058] The xanthenic pigment related to the present invention is represented by the following general formula (1). In general formula (1), R 1 and R 2 Each represents independently a “naphthyl group having 6 to 30 carbon atoms that may have substituents” or a “phenyl group having 6 to 30 carbon atoms that may have substituents”. provided that R 1 and R 2 At least one of them is a “naphthyl group having 6 to 30 carbon atoms that may have substituents”. Specifically, R 1 In the case of this “phenyl group having 6 to 30 carbon atoms that may have a substituent,” R 2 is a “naphthyl group having 6 to 30 carbon atoms that may have substituents”. Also, R 2 If is a “phenyl group having 6 to 30 carbon atoms that may have a substituent,” then R 1 is a “naphthyl group having 6 to 30 carbon atoms that may have substituents”. Also, R 1 and R 2 Both sides may be “naphthyl groups having 6 to 30 carbon atoms that may have substituents”.

[0059] [Chemical Formula 9]

[0060]

[0061] In general formula (1), the “number of carbon atoms” in the “naphthyl group having 6 to 30 carbon atoms that may have substituents” may be, for example, 10 to 30, 10 to 25, 10 to 20, 10 to 18, 10 to 15, or 10 to 12, or 10. In general formula (1), the “number of carbon atoms” in the “phenyl group having 6 to 30 carbon atoms that may have substituents” may be, for example, 6 to 25, 6 to 20, or 6 to 18.

[0062] In general formula (1), the “substituent” in “a naphthyl group having 6 to 30 carbon atoms that may have a substituent” or “a phenyl group having 6 to 30 carbon atoms that may have a substituent” is specifically,

[0063] Hydroxyl group (-OH), -COOM (M is an alkali metal atom such as lithium (Li), sodium (Na), potassium (K), etc.), carboxyl group (-COOH), nitro group (-NO2), nitroso group (-NO), cyano group (-CN), -SO3M (M is an alkali metal atom such as lithium (Li), sodium (Na), potassium (K), etc.), sulfonic acid group (-SO3H), thiol group (-SH),

[0064] Unsubstituted amino group; a monosubstituted amino group with 0 to 20 carbon atoms bonded via an interposition of -NH-;

[0065] A disubstituted amino group with 0 to 20 carbon atoms bonded via -N<;

[0066] A group having a sulfonyl group (-S(=O)2-) such as a sulfonamide (-S(=O)2-NH2) group, mesyl group, or tosyl group;

[0067] Straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, n-hexyl, isohexyl, heptyl, n-octyl, t-octyl, isooctyl, nonyl, and decyl groups;

[0068] Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, etc.;

[0069] Straight or branched alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, t-butoxy groups, n-pentyloxy groups, n-hexyloxy groups;

[0070] Cycloalkoxy groups such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy;

[0071] A linear or branched alkenyl group formed by the multiple bonding of vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, or their alkenyl groups;

[0072] Acyl groups such as formyl, acetyl, propionyl, acryl, and benzoyl groups;

[0073] Aromatic hydrocarbon groups such as phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, triphenylenyl, indenyl, and fluorenyl groups;

[0074] Pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, pyrazinyl group, pyridazinyl group, piperidinyl group, piperazinyl group, quinolyl group, isoquinolyl group, naphthiridinyl group, indolyl group, benzimidazolyl group, carbazonyl group, carbolinyl group, acrridinyl group, phenanthrolinyl group, phenantridinyl group, hydantoin group, furanyl group, benzofuranyl group, dibenzofuranyl group, pyranyl group, coumarinyl group, isobenzofuranyl group, xanthenyl group, oxantrenyl group, pyranonyl group, thienyl group, thiopyranyl group, benzothienyl group, dibenzothienyl group, thioxanthenyl group, oxazolyl group, Complex ring groups such as benzoxazolyl groups, morpholinyl groups, thiazolyl groups, benzothiazolyl groups, etc.;

[0075] 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 used.

[0076] These “substituents” may include only one or multiple substituents, and if multiple substituents are included, they may be identical or different from each other. Also, these “substituents” may have the substituents exemplified above. Additionally, if a “substituent” includes a carbon atom, that carbon atom is included in the “number of carbon atoms 6 to 30” above.

[0077] In a xanthenic pigment represented by general formula (1), R 1 or R 2 It is preferable that the univalent group is any one of the following general formulas (2) to (4). The univalent group represented by general formula (2) is R 3 ~ R 9 It is a naphthyl group having a group represented by , and the 1-valent group represented by general formula (3) is R 10 ~ R 16 It is a naphthyl group having a group represented by , and the 1-valent group represented by general formula (4) is R 17 ~ R21 It is a phenyl group having a group represented by , and each dashed line represents a connecting part.

[0078] [Chemical Formula 10]

[0079]

[0080] [Chemical Formula 11]

[0081]

[0082] [Chemical Formula 12]

[0083]

[0084] In general formulas (2) to (4), R 3 ~ R 21 Each independently, -H, -OH, -COO - , -COOM, -NO2, -NO, -CN, -SO3M, -SH,

[0085] Amino groups having 0 to 20 carbon atoms that may have substituents,

[0086] A sulfonyl group having 0 to 20 carbon atoms that may have substituents,

[0087] A straight-chain or branched alkyl group having 1 to 20 carbon atoms that may have substituents,

[0088] A cycloalkyl group having 3 to 20 carbon atoms that may have substituents,

[0089] A straight-chain or branched alkoxy group having 1 to 20 carbon atoms that may have substituents,

[0090] A cycloalkoxy group having 3 to 20 carbon atoms that may have substituents,

[0091] A straight-chain or branched alkenyl group having 2 to 20 carbon atoms that may have substituents,

[0092] An acyl group having 1 to 20 carbon atoms that may have substituents,

[0093] An aromatic hydrocarbon group having 6 to 20 carbon atoms that may have substituents, or

[0094] It is preferable that it be a complex ring having 2 to 20 carbon atoms that may have substituents.

[0095] Here, M represents a hydrogen atom (H); an alkali metal atom such as a lithium atom (Li), a sodium atom (Na), or a potassium atom (K), and M is preferably a hydrogen atom or a sodium atom. In addition, R 3 ~ R 21 In the case of including this carbon atom, that carbon atom is included in the “6 to 30 carbon atoms” in the “6 to 30 carbon atoms that may have substituents” or “6 to 30 carbon atoms that may have substituents” in the general formula (1).

[0096] In general formulas (2) to (4), R 3 ~ R 21 Examples of “amino groups having 0 to 20 carbon atoms that may have substituents” represented by include unsubstituted amino groups (-NH2), monosubstituted amino groups, disubstituted amino groups, etc. The number of carbon atoms in a monosubstituted amino group or a disubstituted amino group is, for example, 1 to 20, but may be 1 to 10 or 2 to 6. The amino group having 0 to 20 carbon atoms that may have substituents may be a group to which an aromatic hydrocarbon group having 6 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or a complex ring group having 2 to 20 carbon atoms, as described below, is bonded via -NH- or -N<. Examples of monosubstituted amino groups include ethylamino groups, acetylamino groups, phenylamino groups, etc. Examples of substituted amino groups include dialkylamino groups having 2 to 20 carbon atoms, such as dimethylamino groups, diethylamino groups, and dibutylamino groups; diphenylamino groups, acetylphenylamino groups, etc.

[0097] In general formulas (2) to (4), R 3 ~ R 21 The “sulfonyl group that may have substituents having 0 to 20 carbon atoms” represented by is -SO2-R 100 (or -S(=O)2-R 100 Substituent R represented by ) 100 It means representing a sulfonyl group having R 100 It may be a pattern containing carbon atoms, or a pattern not containing carbon atoms. R 100 In the case of a carbon-containing group, R 100 The number of carbon atoms is 1 to 20, and may be 1 to 10 or 1 to 7. Examples of sulfonyl groups that may have a substituent with 0 to 20 carbon atoms include sulfonamide groups (-S(=O)2-NH2), mesyl groups, tosyl groups, etc.

[0098] In general formulas (2) to (4), R 3 ~ R 21 In the “straight-chain or branched alkyl group having 1 to 20 carbon atoms that may have a substituent” represented by, specifically, straight-chain alkyl groups such as methyl, ethyl, n-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and branched alkyl groups such as isopropyl, isobutyl, s-butyl, t-butyl, isooctyl, and t-octyl groups.

[0099] In general formulas (2) to (4), R 3 ~ R 21Specifically, among the “cycloalkyl groups having 3 to 20 carbon atoms that may have substituents” represented by, the “cycloalkyl groups having 3 to 20 carbon atoms” can be cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cyclodecyl groups, cyclododecyl groups, etc.

[0100] In general formulas (2) to (4), R 3 ~ R 21 In the “straight-chain or branched alkoxy group having 1 to 20 carbon atoms that may have a substituent” represented by, specifically, straight-chain alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy; and branched alkoxy groups such as isopropoxy, isobutoxy, s-butoxy, t-butoxy, isooctyloxy, and t-octyloxy.

[0101] In general formulas (2) to (4), R 3 ~ R 21 Specifically, among the “cycloalkoxy groups having 3 to 20 carbon atoms that may have substituents” represented by, the “cycloalkoxy groups having 3 to 20 carbon atoms” can be cyclopropoxy groups, cyclobutoxy groups, cyclopentyloxy groups, cyclohexyloxy groups, etc.

[0102] In general formulas (2) to (4), R 3 ~ R 21 In the “straight-chain or branched alkenyl group having 2 to 20 carbon atoms that may have a substituent” represented by, specifically, the “straight-chain or branched alkenyl group having 2 to 20 carbon atoms” may include vinyl groups, allyl groups, isopropenyl groups, 2-butenyl groups, 1-hexenyl groups, or straight-chain or branched groups in which multiple alkenyl groups of these are bonded.

[0103] In general formulas (2) to (4), R 3 ~ R 21 The “acyl group having 1 to 20 carbon atoms that may have substituents” represented by -(C=O)-R 101 It is a group represented by . Substituent R 101 It may be a group containing a carbon atom or a group not containing a carbon atom. Substituent R 101 In the case of a group containing this carbon atom, substituent R 101 The number of carbon atoms can be, for example, 1 to 20 or 1 to 10. Substituent R 101 Examples include -H, -CH3, -CH2CH2CH3, -CH=CH2, -C6H5 (phenyl group), etc. Specifically, examples of the “acyl group having 1 to 20 carbon atoms that may have a substituent” include the formyl group, acetyl group, propionyl group, acryl group, benzoyl group, etc.

[0104] In general formulas (2) to (4), R 3 ~ R 21 In the “aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent” represented by, the “aromatic hydrocarbon group having 6 to 30 carbon atoms” specifically includes phenyl groups, benzoyl groups, naphthyl groups, biphenyl groups, anthryl groups, phenanthryl groups, pyrenyl groups, triphenylenyl groups, indenyl groups, fluorenyl groups, etc., and may also include acyl groups or amino groups. Here, the term “aromatic hydrocarbon group” in the present invention refers to an aromatic hydrocarbon group and a condensed polycyclic aromatic group, and among these, a phenyl group or a naphthyl group is preferred.

[0105] In general formulas (2) to (4), R 3 ~ R 21Specifically, the “complex ring group having 2 to 20 carbon atoms that may have substituents” represented by , the “complex ring group having 2 to 20 carbon atoms” can be pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthiridinyl group, indolyl group, benzimidazolyl group, carbazonyl group, carboninyl group, acrridinyl group, phenanthrolinyl group, hydantoin group, furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, etc.

[0106] In general formulas (2) to (4), R 3 ~ R 21 Represented by,

[0107] "An amino group having 0 to 20 carbon atoms with a substituent",

[0108] "A sulfonyl group having 0 to 20 carbon atoms with a substituent",

[0109] "A straight-chain or branched alkyl group having 1 to 20 carbon atoms with a substituent",

[0110] "A cycloalkyl group having 3 to 20 carbon atoms with a substituent",

[0111] "A straight-chain or branched alkoxy group having 1 to 20 carbon atoms with substituents",

[0112] "A cycloalkoxy group having 3 to 20 carbon atoms with a substituent",

[0113] "A straight-chain or branched alkenyl group having 2 to 20 carbon atoms with substituents",

[0114] "Acyl groups having 1 to 20 carbon atoms with substituents",

[0115] "An aromatic hydrocarbon group having 6 to 20 carbon atoms with substituents" or

[0116] As for the “substituents” in the “complex ring having 2 to 20 carbon atoms with substituents,”

[0117] Examples of "substituents" in the above-mentioned general formula (1) are identical to those exemplified as "naphthyl groups having 6 to 30 carbon atoms that may have substituents" or "phenyl groups having 6 to 30 carbon atoms that may have substituents." These "substituents" may include only one or multiple substituents, and if multiple substituents are included, they may be identical or different from each other. Also, these "substituents" may have the substituents exemplified above. Furthermore, if a "substituent" includes a carbon atom, that carbon atom is included in the above "0 to 20 carbon atoms," "1 to 20 carbon atoms," "2 to 20 carbon atoms," "3 to 20 carbon atoms," and "6 to 20 carbon atoms." In addition, these substituents may form a ring by being bonded to each other through single bonds, substituted or unsubstituted methylene groups, oxygen atoms, or sulfur atoms.

[0118] In general formula (2) or (3), R 3 ~ R 16 It is preferable that each be independently -H, -SO3H, or -SO3Na.

[0119] R 3 ~ R 9 At least one of them may be -SO3M, and R 5 It is acceptable to be -SO3M. R 10 ~ R 16 At least one of them may be -SO3M, and R 12 or R 13 It is okay to use -SO3M.

[0120] In general formula (4), R 17 ~ R 21It is preferable that each of the following be independently -H, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or an amino group having 0 to 10 carbon atoms that may have a substituent.

[0121] The compound of the xanthenic pigment of the present invention represented by general formula (1) (hereinafter also simply referred to as pigment (1)) comprises all stereoisomers and tautomers that can be produced. Specific examples of pigment (1) are shown in the following formula, but the present invention is not limited to these. In addition, hydrogen atoms are partially omitted in the structural formula.

[0122] [Chemical Formula 13]

[0123]

[0124] [Chemical Formula 14]

[0125]

[0126] [Chemical Formula 15]

[0127]

[0128] [Chemical Formula 16]

[0129]

[0130] [Chemical Formula 17]

[0131]

[0132] [Chemical Formula 18]

[0133]

[0134] [Chemical Formula 19]

[0135]

[0136] [Chemical Formula 20]

[0137]

[0138] [Chemical Formula 21]

[0139]

[0140] [Chemical Formula 22]

[0141]

[0142] [Chemical Formula 23]

[0143]

[0144] [Chemical Formula 24]

[0145]

[0146] [Chemical Formula 25]

[0147]

[0148] [Chemical Formula 26]

[0149]

[0150] [Chemical Formula 27]

[0151]

[0152] An example of a method for manufacturing the xanthenic pigment (pigment (1)) of the present invention represented by general formula (1) is shown below, but is not limited to this method. Specifically, the manufacturing method of the present invention is,

[0153] A method for manufacturing pigment (1) by performing only the following “Process 1”, or,

[0154] This is a method for manufacturing a pigment (1) by carrying out the following “Process 2” after the above “Process 1”.

[0155] Process 1: A compound represented by the following formula (5), and

[0156] Reacting a compound represented by the following general formula (2a) or (3a).

[0157] Process 2: The intermediate obtained in Process 1 above, and,

[0158] Reacting a compound represented by the following general formulas (2a), (3a), or (4a).

[0159] [Chemical Formula 28]

[0160]

[0161] [Chemical Formula 29]

[0162]

[0163] [Chemical Formula 30]

[0164]

[0165] [Chemical Formula 31]

[0166]

[0167] [Equation (2a), (3a) or (4a), R 3 ~ R 21 [It has the same significance as the definitions of the above general formulas (2) to (4).]

[0168] "Process 1" is described below. The starting material is the above formula (5) (3,6-dichloro-9-(2-sulfonatophenyl)xantylium), and an equivalent group (R) represented by the above general formula (2a) or (3a). 3 ~ R 16 By reacting a naphthylamine derivative having ) in any solvent that dissolves these raw materials under conditions such as an appropriate temperature and reaction time, a desired xanthenic pigment or an intermediate thereof can be obtained.

[0169] In addition, the above solvents are not particularly limited, but specifically include esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether, propylene glycol monomethyl ether (PGME), and ethylene glycol monoethyl ether (ethyl cellosolve); 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), etc.; aromatic hydrocarbons such as benzene, toluene, and xylene; amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); and dimethyl sulfoxide (DMSO), etc. These solvents may be used individually or in a mixture of two or more types. Among these, N-methylpyrrolidone is preferred.

[0170] "Process 2" is described below. After carrying out the above "Process 1," the obtained intermediate and an equivalent group (R) represented by the above general formulas (2a), (3a), or (4a) 3 ~ R 16 A naphthylamine derivative compound having ) or, an equivalent group (R 17 ~ R 21 A desired xanthenic pigment can be obtained by reacting an aniline derivative compound having ) in any solvent that dissolves these raw materials under conditions such as an appropriate temperature and reaction time. As the solvent, the same as that exemplified in Process 1 can be used, and among these, N-methylpyrrolidone is preferred.

[0171] In process 1 or process 2, which is a method for manufacturing the above pigment (1), the molar ratio of the starting raw material formula (5) and the general formula (2a), (3a), or (4a) is preferably such that the general formula (2a), (3a), or (4a) is 2 to 20 times molar equivalents for every 1 mol of formula (5).

[0172] The above pigment (1) can be purified by known methods such as purification by column chromatography; purification by adsorption using silica gel, activated carbon, activated clay, etc.; recrystallization by a solvent or various crystallization methods using acid, etc.

[0173] The identification or physical property evaluation of the pigment (1) of the present invention, the intermediate thereof, or various products obtained in process 1 or process 2 may be performed by ultraviolet-visible absorption spectrum analysis (UV-Vis), thermogravimetric-differential thermal analysis (TG-DTA), gas chromatography analysis (GC), thin-layer chromatography analysis (TLC), gas chromatography-mass spectrometry (GC / MS), nuclear magnetic resonance analysis (NMR), etc.

[0174] The xanthene-based pigment (pigment (1)) represented by the general formula (1) in the present invention can form an anodic oxide film on the surface of aluminum, aluminum oxide, or aluminum alloy that does not contain heavy metals such as chromium and exhibits a single color in the purple color family. In addition, the pigment (1) can have sufficient heat resistance and / or light resistance. Therefore, the pigment (1) can be used as a component of a dye composition. The pigment (1) can color aluminum, aluminum oxide, fibers, etc. by using only one type of pigment. In short, the pigment (1) can preferably be used as a pigment compound for coloring aluminum, aluminum oxide, fibers, etc. by using only one type of single-color dye. Two or more types of pigments (1) may be used in combination to obtain various colors by mixing. The dye composition may mix other components for optimal dyeing (coloring using dyes). Specifically, a liquid (solvent) such as water, alcohol, or a solvent; Additives such as surfactants may be used. Water is preferred as the solvent. The pigment (1) may be used as a component of the dye composition by combining it with other pigments. Other pigments are compounds, pigments, dyes, etc. other than the pigment (1), and specifically, examples include ruthenium complexes, coumarin-based pigments, cyanin-based pigments, merocyanin-based pigments, rhodacyanin-based pigments, phthalocyanin-based pigments, porphyrin-based pigments, other xanthen-based pigments, etc. When using a combination of the pigment (1) and other components, it is preferable to use 10 to 200 mass% of the other components relative to the pigment (1), and more preferable to use 20 to 100 mass%. Aluminum oxide is a composition in which aluminum is oxidized and mainly contains aluminum and oxygen, and the composition ratio may be arbitrary, and it contains aluminum oxide, and the crystal system may be single crystal, polycrystalline, amorphous, or a mixture thereof.

[0175] The dye composition of the present invention can be applied as a coloring agent for anodic aluminum oxide. The dye composition described above may also be used as a coloring agent for anodic aluminum oxide alloys. That is, as one embodiment of the present invention, the use (application) of a xanthenic pigment represented by general formula (1) or a dye composition containing said pigment is provided for coloring anodic aluminum oxide or an anodic aluminum oxide alloy. Furthermore, as one embodiment of the present invention, the use of a xanthenic pigment represented by general formula (1) or a dye composition containing said pigment is provided for manufacturing a coloring agent for anodic aluminum oxide or an anodic aluminum oxide alloy.

[0176] When using pigment (1) as a coloring agent for anodic aluminum oxide, etc., in the coloring (dyeing) method, the concentration of pigment (1) in the dye composition containing pigment (1) is preferably 0.02 to 10 mass% based on the total amount of the dye composition, and more preferably 0.05 to 3 mass%. The lower the concentration of pigment (1), the lighter the coloring can be achieved, and the higher the concentration, the more intermediate to darker the coloring can be achieved.

[0177] Here, anodic aluminum oxide refers to aluminum that has undergone a treatment to form a porous oxide layer on the surface of an aluminum that has been electrolytically treated in an electrolyte such as an acidic aqueous solution. A coloring agent for anodic aluminum oxide refers to one that can color (dye) the aluminum surface having these pores by adsorbing a pigment (1) into the pores. Typically, in order to improve the durability and light resistance of the colored aluminum surface, a sealing treatment is performed to block the pores after coloring.

[0178] Examples of aluminum in anodic aluminum oxide include aluminum, aluminum oxide, aluminum alloys with other metals, metals or metal compounds containing aluminum, etc.

[0179] Here, an anodized aluminum alloy refers to an alloy in which anodizing treatment is performed on the surface of an aluminum alloy. In an anodized aluminum alloy, the aluminum alloy refers to an alloy in which aluminum is the main component, and refers to an alloy with metals such as copper, manganese, silicon, magnesium, zinc, and nickel. The compositional ratio of aluminum to other metals is not particularly limited.

[0180] A method for coloring aluminum using a coloring agent for anodic aluminum may use a method known as an anodizing dyeing method. For example, methods described in Japanese Industrial Standard (JIS H 8601: 1999 “Anodic Oxidation Film of Aluminum and Aluminum Alloys”), Patent Document 1, etc. may be used. The method for coloring aluminum is not particularly limited, but an example is shown below.

[0181] First, the aluminum plate is degreased using an aqueous acid solution such as sulfuric acid, oxalic acid, chromic acid, or sulfonic acid, and then washed. Next, the degreased aluminum plate is used as the anode, and an aqueous acid solution is used as the electrolyte to perform electrolysis, thereby forming an anodic oxide film (anodized film) that forms many pores on the surface of the aluminum anode (anodic oxidation treatment), and then washed. Subsequently, after appropriately performing surface conditioning and washing, the aluminum plate is immersed in an aqueous solution of a coloring agent for anodic aluminum containing a dye composition containing the compound of the present invention, and the dye is adsorbed into the pores (dyeing, electrolytic coloring), and the pores on the surface are sealed with aluminum oxide hydrate, etc., to form a sealing material, thereby allowing the aluminum plate to be colored.

[0182] When using two or more dye compositions of the present invention in combination, or when using the dye composition of the present invention in combination with other pigments, a mixed solution of all pigments used may be prepared and the anodic aluminum oxide may be immersed in it, or each pigment solution may be prepared separately and the anodic aluminum oxide may be immersed in each solution in sequence.

[0183] The electrolytic conditions for coloring according to the present invention may be direct current electrolysis or alternating current electrolysis, but direct current electrolysis is preferred. The current density is preferably 0.1 to 10 A / dm², and more preferably 0.5 to 3 A / dm². The current application time is preferably 10 seconds to 60 minutes. The thickness of the anodic oxide film is preferably 2 to 20 μm. Since these anodic oxidation conditions result in a darker color as the current application time is longer and the anodic oxide film is thicker, by adjusting these conditions, it is possible to achieve a color range from light to medium to dark.

[0184] The treatment temperature for each of the above processes is preferably a suitable temperature, and the temperature during anodic oxidation is preferably 0 to 80 ℃. The temperature during dyeing is preferably 10 ℃ to 70 ℃. Other treatment temperatures are preferably 10 to 80 ℃.

[0185] The dye composition in this embodiment can be used in the same way for anodic oxides using metals other than aluminum. For example, as long as it is capable of adsorbing the dye into the anodic pores, such as magnesium, zinc, titanium, zirconium, etc., it can also be applied to non-metals such as conductive plastics.

[0186] The coloring agent for anodic aluminum of the present embodiment can be evaluated by measuring the characteristics of a sample colored on aluminum, such as color, lightfastness, and heat resistance. Color can be evaluated visually for color quality or uniformity, or concentration (K / Sd) and color quality (L) can be evaluated using a colorimeter. * , a * , b * ) and color difference (ΔE * It may be measured as ).

[0187] The colors that can be produced using the coloring agent for anodic aluminum oxide of the present embodiment may include purple, bluish-purple, reddish-purple, and other purple shades. These may also produce colors with different shades, such as light colors (e.g., light purple) or dark colors (e.g., dark purple). The coloring agent for anodic aluminum oxide of the present embodiment may also produce mixed colors (intermediate colors) by using the compound described above in combination with other pigments.

[0188] The lightfastness test of aluminum colored using the coloring agent for anodic aluminum of the present embodiment may be performed by using a testing device that mimics sunlight including ultraviolet light, irradiating the sample with light for a certain period of time, and measuring the change in color of the colored aluminum before and after the test. Specifically, using a colorimeter, etc., CIE L * a * b * Color difference ΔE before and after the light irradiation test obtained by measuring color taste with a colorimeter * ab (or ΔE * It may be evaluated by ). For the determination of lightfastness, the color of colored aluminum may be evaluated by visual inspection using a gray scale according to the method specified in the Japanese Industrial Standard (JIS L 0804 “Gray Scale for Discoloration and Fading”).

[0189] For the heat resistance test of aluminum colored using the coloring agent for anodic aluminum of the present embodiment, methods such as heating for a suitable period of time in a range of 30 minutes to 50 hours in a constant temperature oven or hot air dryer in a temperature range of 50 to 300°C, etc., can be used to evaluate the change in color before and after the test in the same way as the light resistance test.

[0190] Colored aluminum using the coloring agent for anodic aluminum of the present embodiment is used in various types of aluminum plate materials and products using aluminum cladding.

[0191] Examples

[0192] The present invention will be described in detail below by way of examples, but is not limited to the following examples. In addition, the maximum absorption wavelength (λmax) (nm) measured by ultraviolet-visible absorption spectrum analysis (UV-Vis) of an aqueous solution of a compound (pigment) in the examples is shown.

[0193] [Synthesis Example 1] Synthesis of Pigment (1-1)

[0194] 40 g of 3,6-dichloro-9-(2-sulfonatophenyl)xanthalium (or dichlorosulfofluorane, product name: DCSF, manufactured by Taiyo Fine Chemical Co., Ltd.), 73.2 g of 5-amino-2-naphthalenesulfonic acid, and 240 ml of N-methylpyrrolidone (NMP) were added to a reaction vessel and stirred at 140 °C for 20 hours. The reaction mixture was solvent removed at 120 °C under reduced pressure and concentrated. 300 ml of 30% hydrochloric acid was added to the residue and stirred at room temperature for 30 minutes. The precipitated solid was filtered and dried to obtain the desired pigment (1-1) as a dark purple powder (36.8 g) (λmax: 539 nm).

[0195] [Synthesis Example 2] Synthesis of Pigment (1-2)

[0196] 8.5 g of DCSF, 22.5 g of 6-amino-2-naphthalenesulfonic acid, and 40 ml of NMP were placed in a reaction vessel and stirred at 160 °C for 21 hours. After cooling the reaction mixture to below 30 °C, 50 ml of acetonitrile was added and stirred for 30 minutes, after which the precipitated solid was filtered. 60 ml of 17.5% hydrochloric acid was added and stirred at room temperature for 30 minutes, after which the precipitated crystals were filtered and dried to obtain the desired pigment (1-2) as a dark purple powder (18.1 g) (λmax: 567 nm).

[0197] [Synthesization Example 3] Synthesis of Pigment (1-3)

[0198] 8.0 g of DCSF, 9.7 g of 7-amino-2-naphthalenesulfonic acid, and 30 ml of NMP were added to a reaction vessel and stirred at 60°C for 3 hours. The reaction mixture was cooled to below 30°C, and the precipitated solid was filtered and dried to obtain 6.6 g of intermediate. Subsequently, 5.0 g of the intermediate, 6.8 g of 2-amino-5-(diethylamino)toluene, and 20 ml of NMP were added to another reaction vessel and stirred at 120°C for 4 hours. The reaction mixture was added to 200 ml of 5% hydrochloric acid and stirred at room temperature for 30 minutes. The precipitated solid was filtered and placed in 50 ml of water, and a 48% sodium hydroxide aqueous solution was added to neutralize it. The aqueous solution was dried under reduced pressure at 80°C for 24 hours or more to obtain the desired pigment (1-3) as a blackish-purple powder (5.5 g) (λmax: 552 nm).

[0199] [Synthesis Example 4] Synthesis of Pigment (1-4)

[0200] 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. The reaction mixture was added to 200 ml of water, and 100 ml of 35% hydrochloric acid was added to precipitate the pigment. The solid was removed by filtration, and after drying, the desired pigment (1-4) was obtained as a bluish-purple powder (14.3 g) (λmax: 563 nm).

[0201] [Example 1]

[0202] Manufacture of Colored Aluminum

[0203] Colored aluminum was prepared by performing anodizing treatment on an aluminum substrate in the following order. In addition, the treatment time and dye compound concentration were set during the anodizing and dyeing processes.

[0204] (Degreasing) A degreasing solution was prepared by mixing 150 ml of degreasing agent (manufactured by Okuno Pharmaceutical Industry Co., Ltd., Top ADD-100), 70 ml of 98% sulfuric acid, and 1000 ml of water in a container, and an aluminum substrate for dyeing cut to a suitable size was immersed in it, and degreasing treatment was performed at 60°C for 3 minutes, and then washed with water.

[0205] (Anodic oxidation) An electrolyte solution of 180 g / ℓ was prepared using 98% sulfuric acid, an aluminum substrate was connected to the electrode of an electrolytic device and immersed in the electrolyte bath, and anodic oxidation was performed under conditions of a temperature of 19 to 21°C and a current density of 1.0 A / dm² or less for a duration of operation, thereby obtaining an anodic oxidation film of the following thickness. After oxidation, the substrate was washed with water.

[0206] Anodization conditions: energized for 15 minutes. After anodizing: 5 µm

[0207] (Surface conditioning) A surface conditioning solution with a concentration of 50 ml / L was prepared using a surface conditioning agent (manufactured by Okuno Pharmaceutical Industry Co., Ltd., TAC Somal 121) and water, and an aluminum substrate was immersed at 45°C for 1 minute. After immersion, the aluminum substrate was washed with water.

[0208] (Dyeing) Using the pigment (1-1) obtained in Synthesis Example 1, an aqueous dyeing solution containing pigments at the following concentrations was prepared as the dye composition of the present invention, and the aluminum substrate was dyed at a temperature (dry bath temperature) of 55°C while immersing it for the following dyeing time. After dyeing, the aluminum substrate was washed with water.

[0209] Dyeing conditions: Pigment concentration 2.0 wt% Dyeing time: 30 seconds

[0210] (Sealing) A sealing solution of 40 ml / ℓ was prepared using a sealing agent (Okuno Pharmaceutical Industry Co., Ltd., Top Seal H-298) and water, and sealing treatment was performed at approximately 90°C for 15 minutes. After sealing treatment, it was dried with hot air.

[0211] Color Evaluation

[0212] The color of a colored aluminum plate colored using pigment (1-1) is measured by the naked eye and a colorimeter (device name: Konica Minolta spectrophotometer model: CM-3700A) using CIE L * a * b * It was evaluated using a color system. The results of the evaluated colors are shown in Table 1.

[0213] [Examples 2 to 4]

[0214] Colored aluminum plates were prepared in the same manner as in Example 1, except that pigments (1-2), (1-3), or (1-4) were used instead of pigment (1-1), and the color was evaluated. The results are summarized in Table 1.

[0215] [Reference Examples 1 to 4]

[0216] Instead of the pigment (1-1), the following pigments represented by the following formula, which are not part of the present invention (the maximum absorption wavelength (λmax) (nm) of the aqueous solution is also indicated):

[0217] (D-1) CI Acid Red 289 (λmax: 526 ㎚),

[0218] (D-2) CI Acid Violet 102 (λmax: 533 ㎚),

[0219] (D-3) CI Acid Violet 9 (λmax: 529 ㎚),

[0220] (D-4) CI Acid Red 92 (λmax: 538 ㎚)

[0221] Regarding this, colored aluminum was manufactured under the same manufacturing conditions as in Example 1, and the results of the color evaluation are summarized in Table 1.

[0222] [Chemical Formula 32]

[0223]

[0224] [Chemical Formula 33]

[0225]

[0226] [Chemical Formula 34]

[0227]

[0228] [Chemical Formula 35]

[0229]

[0230]

[0231] [Example 5]

[0232] <Evaluation of Lightfastness>

[0233] A lightfastness test was performed on a colored aluminum plate colored using a pigment (1-3) by the following method. Using a xenon fade meter / ATLAS Ci3000 + Xenon Weather Ometer (manufactured by Atlas), the colored aluminum plate was irradiated for 50, 100, and 200 hours under conditions of radiant intensity: 300–400 nm, 60 W / m², temperature inside the test chamber: 38 ℃, humidity: 50 %, and black panel (BP) temperature: 63 ℃. The color and color difference ΔE before and after light irradiation were measured using a colorimeter. * Measurements were performed, and lightfastness was also determined by visual judgment of colorfastness based on grayscale grades (JIS L 0804 "Grayscale for Color Fading"). Grade 5 is the highest and Grade 1 is the lowest; the higher the grade, the darker the color (color difference ΔE * (Because it is small) it indicates that the color before the investigation is maintained. In the evaluation method of the present invention, the water grade judgment result is divided into three stages, evaluated according to the following judgment criteria, and the results are shown in Table 2.

[0234] Grayscale Judgment Criteria: Correspondence between the water supply and the evaluation in the present invention

[0235] Grade 5 ~ Grade 4: A (particularly good light resistance)

[0236] Grade 3: B (Normal level of light resistance)

[0237] Grade 2 or lower: C (Low light resistance)

[0238] [Reference Examples 5 to 7]

[0239] For colored aluminum prepared using the above pigments (D-2) to (D-4) instead of the pigment (1-3), the results of evaluating light resistance in the same way as in Example 4 are summarized in Table 2.

[0240]

[0241] From the results of Tables 1 and 2, by using an anodic aluminum oxide coloring agent composed of a dye composition containing the pigment of the present invention, it was possible to form a purple film on aluminum that has light resistance comparable to that of conventional products.

[0242] (Heat resistance test)

[0243] [Examples 6–8]

[0244] For the pigments (1-1), (1-2), and (1-4), a heat resistance test was performed on an aluminum plate colored in the same manner as in Example 1, except that the anodic oxidation film thickness and dyeing time were dyed under three conditions: light color (7 μm for 30 seconds), medium color (11 μm for 2 minutes), and 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 Co., Ltd., model: 87L EOP-450V).

[0245] Dryer internal temperature and heating time: 200℃ - 5 hours, or 250℃ - 3 hours

[0246] The heat resistance evaluation method of the present invention involved measuring the color difference of colored aluminum samples before and after heating using the colorimeter below, and also evaluating it visually according to the following judgment criteria. The results are shown in Table 2.

[0247] Device: Colorimeter (Spectrophotometer manufactured by Konica Minolta Corporation, Model: CM-3700A)

[0248] Color difference calculation formula: ΔE * ab (L * a * b * , CIE 1976)

[0249] and ΔE * 00 (CIE DE2000)

[0250] Field of view: 10°

[0251] Heat resistance judgment criteria: Color difference E * ab The smaller the value, the better the heat resistance.

[0252] A : Good heat resistance ΔE * ≤ 2.0

[0253] B: Normal level heat resistance 2.0 <ΔE * ≤ 5.0

[0254] C : Low heat resistance ΔE * > 5.0

[0255]

[0256] [Reference Examples 8 to 11]

[0257] Table 3 summarizes the results of evaluating the heat resistance of samples colored in the same way as in Examples 6 to 9 for compounds (D-1) to (D-4) of Reference Examples 1 to 2.

[0258] From the results of Table 3, by using an anodic aluminum coloring agent composed of a dye composition containing the compound of the present invention, it was possible to form a purple, bluish-purple, or blue-colored film on aluminum, thereby forming a film with high heat resistance. It has heat resistance comparable to that of conventional copper-based purple to blue xanthen pigments. Industrial applicability

[0259] According to the dye composition containing a xanthenic pigment related to the present invention, it can be used in various materials as a coloring agent that does not contain heavy metals such as chromium and has excellent light resistance and heat resistance. In particular, a coloring agent for anodic aluminum oxide that forms a single purple-colored colored film can be obtained. Furthermore, by using the coloring agent, an anodic aluminum oxide film that is single-colored in a purple color and has excellent light resistance and heat resistance can be obtained.

Claims

Claim 1 A coloring agent for anodic aluminum oxide containing a dye composition containing a xanthenic pigment represented by the following general formula (1). [In Equation (1), R 1 and R 2 Each is independently one of a type represented by the following general formulas (2) to (4), provided that R 1 and R 2 At least one of them is a group represented by general formula (2) or (3).] [Among equations (2) to (4), R 3 , R 4 and R 6 ~ R 21 Each independently -H, -OH, -COOM, -NO2, -NO, -CN, -SO3M, -SH, an amino group having 0 to 20 carbon atoms that may have substituents, a sulfonyl group having 0 to 20 carbon atoms that may have substituents, a straight-chain or branched alkyl group having 1 to 20 carbon atoms that may have substituents, a cycloalkyl group having 3 to 20 carbon atoms that may have substituents, a straight-chain or branched alkoxy group having 1 to 20 carbon atoms that may have substituents, a cycloalkoxy group having 3 to 20 carbon atoms that may have substituents, a straight-chain or branched alkenyl group having 2 to 20 carbon atoms that may have substituents, an acyl group having 1 to 20 carbon atoms that may have substituents, and a carbon having substituents Represents an aromatic hydrocarbon group having 6 to 20 atoms, or a complex ring group having 2 to 20 carbon atoms that may have substituents, and R 5 is -SO3M, where M represents a hydrogen atom or an alkali metal atom, provided that in Formula (3), R 12 or R 13 It is -SO3M. Claim 2 In claim 1, in the above general formula (2) or (3), R 3 , R 4 and R 6 ~ R 16 These, independently, are -H, -SO3H, or -SO3Na, and R 5 is -SO3H or -SO3Na, provided that R 12 or R 13 Colorant for anodized aluminum, which is -SO3H or -SO3Na. Claim 3 In claim 1 or 2, in the above general formula (4), R 17 ~ R 21 A coloring agent for anodic aluminum oxide, each independently having -H, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or an amino group having 0 to 10 carbon atoms that may have a substituent. Claim 4 A method for coloring anodized aluminum, anodized aluminum oxide, or anodized aluminum alloy, characterized by using a dye composition containing 0.02 to 10 mass% of a xanthenic pigment represented by the following general formula (1). [In Equation (1), R 1 and R 2 Each represents, independently, a naphthyl group having 6 to 30 carbon atoms that may have substituents, or a phenyl group having 6 to 30 carbon atoms that may have substituents, provided that R 1 and R 2 At least one of them is a naphthyl group having 6 to 30 carbon atoms that may have substituents. Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 delete

Images