WO2019189209A1 - Composé de sel complexe, composition de colorant, agent de coloration et procédé de coloration pour aluminium anodisé, et procédé de production dudit composé - Google Patents

Composé de sel complexe, composition de colorant, agent de coloration et procédé de coloration pour aluminium anodisé, et procédé de production dudit composé Download PDF

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WO2019189209A1
WO2019189209A1 PCT/JP2019/012916 JP2019012916W WO2019189209A1 WO 2019189209 A1 WO2019189209 A1 WO 2019189209A1 JP 2019012916 W JP2019012916 W JP 2019012916W WO 2019189209 A1 WO2019189209 A1 WO 2019189209A1
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Prior art keywords
group
carbon atoms
substituent
compound
aluminum
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English (en)
Japanese (ja)
Inventor
吉田　哲也
智耶 村上
力丸 永山
和彦 関根
勝美 阿部
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Hodogaya Chemical Co Ltd
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Hodogaya Chemical Co Ltd
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Priority to KR1020207026374A priority Critical patent/KR102793960B1/ko
Priority to JP2020510930A priority patent/JP7219754B2/ja
Priority to CN201980021997.XA priority patent/CN111971347B/zh
Publication of WO2019189209A1 publication Critical patent/WO2019189209A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C09B45/16—Monoazo compounds containing chromium

Definitions

  • the present invention relates to a complex salt compound, a dye composition containing the compound, a colorant for an anodized aluminum comprising the dye composition, a method for coloring an anodized aluminum using the dye composition, and a method for producing the compound. .
  • the aluminum surface is energized as an anode in an electrolytic solution containing water and a suitable acid, and the aluminum surface is made of a porous aluminum oxide layer (oxidized).
  • an electrolytic coloring method using an inorganic compound or a metal compound, an inorganic dye, an organic dye (azo dye, A dyeing method using a complex salt compound dye of a dye molecule and a metal atom, an acid dye, a direct dye or the like) as a colorant has been used (see Patent Documents 1 to 14).
  • anodized aluminum is changed to blue, green, yellow, red, etc. by using an electrolyte containing an organic or inorganic acid without using a general dye and changing the voltage condition of anodization.
  • Coloring methods Patent Documents 11 to 13, etc. have been developed, but there are limitations on the types of colors.
  • the anodized aluminum colored film using dyes has not been provided with a clear and light-fast blue-green, green or yellow-green single-color dye that the market demands so far. It has been blended and used (for example, TAC Green GM (1), TAC Green SBM (2), both manufactured by Okuno Pharmaceutical Co., Ltd.).
  • TAC Green GM (1), TAC Green SBM (2), both manufactured by Okuno Pharmaceutical Co., Ltd. a colorant that develops a desired color using a monochromatic dye is required.
  • a colorant for anodized aluminum using an anthraquinone green azo dye (Patent Document 9) or a phthalocyanine green pigment (Patent Document 14) has been proposed.
  • the current situation is that the light resistance has not reached the performance required by the market.
  • One aspect of the present invention provides a complex salt compound having a novel structure capable of forming an anodic oxide film having excellent light resistance and a blue-green color on a surface of aluminum, an aluminum oxide, or an aluminum alloy.
  • a pigment (dye) for aluminum anodization In order to solve the above problems, the inventors have intensively studied a pigment (dye) for aluminum anodization, and as a result, a complex salt compound (azo dye) having a specific structure is used as a colorant for anodized aluminum. It has been found that a blue-green system color such as blue, blue-green, and green can be colored with a monochromatic dye on aluminum oxide, and a film excellent in light resistance can be formed. That is, the present invention relates to the following inventions.
  • R 1 to R 10 are each independently —H, —SO 3 — , —NO 2 , —NO, —CN, —OH, —COO ⁇ , —COOH, —SH, —F
  • R 5 is —NH 2 or NHCOR 5a , and R 5a is an alkyl group, R 6 is —NHCO—Ph, R 9 is —SO 3 — and / or A compound wherein R 2 or R 3 is —CH 3 .
  • R 1 to R 4 are each independently —H, —SO 3 — , —NO 2 , an optionally substituted amino group having 0 to 10 carbon atoms.
  • R 5 is —H or an optionally substituted amino group having 0 to 10 carbon atoms, and R 6 may be —H, —SO 3 — or a substituent.
  • the compound according to [1] or [2], which is an amino group having 0 to 10 carbon atoms, and any one or two of R 7 to R 10 is —SO 3 — .
  • [5] A colorant for anodized aluminum containing the dye composition according to [4].
  • Anodized aluminum, anodized aluminum oxide or anode comprising using a dye composition containing 0.02 to 10% by mass of the compound according to any one of [1] to [3] Coloring method of aluminum oxide alloy.
  • a compound represented by the general formula (I) is a diazotized product obtained by diazotizing a compound represented by the following formula (II), a compound represented by the following formula (III) and / or a salt thereof.
  • a complex salt compound having a novel structure capable of forming an anodic oxide film having excellent light resistance and a blue-green color on a surface of aluminum, an aluminum oxide or an aluminum alloy.
  • a colorant for anodized aluminum that is capable of forming a monochromatic colored film having excellent light resistance and exhibiting a blue-green system such as blue, blue-green, and green. Can be obtained. Further, by using the colorant, it is possible to obtain an anodized aluminum film excellent in light resistance, which is colored blue-green such as blue, blue-green, and green.
  • an anodized aluminum film excellent in heat resistance can be formed in addition to light resistance.
  • the compound according to the present embodiment is a compound represented by the following general formula (1) (hereinafter also referred to as “compound (1)”).
  • R 1 to R 10 are each independently —H, —SO 3 — , —NO 2 , —NO, —CN, —OH, —COO ⁇ , —COOH, —SH, —F, An optionally substituted amino group having from 0 to 20 carbon atoms, an optionally substituted sulfonyl group having from 0 to 20 carbon atoms, an optionally substituted carbon atom; A linear or branched alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, and an optionally substituted carbon atom having 1 to 20 carbon atoms A linear or branched alkoxy group, a cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent, a straight chain having 2 to 20 carbon atoms which may have a substituent or Branched alkenyl group, optionally substituted acyl group having 1 to 20 carbon atoms Represents
  • R 5 is —NH 2 or NHCOR 5a , R 5a is an alkyl group, R 6 is —NHCO—Ph, R 9 is —SO 3 — , and / or Or, R 2 or R 3 is —CH 3 .
  • the anion portion may have one type of structure in the range of the general formula (1), or may have a plurality of different types of structures, and preferably has one type of structure. That is, a plurality of R 1 to R 10 and Y may be the same or different. Further, the non-color-forming cation part may be one kind or a mixture of plural kinds, and preferably one kind. That is, when k is 2 to 8, a plurality of Xs may be the same or different.
  • examples of the “optionally substituted amino group having 0 to 20 carbon atoms” include, for example, an unsubstituted amino group (—NH 2 ), a monosubstituted amino group, and a disubstituted amino group. Etc.
  • the number of carbon atoms in the monosubstituted amino group or disubstituted amino group is, for example, 1 to 20, 1 to 10, or 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 30 carbon atoms, which will be described later, or a ring forming atom having 5 to 30 atoms, via —NH—.
  • bonded may be sufficient.
  • the monosubstituted amino group include an ethylamino group, an acetylamino group, and a phenylamino group.
  • the disubstituted amino group include a diethylamino group, a diphenylamino group, and an acetylphenylamino group.
  • the monosubstituted amino group may be a group represented by —NHCOR 5a .
  • the substituent R 5a is an alkyl group.
  • the “sulfonyl group optionally having a substituent having 0 to 20 carbon atoms” is represented by —SO 2 —R 100 (or —S ( ⁇ O) 2 —R 100 ).
  • Substituent R 100 may be a group containing a carbon atom or a group not containing a carbon atom.
  • the number of carbon atoms of the substituent R 100 is 1 to 20, 1 to 10, or 1 to 7.
  • a linear alkyl group such as methyl group, ethyl group, n-propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; isopropyl group
  • branched alkyl groups such as isobutyl group, s-butyl group, t-butyl group, isooctyl group and t-octyl group.
  • the “cycloalkyl group having 3 to 20 carbon atoms” in the “cycloalkyl group having 3 to 20 carbon atoms which may have a substituent” specifically includes a cyclopropyl group, Examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group.
  • linear or branched alkoxy group having 1 to 20 carbon atoms in “optionally substituted linear or branched alkoxy group having 1 to 20 carbon atoms”.
  • Examples include chain alkoxy groups; branched alkoxy groups such as isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group, and t-octyloxy group.
  • the “cycloalkoxy group having 3 to 20 carbon atoms” in the “optionally substituted cycloalkoxy group having 3 to 20 carbon atoms” specifically includes a cyclopropoxy group, Examples thereof include a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and the like.
  • linear or branched alkenyl group having 2 to 20 carbon atoms in “optionally substituted linear or branched alkenyl group having 2 to 20 carbon atoms”.
  • Specific examples of "" include a vinyl group, an allyl group, an isopropenyl group, a 2-butenyl group, a 1-hexenyl group, or a linear or branched group in which a plurality of these alkenyl groups are bonded.
  • the “acyl group having 1 to 20 carbon atoms which may have a substituent” is a group represented by —C ⁇ O—R 101 .
  • Substituent R 101 may be a group containing a carbon atom or a group not containing a carbon atom.
  • the number of carbon atoms of the substituent R 101 may be, for example, 1-20, or 1-10.
  • the acyl group having 1 to 20 carbon atoms which may have a substituent is an aromatic hydrocarbon group having 6 to 30 carbon atoms, which will be described later, or a ring forming atom having 5 to 30 atoms, via an acyl group.
  • a group to which a heterocyclic group is bonded may be used.
  • substituent R 101 include —H, —CH 3 , —CH 2 CH 2 CH 3 , —CH ⁇ CH 2 , and —C 6 H 5 (—Ph).
  • the “acyl group having 1 to 20 carbon atoms” in the “optionally substituted acyl group having 1 to 20 carbon atoms” specifically includes formyl group, acetyl group, propionyl group, acrylyl group. And benzoyl group.
  • the “aromatic hydrocarbon group having 6 to 30 carbon atoms” in the “optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms” specifically includes Examples thereof include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, an indenyl group, and a fluorenyl group.
  • the “aromatic hydrocarbon group” in the present specification represents an aromatic hydrocarbon group and a condensed polycyclic aromatic group, and among these, a phenyl group or a naphthyl group is preferable.
  • the “heterocyclic group having 5 to 30 ring atoms” in the “optionally substituted heterocyclic group having 5 to 30 ring atoms” specifically includes a pyridyl group. , Pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzoimidazolyl group, carbazonyl group, carbolinyl group, acridinyl 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 and the like
  • amino group having 0 to 20 carbon atoms having substituent “sulfonyl group having 0 to 20 carbon atoms having substituent”, “straight chain having 1 to 20 carbon atoms having substituent” Or a branched or branched alkyl group ”,“ a cycloalkyl group having 3 to 20 carbon atoms having a substituent ”,“ a linear or branched alkoxy group having 1 to 20 carbon atoms having a substituent ”,“ A cycloalkoxy group having 3 to 20 carbon atoms having a substituent ", a linear or branched alkenyl group having 2 to 20 carbon atoms having a substituent", and 1 to 20 carbon atoms having a substituent.
  • R 1 may be, for example, —H.
  • R 2 represents, for example, —H, —SO 3 — , —CN, —NO, —NO 2 , a straight chain having 1 to 20 carbon atoms (or 1 to 10 carbon atoms) which may have a substituent.
  • a linear or branched alkyl group for example, —CH 3
  • a linear or branched alkoxy group having 1 to 20 carbon atoms (or 1 to 10 carbon atoms) which may have a substituent.
  • R 3 is, for example, —H, —NO 2 , an optionally substituted cycloalkoxy group having 3 to 20 carbon atoms, an optionally substituted carbon atom having 1 to 20 carbon atoms (or A linear or branched alkoxy group having 1 to 10 carbon atoms, or a linear or branched chain having 1 to 20 carbon atoms (or 1 to 10 carbon atoms) which may have a substituent.
  • an alkyl group eg, —CH 3
  • R 4 may be, for example, —H, —NO 2 , or F.
  • R 2 or R 3 may be —CH 3 .
  • R 1 , R 3 and R 4 may each be —H.
  • R 3 is —CH 3
  • R 1 , R 2 and R 4 may each be —H.
  • R 1 to R 4 each represent a substituent as described above, and adjacent groups are each represented by a single bond, a bond via an oxygen atom (—O—) or a sulfur atom.
  • a ring may be formed by bonding to each other via a bond (—S—).
  • M represents a chromium atom (Cr), an iron atom (Fe), a cobalt atom (Co), a silicon atom (Si) or an aluminum atom (Al), preferably a Cr atom or a Co atom. Cr atoms are more preferred.
  • X is a non-chromogenic cation, specifically, hydrogen ion (H + ), lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), etc.
  • K represents the number of the non-color-forming cation “X”, represents an integer of 1 to 8, and is preferably an integer of 3 to 7.
  • k is a value such that the general formula (1) becomes neutral as a whole.
  • R 5 is preferably —H or an optionally substituted amino group having 0 to 10 carbon atoms, more preferably —H or —NH 2 .
  • R 6 is preferably —H, —SO 3 —, or an optionally substituted amino group having 0 to 10 carbon atoms.
  • One or two either R 7 ⁇ R 10 are, -SO 3 - is preferably, any two of R 7 ⁇ R 10 is -SO 3 - if it is, R 7 and R 10 Is more preferably —SO 3 — .
  • R 5 may be —NH 2 or NHCOR 5a .
  • the substituent R 5a may be, for example, a group exemplified as the above-described linear or branched alkyl group having 1 to 20 carbon atoms, and may be a methyl group.
  • R 6 when R 5 is —NH 2 or NHCOR 5a , for example, R 6 may be —H or SO 3 — , and R 7 is —H, —SO 3 — R 8 may be —H, —SO 3 ⁇ , —COO — , and R 9 is —H, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, or a substituent. May be an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 10 may be —H, —SO 3 ⁇ , or an optionally substituted carbon atom having 1 to It may be 20 acyl groups.
  • R 6 may be —NHCO—Ph.
  • “Ph” means a phenyl group.
  • R 5 , R 8 and R 9 may each be —H and R 10 may be —SO 3 — .
  • R 9 may be —SO 3 — .
  • R 5 , R 6 , R 7 , R 8 and R 10 may each be —H.
  • the compound of the present invention represented by the general formula (1) includes all possible stereoisomers, and any isomer can be suitably used as the compound of the present invention.
  • any isomer can be suitably used as the compound of the present invention.
  • the compound of the present invention is represented by the general formula (1) and the general formula (1-a).
  • a mixture of two or more selected from these stereoisomers may be included.
  • the compound (1) may be a compound represented by the formulas (A-1) to (A-24). From the viewpoint of further improving light resistance and further improving heat resistance, the compound (1-3) or It may be a compound represented by (A-4).
  • the compound (1) can be produced as a 1: 2 type complex salt compound by preparing and reacting in the following manner, complexing and salting out.
  • the compound containing an atom represented by M is a compound containing a Cr, Fe, Co, Si or Al atom, and one kind of compound may be used alone, or two or more kinds of compounds are combined. May be used.
  • Specific examples of the compound containing an atom represented by M include, for example, chromium acetate.
  • the method for producing the compound (1) includes the following general formula (I): [In the formula (I), R 1 to R 10 and Y are as defined above. ] A compound represented by the formula (compound (I)) and a compound containing a Cr, Fe, Co, Si, or Al atom. As described above, the compound (I) is represented by the diazotized compound (compound (IV)) obtained by diazotizing the compound represented by the following formula (II) (compound (II)) and the following formula (III). And a compound obtained by diazo coupling reaction with a compound (compound (III)) and / or a salt thereof.
  • Compound (1) can be purified by known methods such as purification by column chromatography; adsorption purification using silica gel, activated carbon, activated clay, etc .; recrystallization using a solvent, crystallization method and the like.
  • UV-Vis absorption spectrum analysis UV-Vis
  • TG-DTA thermogravimetry-differential thermal analysis
  • GC gas chromatography analysis
  • NMR nuclear magnetic resonance analysis
  • Compound (1) can be used as a component of the dye composition.
  • Compound (1) can also color aluminum, fibers, and the like when used alone. That is, the compound (1) can be suitably used as a coloring compound for coloring aluminum, fibers, etc., using one kind of single-color dye alone. Two or more kinds of compounds (1) may be used in combination in order to obtain various colors by color mixing.
  • the dye composition may be mixed with other components for optimal dyeing (coloring with a dye). Specific examples include liquids (solvents) such as water, alcohol, and solvents; additives such as surfactants; and the like. As the solvent, water is preferable.
  • Compound (1) may be used as a component of a dye composition in combination with other pigments.
  • the other dyes are compounds other than the compound (1), pigments, dyes, and the like, and specifically, ruthenium complexes, coumarin dyes, cyanine dyes, merocyanine dyes, rhodacyanine dyes, phthalocyanine dyes, Examples include porphyrin dyes and xanthene dyes.
  • the amount of the other component used relative to the compound (1) is preferably 10 to 200% by mass, more preferably 20 to 100% by mass. .
  • the dye composition according to this embodiment can be applied as a colorant for anodized aluminum.
  • the concentration of the compound (1) in the dye composition containing the compound (1) in the coloring (dyeing) method is based on the total amount of the dye composition. 0.02 to 10% by mass is preferable, and 0.05 to 1% by mass is more preferable.
  • the anodized aluminum means aluminum that has been subjected to a treatment for forming an oxide layer having pores on the surface of the electrolytically treated aluminum in an electrolytic solution such as an acid aqueous solution.
  • the colorant for anodized aluminum is colored (dyed) by adsorbing the compound (1) into the pores using the dye composition containing the compound (1) on the surface of the aluminum having pores. It means something that can be done.
  • a sealing treatment for closing the pores after coloring is performed.
  • Examples of aluminum in anodized aluminum include aluminum, aluminum oxide, and aluminum-containing metals or metal compounds such as aluminum alloys with other metals.
  • a method for coloring aluminum using a colorant for anodized aluminum a method known as an alumite dyeing method can be used.
  • the methods described in Japanese Industrial Standard JIS H 8601: 1999 “Aluminum and Aluminum Alloy Anodized Film”), Patent Documents 1 to 3, 8 and the like can be used.
  • the coloring method of aluminum is not specifically limited, an example is shown below.
  • the aluminum plate is degreased using an acid aqueous solution such as sulfuric acid, oxalic acid, chromic acid, or sulfonic acid, and washed with water.
  • an acid aqueous solution such as sulfuric acid, oxalic acid, chromic acid, or sulfonic acid
  • the degreased aluminum plate is used as an anode and electrolysis is performed using an acid aqueous solution as an electrolytic solution to form an anodized film (anodized film) that forms many pores on the surface of the aluminum anode (anodizing treatment). ) Wash with water.
  • a coloring agent aqueous solution for anodized aluminum containing the dye composition containing the compound of the present invention is immersed in a coloring agent aqueous solution for anodized aluminum containing the dye composition containing the compound of the present invention, and the dye is adsorbed in the pores (dyeing, It can be colored by electrolytically coloring) and sealing the surface pores with aluminum oxide hydrate to form a sealing substance.
  • a mixed solution of all pigments to be used may be prepared and immersed in anodized aluminum.
  • each dye solution may be prepared separately, and anodized aluminum may be immersed in each solution in order.
  • the electrolysis conditions during coloring may be direct current electrolysis or alternating current electrolysis, and direct current electrolysis is preferred.
  • the current density is preferably from 0.1 to 10 A / dm 2, and more preferably from 0.5 to 3 A / dm 2 .
  • the energization time is preferably 10 seconds to 60 minutes.
  • the thickness of the anodized film is preferably 2 to 20 ⁇ m.
  • the treatment temperature in each of the above steps is preferably a suitable temperature, and the temperature during anodization is preferably 0 to 80 ° C.
  • the temperature during dyeing is preferably 10 ° C to 70 ° C.
  • Other treatment temperatures are preferably 10 to 80 ° C.
  • the dye composition according to this embodiment can be used in the same manner for anodic oxides using metals other than aluminum.
  • any material such as magnesium, zinc, titanium, and zirconium that can adsorb the dye to the anodized pores can be applied to nonmetals such as conductive plastics.
  • the colorant for anodized aluminum can evaluate the characteristics of a sample colored on aluminum by measuring the hue, light resistance, heat resistance, and the like. Hue can be visually evaluated for color and uniformity, and can be measured with a color difference meter as density (K / Sd), color (L * , a * , b * ) and color difference ( ⁇ E * ). Good.
  • colorant for anodized aluminum green, blue, purple, light colors (light green, etc.) or dark colors (black green, etc.) of different shades can be represented.
  • a mixture of the above-described compounds and other pigments which are mixed colors (yellowish green, Kusumi blue, black, gray (gray), intermediate colors such as brown, etc. ) Can also be expressed.
  • the intermediate color black and ash are preferable.
  • the light resistance test of aluminum colored using the colorant for anodized aluminum according to the present embodiment is performed by irradiating the sample with light for a certain period of time using a testing machine that simulates sunlight including ultraviolet light, before and after the test.
  • the change in hue of the colored aluminum may be evaluated by measuring with a color difference meter or the like.
  • the color fastness of the dyed aluminum may be determined visually using a gray scale according to a method defined by Japanese Industrial Standard (Gray Scale for Discoloration, JIS L 0804).
  • the heat resistance test of aluminum colored with the colorant for anodized aluminum according to the present embodiment is suitable within a range of 30 minutes to 50 hours, for example, in a constant temperature oven or hot air dryer in a temperature range of 50 to 300 ° C.
  • a method of evaluating a change in hue before and after the test as in the light resistance test such as a method of heating for a certain period of time.
  • Colored aluminum using the colorant for anodized aluminum according to the present embodiment is used for a wide variety of aluminum plate materials, aluminum exteriors, and the like.
  • Coupler component A reaction vessel was charged with 30 g of 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid, 200 mL of water, and 18.9 g of a 24 wt% aqueous sodium hydroxide solution. The resulting reaction liquid was stirred at 10 ° C. for 1 hour to obtain a coupler component liquid.
  • the diazo component liquid was put into the stirring coupler component liquid and stirred for 1 hour to carry out a diazo coupling reaction.
  • the completion of the reaction was confirmed by thin layer chromatography (TLC).
  • the purity of the product was confirmed by high performance liquid chromatography (HPLC) by the observed retention time peak position and area of typical azo dyes.
  • Example 1 Colored aluminum was produced by anodizing the aluminum substrate by the following procedure. In the anodic oxidation and dyeing steps, two types of dyeing conditions were set by changing the treatment time and the dye compound concentration. (Degreasing) Dyeing agent prepared by mixing a container with 150 mL of a degreasing agent (Okuno Pharmaceutical Co., Ltd., Top ADD-100), 70 mL of 98% sulfuric acid, and 1000 mL of water as a degreasing solution, and then cutting to an appropriate size The substrate was immersed, degreased at 60 ° C. for 3 minutes, and washed with water after the treatment.
  • a degreasing agent prepared by mixing a container with 150 mL of a degreasing agent (Okuno Pharmaceutical Co., Ltd., Top ADD-100), 70 mL of 98% sulfuric acid, and 1000 mL of water as a degreasing solution, and then cutting to an appropriate size
  • the substrate
  • An electrolyte solution of 180 g / L was prepared using 98% sulfuric acid, an aluminum substrate was connected to the electrode of the electrolysis apparatus, and immersed in an electrolyte bath, temperature 20 ⁇ 1 ° C., current density 1.0 A / Anodization was performed under the condition of the following energization time of dm 2 to obtain an anodized film having the following thickness. After oxidation, it was washed with water.
  • a surface adjustment liquid having a concentration of 50 mL / L was prepared using a surface conditioner (manufactured by Okuno Pharmaceutical Co., Ltd., TAC Somar 121) and water, and an aluminum substrate was immersed at 45 ° C. for 1 minute. After immersion, the aluminum substrate was washed with water.
  • Light Resistance Test A light resistance test was performed on the colored aluminum plate colored with the compound (A-1) by the following method. Xenon fade meter / ATLAS Ci3000 + Xenon Weather Ometer (manufactured by Atlas Co., Ltd.), irradiance: 300 to 400 nm, 60 W / m 2 , test chamber temperature: 38 ° C., humidity: 50%, black panel (BP) temperature: 63 With respect to the results obtained by irradiating a colored aluminum plate for 50 hours under the condition of ° C., a visual determination of the color fastness (gray scale for fading color, JIS L 0804) was performed based on the gray scale series.
  • the fifth grade is the highest and the first grade is the lowest. The higher the grade, the deeper the color and the higher the hue before irradiation.
  • the determination result of the series is divided into three stages, evaluated according to the following determination criteria, and the results are summarized in Table 1. Gray scale criteria: Correspondence between series and evaluation (A, B, C) in the present invention Grade 5 to Grade 4: A (particularly good light resistance) Third grade: B (normal level of light resistance) Grade 2 or lower: C (low light resistance)
  • Examples 2 to 8, Comparative Examples and Reference Examples A colored aluminum plate was prepared in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of the compound (A-1), and the hue and light resistance were evaluated. The measurement results are summarized in Table 1.
  • Example 3 Using the compound (A-3), a heat resistance test was performed on the colored aluminum plate colored under the dyeing condition (2) of the above-mentioned example by the following method.
  • the sample was heated under the following exposure conditions using a constant temperature dryer (manufactured by AS ONE Corporation, model: 87L EOP-450V). Dryer internal temperature and heating time: 200 ° C.-5 hours, or 250 ° C.-3 hours
  • the heat resistance evaluation method of the present invention uses the following color difference meter to measure the color difference of the colored aluminum sample before and after heating, and visually. Evaluation was made according to the following criteria. The results are shown in Table 2.
  • Color difference meter (Spectral color difference meter manufactured by Konica Minolta, model: CM-3700A) Color difference calculation formula: ⁇ E * ab (L * a * b * , CIE 1976) and ⁇ E * 00 (CIE DE2000) Viewing angle: 10 ° Criteria for heat resistance: A: Good heat resistance (no discoloration or fading) B: Normal level of heat resistance (not discolored but slightly discolored) C: Low heat resistance (fading and discoloration)
  • Example 4 A heat resistance test was conducted in the same manner as in Example 3 except that the compound (A-4) was used. Although it became a slightly blackish green after heating at 250 ° C., it had a normal level of heat resistance. The results are summarized in Table 2.
  • a green and highly heat-resistant film could be formed on aluminum by using an anodized aluminum colorant comprising a dye composition containing the compound of the present invention.
  • the heat resistance of the film using the pigment of the example is superior to that using a conventional green pigment, and is comparable to that using a conventional black pigment.
  • the dye composition containing the compound according to the present invention it is possible to obtain a colorant for anodized aluminum that is excellent in light resistance and can form a monochromatic, blue-green colored film.
  • the colorant according to the present invention it is possible to obtain an anodized aluminum film that is monochromatic and blue-green and excellent in light resistance.
  • the colored film obtained using the dye composition containing the compound according to the present invention is also excellent in heat resistance.

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Abstract

La présente invention concerne un composé représenté par la formule générale (1) [dans laquelle R1 à R10 représentent indépendamment ―H, ―SO3 -, un groupe amino qui a de 0 à 20 atomes de carbone et qui peut avoir un substituant en ―NO2, ou similaire ; M représente un atome de Cr ou similaire ; X représente un cation non chromogène ; k représente un nombre entier compris entre 1 et 8 ; et Y représente ―O― ou ―O―(C=O)―], où R5 représente -NH2 ou NHCOR5a, et R5a représente un groupe alkyle, R6 représente -NHCO-Ph, R9 représente -SO3 - et/ou R2 ou R3 représente -CH3.
PCT/JP2019/012916 2018-03-27 2019-03-26 Composé de sel complexe, composition de colorant, agent de coloration et procédé de coloration pour aluminium anodisé, et procédé de production dudit composé Ceased WO2019189209A1 (fr)

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