JP7165313B2 - coloring method - Google Patents

Description

The present invention relates to a coloring method for coloring a substrate using a raw material solution.

A technique for coloring a substrate by forming a colored film on the substrate is known, and methods for forming the colored film include the sputtering method, the inkjet method, the sol-gel method, the spray method, and the like. For example, Patent Literature 1 describes manufacturing a colored film-coated glass by forming an aluminum metal layer, a cobalt oxide layer, and an aluminum metal layer in this order on a glass substrate using a sputtering method. However, since the sputtering method described in Patent Document 1 requires a vacuum apparatus, there are problems such as an increase in cost, and the method is not fully satisfactory.

Further, Patent Document 2 describes forming a colored coating film by applying a curable resin composition for coloring containing an organic pigment and optionally a dye onto a glass substrate by spin coating and then heating the composition. It is However, in the method described in Patent Document 2, after applying the curable resin composition for coloring on the substrate, it is essential to dry by heating or the like, and such a drying process increases the labor of the work. In addition, there is a problem that cracks occur in the colored film and aggregation of the colorant occurs during drying, which adversely affects the uniformity and surface flatness of the obtained colored film. In addition, the coloring method described in Patent Document 2 requires the use of a resin as a binder, which causes problems such as an increase in cost and an adverse effect on the color tone of the resulting colored film. Moreover, when there is no affinity between the colorant and the binder resin, the dispersibility is lowered, and a colored film having sufficient transparency cannot be obtained.

In Patent Document 3, in the manufacturing process of glass products, a coating liquid containing a metal compound is sprayed onto the surface of a glass substrate before cooling, and the temperature of the glass surface is used to form a coating, thereby producing a colored glass product. It is described to make a However, in the method described in Patent Document 3, the coating liquid is sprayed using a spray gun, and it is difficult to form a uniform colored film on the substrate, and there are also problems with the flatness of the film. . In addition, it is difficult to uniformly disperse the metal compound as the coloring agent, and there is a problem that the original coloring power and transparency cannot be exhibited. Moreover, the method described in Patent Document 3 is difficult to apply to glass products after the manufacturing process, and is not satisfactory.

Therefore, there has been a desire for a coloring method that can uniformly and satisfactorily color a substrate without the above-described problems and with industrial advantages.

Japanese Patent Application Laid-Open No. 2003-095701 JP 2015-086379 A JP 2008-074477 A

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel coloring method capable of coloring a substrate uniformly and satisfactorily in an industrially advantageous manner.

As a result of intensive studies to achieve the above object, the present inventors have found that a substrate is colored by forming a colored film on the substrate using mist or droplets of a raw material solution containing at least a coloring agent and a solvent. In the above method, when a solvent containing a nonpolar solvent and a polar solvent having a higher boiling point than the nonpolar solvent is used as the solvent, a raw material solution suitable for atomization or dropletization is obtained, and the film formation is performed. When coloring is performed by thermally reacting the mist or the droplets on the substrate, the substrate can be colored efficiently, uniformly and well without using a resin as a binder. The inventors have found that the resulting colored film is also excellent in transparency, and that such a coloring method can solve the above-described conventional problems at once.
Moreover, after obtaining the above knowledge, the inventors of the present invention conducted further studies and completed the present invention.

（式中、Ｒ^１～Ｒ^６は、それぞれ同一または異なって、水素原子または置換基を有していてもよい炭化水素基を表し、Ｒ^１～Ｒ^６から選ばれる任意の２つの基が結合して環を形成してもよい。）
［８］ 前記無極性溶媒と前記極性溶媒との沸点差が５０℃以上である前記［１］～［７］のいずれかに記載の着色方法。
［９］ 前記熱反応を、前記極性溶媒の沸点以下の温度で行う前記［１］～［８］のいずれかに記載の着色方法。
［１０］ 前記熱反応を、キャリアガスを前記ミストまたは前記液滴に供給し、ついで、該キャリアガスを用いて前記ミストまたは前記液滴を前記基体まで搬送した後に行う前記［１］～［９］のいずれかに記載の着色方法。
［１１］ 前記ミストまたは前記液滴が、超音波振動を用いて得られたものである前記［１］～［１０］のいずれかに記載の着色方法。 Specifically, the present invention relates to the following inventions.
[1] A method for coloring a substrate by forming a colored film on the substrate using a mist or droplets of a raw material solution containing at least a coloring agent and a solvent, wherein the solvent is a nonpolar solvent and A coloring method comprising: a polar solvent having a boiling point higher than that of the non-polar solvent; and forming the film by thermally reacting the mist or the liquid droplets on the substrate.
[2] The coloring method according to [1], wherein the coloring agent is a pigment.
[3] The coloring method according to [1] or [2], wherein the coloring agent is an organic pigment.
[4] The coloring method according to any one of [1] to [3], wherein the volume ratio of the nonpolar solvent to the polar solvent is 5:1 to 1:1.
[5] The coloring method according to any one of [1] to [4], wherein the volume ratio of the nonpolar solvent to the polar solvent is 4:1 to 7:3.
[6] The coloring method according to any one of [1] to [5], wherein the polar solvent is an aprotic polar solvent.
[7] The coloring method according to any one of [1] to [6], wherein the nonpolar solvent is represented by the following formula (1).

(Wherein, R ¹ to R ⁶ are each the same or different and represent a hydrogen atom or a hydrocarbon group optionally having a substituent, and any two groups selected from R ¹ to R ⁶ are bonded may form a ring.)
[8] The coloring method according to any one of [1] to [7], wherein the boiling point difference between the nonpolar solvent and the polar solvent is 50°C or more.
[9] The coloring method according to any one of [1] to [8], wherein the thermal reaction is performed at a temperature not higher than the boiling point of the polar solvent.
[10] The above [1] to [9] wherein the thermal reaction is performed after a carrier gas is supplied to the mist or the droplets, and then the mist or the droplets are conveyed to the substrate using the carrier gas. ] The coloring method according to any one of the above.
[11] The coloring method according to any one of [1] to [10], wherein the mist or the droplets are obtained by using ultrasonic vibration.

According to the coloring method of the present invention, a substrate can be uniformly and satisfactorily colored industrially.

1 is a schematic configuration diagram of a film forming apparatus used in Examples. FIG. It is a figure which shows the result of the ultraviolet-visible absorption measurement in an Example.

The coloring method of the present invention is a method for coloring a substrate by forming a colored film on the substrate using mist or droplets of a raw material solution containing at least a coloring agent and a solvent, wherein the solvent is It is characterized by containing a non-polar solvent and a polar solvent having a higher boiling point than the non-polar solvent, and performing the film formation by thermally reacting the mist or the droplets on the substrate.

(substrate)
The substrate is not particularly limited as long as it can support the film to be deposited. The material of the substrate is also not particularly limited as long as it does not interfere with the object of the present invention, and may be a known substrate, an organic compound, or an inorganic compound. It may be a porous structure.

A substrate having at least one film selected from a metal film, a semiconductor film, a conductive film and an insulating film formed on part or all of the surface can also be suitably used as the substrate. The constituent metal of the metal film is, for example, one selected from gallium, iron, indium, aluminum, vanadium, titanium, chromium, rhodium, nickel, cobalt, zinc, magnesium, calcium, silicon, yttrium, strontium and barium, or Two or more kinds of metals and the like are included. Examples of constituent materials of the semiconductor film include simple elements such as silicon and germanium, compounds containing elements of Groups 3 to 5 and Groups 13 to 15 of the periodic table, metal oxides, and metal sulfides. , metal selenide, or metal nitride. Examples of materials constituting the conductive film include tin-doped indium oxide (ITO), fluorine-doped indium oxide (FTO), zinc oxide (ZnO), aluminum-doped zinc oxide (AZO), and gallium-doped zinc oxide (GZO). , tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), and tungsten oxide (WO ₃ ). More preferably, it is an indium oxide (ITO) film. Materials constituting the insulating film include, for example, aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), silicon nitride (Si ₃ N ₄ ), silicon oxynitride (Si ₄ O ₅ N ₃ ) and the like.

The means for forming the metal film, the semiconductor film, the conductive film, and the insulating film is not particularly limited, and known means may be used. Examples of such forming means include mist CVD method, sputtering method, CVD method (vapor phase growth method), SPD method (spray pyrolysis deposition method), vapor deposition method, ALD (atomic layer deposition) method, coating method ( For example, dipping, dropping, doctor blade, inkjet, spin coating, brush coating, spray coating, roll coater, air knife coating, curtain coating, wire bar coating, gravure coating, inkjet coating, etc.).

The shape of the substrate may be any shape, and is effective for all shapes. Cylindrical, helical, spherical, ring-shaped, etc. are mentioned, and in the present invention, a substrate is preferable. The thickness of the substrate is not particularly limited in the present invention, but is preferably 0.5 μm to 100 mm, more preferably 1 μm to 10 mm. The substrate is plate-shaped and is not particularly limited as long as it serves as a support for the film to be deposited. It may be an insulator substrate, a semiconductor substrate, a metal substrate, or a conductive substrate.

Further, in the present invention, it is preferable to use a transparent substrate as the substrate. The transparent substrate may be made of an inorganic material or an organic material. Examples of the inorganic material include glass (soda glass, borosilicate glass, crown glass, barium-containing glass, strontium-containing glass, boron-containing glass, low-alkali glass, alkali-free glass, crystallized transparent glass, silica glass, quartz glass, , heat-resistant glass, etc.), alumina, sapphire, zirconia, titania, yttrium oxide, and the like. Examples of the organic material include polymethylmethacrylate-based resins, styrene-based resins, vinyl chloride-based resins, polyester-based resins (including polyarylate-based resins and liquid crystal polymers), polyamide-based resins, polycarbonate-based resins, and polysulfone-based resins. , polyethersulfone-based resins, polyimide-based resins, cellulose derivatives, fluorine resins, and the like. In the present invention, the substrate is preferably a transparent substrate, more preferably a glass substrate. According to the coloring method of the present invention, even when coloring such a transparent substrate, it is possible to uniformly and satisfactorily color the transparent substrate while maintaining the transparency.

(mist or droplets)
The mist or droplets are usually obtained by atomizing or dropletizing the raw material solution. The atomization means or dropletization means is not particularly limited as long as it can atomize or dropletize the raw material solution, and may be any known means. A dropletizing means is preferred. The mist or droplets obtained using ultrasonic waves have an initial velocity of zero and are preferable because they float in the air. Since it is a possible mist, there is no damage due to collision energy, so it is very suitable. The droplet size is not particularly limited, and may be droplets of several millimeters, preferably 50 μm or less, more preferably 100 nm to 10 μm.

(raw material solution)
The raw material solution is not particularly limited as long as it contains at least the colorant and the solvent and can be atomized or dropletized. The raw material solution may further contain an inorganic material or an organic material as long as the object of the present invention is not hindered. Moreover, the raw material solution may further contain both inorganic materials and organic materials.

(coloring agent)
The coloring agent is not particularly limited as long as it can color the base. Examples of the coloring agent include dyes such as direct dyes, acid dyes, basic dyes, disperse dyes, vat dyes and reactive dyes, and pigments such as inorganic pigments and organic pigments. In the present invention, the coloring agent is preferably a pigment, more preferably an organic pigment.

(dye)
Examples of the direct dyes include azo direct dyes, thiazole direct dyes, anthraquinone direct dyes, oxazine direct dyes and phthalocyanine direct dyes. Examples of the acid dyes include anthraquinone acid dyes, phthalocyanine acid dyes, quinoline acid dyes, azine acid dyes, indigoid acid dyes, xanthene acid dyes, and triphenylmethane acid dyes. Examples of the basic dyes include azo-based basic dyes, azine-based basic dyes, acridine-based basic dyes, methine-based basic dyes, thiazole-based basic dyes, thiazine-based basic dyes, and oxazine-based basic dyes. , anthraquinone-based basic dyes, xanthene-based basic dyes, triarylmethane-based basic dyes, and the like. Examples of oil-soluble dyes include anthraquinone-based oil-soluble dyes, phthalocyanine-based oil-soluble dyes, quinoline-based oil-soluble dyes, azine-based oil-soluble dyes, indigoid-based oil-soluble dyes, methine-based oil-soluble dyes, azo-based oil-soluble dyes, Examples include aminoketone-based oil-soluble dyes, xanthene-based oil-soluble dyes, triphenylmethane-based oil-soluble dyes, and the like. Examples of the disperse dyes include anthraquinone disperse dyes, quinoline disperse dyes, indigoid disperse dyes, quinophthalone disperse dyes, methine disperse dyes, azo disperse dyes, aminoketone disperse dyes and xanthene disperse dyes. be done. Examples of the vat dyes include indanthrone-based vat dyes, pyranthrone-based vat dyes, benzanthrone-based vat dyes, anthraquinonecarbazole-based vat dyes, anthraquinoxazole-based vat dyes, indigo-based vat dyes, and the like. mentioned. Examples of the reactive dyes include pyrazolone azo reactive dyes, benzene azo reactive dyes, naphthalene azo reactive dyes, pyridone azo reactive dyes, J acid azo reactive dyes, H acid azo reactive dyes, and K acid azo reactive dyes. , anthraquinone reactive dyes, metal complex monoazo reactive dyes, formazan reactive dyes, phthalocyanine reactive dyes, disazo reactive dyes, azine reactive dyes and dioxazine reactive dyes.

(pigment)
Examples of the inorganic pigment include barium (Ba), copper (Cu), iron (Fe), manganese (Mn), chromium (Cr), cobalt (Co), nickel (Ni), zirconium (Zr), vanadium ( V), molybdenum (Mo), zinc (Zn), selenium (Se), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), palladium (Pd), silver (Ag), cadmium ( Cd), indium (In), tin (Sn), antimony (Sb), mercury (Hg), lead (Pb), bismuth (Bi), silicon (Si) and one or two selected from aluminum (Al) Metal oxides, composite oxides, metal chlorides, metal nitrides, metal carbides, metal hydroxides, metal sulfides, metal lead sulfates, metal complex salts or metal carbonates, or carbons (carbon black) of the above metals, Examples include metal powders.
The organic pigment is not particularly limited as long as it can color the substrate, as long as it does not interfere with the object of the present invention. Examples of the organic pigments include azo pigments and polycyclic pigments. Examples of the azo pigments include insoluble azo pigments, condensed azo pigments, soluble azo pigments, and derivatives thereof. Examples of the polycyclic pigment include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, and pyranthrone pigments. , anthanthrone-based pigments, flavanthrone-based pigments, indanthrone-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, metal complex-based pigments, fullerene-based pigments, and derivatives thereof. The above etc. are mentioned.

Examples of the insoluble azo pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22, 23, 31, 32, 37, 38, 41, 95, 111, 112, 114, 119, 136, 146, 147, 148, 150, 164, 170, 184, 187, 188, 210, 212, 213, 222, 223, 238, 245, 253, 256, 258, 261, 266, 267, 268, 269, C.I. I. Pigment Orange 1, 2, 5, 6, 13, 15, 16, 22, 24, 34, 38, 44, C.I. I. Pigment Violet 13, 25, 44, 50, C.I. I. Pigment Brown 1, C.I. I. Pigment Yellow 1, 2, 3, 5, 6, 10, 12, 13, 14, 17, 49, 55, 60, 63, 65, 73, 74, 75, 81, 83, 87, 90, 97, 98, 106, 111, 113, 114, 116, 121, 124, 126, 127, 130, 136, 152, 165, 167, 170, 171, 172, 174, 176, 188, or C.I. I. Pigment Blue 25 and the like. Examples of the condensed azo pigment include C.I. I. Pigment Yellow 93, 94, 95, 128, 166, C.I. I. Pigment Orange 31, C.I. I. Pigment Red 144, 166, 214, 220, 221, 242, 248, 262, C.I. I. Pigment Brown 23, 41, 42 and the like. Examples of the soluble azo pigment include C.I. I. Pigment Yellow 93, 94, 95, 128, 166, C.I. I. Pigment Orange 31, C.I. I. Pigment Red 144, 166, 214, 220, 221, 242, 248, 262, or C.I. I. Pigment Brown 23, 41, 42 and the like.

The phthalocyanine-based pigment is not particularly limited as long as it has a phthalocyanine skeleton. Moreover, the central metal contained in the phthalocyanine pigment is not particularly limited as long as it is a metal capable of forming a phthalocyanine skeleton. Among them, magnesium, titanium, iron, cobalt, nickel, copper, zinc and aluminum are preferably used as the central metal. Specific examples of the phthalocyanine pigment include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:5, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 17:1, C.I. I. Pigment Blue 75, C.I. I. Pigment Blue 79, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 37, chloroaluminum phthalocyanine, hydroxyaluminum phthalocyanine, aluminum phthalocyanine oxide, or zinc phthalocyanine.

The perylene-based pigment is not particularly limited as long as it has a perylene skeleton. Specific examples of the perylene pigment include C.I. I. Pigment Red 123, 149, 155, 178, 179, 190, 224, C.I. I. Pigment Violet 29, or C.I. I. Pigment Black 31, 32 and the like. The perinone-based pigment is not particularly limited as long as it has a perinone skeleton. Specific examples of the perinone pigment include, for example, C.I. I. Pigment Orange 43, C.I. I. Pigment Red 123, 149, 178, 179, 189, 190, 194, 224, C.I. I. Pigment Violet 29, 3, or Vat Red 14. The anthraquinone pigment is not particularly limited as long as it has an anthraquinone skeleton. Specific examples of the anthraquinone pigment include C.I. I. Pigment Red 89, 177 and the like.

The quinacridone pigment is not particularly limited as long as it has a quinacridone skeleton. Specific examples of the quinacridone pigment include C.I. I. Pigment Violet 19, 42, C.I. I. Pigment Red 122, 192, 202, 206, 207, 209, or C.I. I. Pigment Orange 48, 49 and the like. The dioxazine pigment is not particularly limited as long as it has a dioxazine skeleton. Specific examples of the dioxazine pigment include C.I. I. Pigment Violet 23, 37 and the like.

The indigo pigment is not particularly limited as long as it has an indigo skeleton. Specific examples of the indigo pigment include C.I. I. Pigment Blue 63, 73015:X and the like. The thioindigo-based pigment is not particularly limited as long as it has a thioindigo skeleton. Specific examples of the thiondigo-based pigment include, for example, C.I. I. Pigment Red 88, 181 and the like. The isoindolinone pigment is not particularly limited as long as it has an isoindolinone skeleton. The pyranthrone-based pigment is not particularly limited as long as it has a pyranthrone skeleton. Specific examples of the pyranthrone-based pigment include, for example, C.I. I. Pigment Red 216, 226, C.I. I. Pigment Orange 40, 51 and the like. The anthrone-based pigment is not particularly limited as long as it has an anthurone skeleton. Specific examples of the anthanthrone-based pigment include, for example, C.I. I. Pigment Red 168, C.I. I. Pigment Violet 31, Vat Orange 3, and the like. The flavanthrone-based pigment is not particularly limited as long as it has a flavanthrone skeleton. Specific examples of the flavanthrone-based pigment include, for example, C.I. I. Pigment Yellow 24, Vat Yellow 1, and the like.

The indanthrone-based pigment is not particularly limited as long as it has an indanthrone skeleton. Specific examples of the indanthrone-based pigment include, for example, C.I. I. Pigment Blue 60, 64, Vat Blue 4, and the like. The isoindolinone-based pigment is not particularly limited as long as it has an isoindolinone skeleton. Specific examples of the isoindolinone pigment include, for example, C.I. I. Pigment Yellow 109, 110, 173, or C.I. I. Pigment Orange 61 and the like. The quinophthalone-based pigment is not particularly limited as long as it has a quinophthalone skeleton. Specific examples of the quinophthalone-based pigment include, for example, C.I. I. Pigment Yellow 138 and the like. Specific examples of the metal complex pigment include C.I. I. Pigment Green 10, C.I. I. Pigment Yellow 117, 129, 150, 153, 177, 179, 257, 271, or C.I. I. Pigment Orange 59, 65, 68 and the like.

The fullerene-based pigment is not particularly limited as long as it has a fullerene skeleton. It may be a chemically modified fullerene derivative or a chemically unmodified fullerene, but in the present invention, a chemically unmodified fullerene is preferred. In the present invention, film formation can be performed satisfactorily even when chemically unmodified fullerene is used. Examples of the fullerene include C36 fullerene, C60 fullerene, C70 fullerene, C76 fullerene, C78 fullerene, C82 fullerene, C84 fullerene, C90 fullerene, and C96 fullerene. In the present invention, the fullerene is preferably C60 fullerene.

In the present invention, the organic pigment is preferably a polycyclic pigment, and more preferably a fullerene pigment, because it can color the substrate more uniformly and satisfactorily.

Also, the colorant may further contain other pigments or dyes. The other pigments or dyes described above may be pigments or dyes other than the pigments or dyes exemplified above.

The mixing ratio of the coloring agent in the raw material solution is not particularly limited, but is preferably 0.001% by weight to 80% by weight, more preferably 0.01% by weight to 80% by weight.

The non-polar solvent can be used as a solvent, and is not particularly limited as long as it has a boiling point lower than that of the polar solvent and does not have polarity. Examples of the nonpolar solvent include hydrocarbon compounds and aromatic compounds. In the present invention, the nonpolar solvent is preferably an aromatic compound because it can form a film more satisfactorily, and more preferably a compound represented by the following formula (1). .

（式中、Ｒ^１～Ｒ^６は、それぞれ同一または異なって、水素原子または炭化水素基を表し、Ｒ^１～Ｒ^６から選ばれる任意の２つの基が結合して環を形成してもよい。）

(wherein R ¹ to R ⁶ are the same or different and each represents a hydrogen atom or a hydrocarbon group, and any two groups selected from R ¹ to R ⁶ may combine to form a ring. .)

In the present invention, the nonpolar solvent is preferably an alkylaromatic compound. The alkyl aromatic compound is not particularly limited as long as it is an aromatic compound having one or more alkyl groups.

The "alkyl group" in the present invention is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, n-propyl, 2-propyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 1- ethylpropyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 1-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl , 1-ethylbutyl, 2-ethylbutyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. The alkyl group is more preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

Hydrocarbon groups include, for example, alkyl groups, aryl groups, aralkyl groups, and the like.

Examples of the alkyl group include the alkyl groups described above.

As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable. Specific examples of aryl groups include phenyl, indenyl, pentalenyl, naphthyl, azulenyl, fluorenyl, phenanthrenyl, anthracenyl, acenaphthylenyl, biphenylenyl, naphthacenyl, pyrenyl, and the like. The aryl group is more preferably an aryl group having 6 to 14 carbon atoms.

As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferred. Specific examples of the aralkyl group include benzyl, phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl, 4-phenylbutyl, 1- Phenylpentylbutyl, 2-phenylpentylbutyl, 3-phenylpentylbutyl, 4-phenylpentylbutyl, 5-phenylpentylbutyl, 1-phenylhexylbutyl, 2-phenylhexylbutyl, 3-phenylhexylbutyl, 4-phenylhexyl Butyl, 5-phenylhexylbutyl, 6-phenylhexylbutyl, 1-phenylheptyl, 1-phenyloctyl, 1-phenylnonyl, 1-phenyldecyl, 1-phenylundecyl, 1-phenyldodecyl, 1-phenyltridecyl or 1-phenyltetradecyl and the like. The aralkyl group is more preferably an aralkyl group having 7 to 12 carbon atoms.

In the present invention, it is also preferred that any two groups selected from R ¹ to R ⁶ in the formula (1) are condensed to form a ring. Examples of the ring formed by condensing any two groups selected from R ¹ to R ⁶ include 5- to 20-membered rings. Preferable rings to be formed include, for example, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclododecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring and cycloheptadecane ring. monocyclic ring; condensed ring such as dihydronaphthalene ring, indene ring or indane ring; Moreover, these rings may be substituted with a hydrocarbon group or the like. Specific examples of the hydrocarbon group include those described above for the hydrocarbon group.

Specific examples of the alkylaromatic compounds include alkylbenzenes such as toluene, xylene, trimethylbenzene, ethylbenzene, ethyltoluenes, ethylxylenes, diethylbenzenes, and propylbenzenes, methylnaphthalenes, ethylnaphthalenes, Alkylnaphthalenes such as dimethylnaphthalenes, and other alkylbiphenyls and alkylanthracenes are included. In the present invention, the alkylaromatic compound is preferably trimethylbenzene. Examples of the trimethylbenzene include 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene and the like. In the present invention, the trimethylbenzene is preferably 1,3,5-trimethylbenzene.

The boiling point of the non-polar solvent is not particularly limited as long as it is lower than the boiling point of the polar solvent. In the present invention, the boiling point of the nonpolar solvent is preferably 200°C or lower, more preferably 100°C to 200°C. Here, the boiling point means the boiling point under atmospheric pressure.

The polar solvent is not particularly limited as long as it can be used as a solvent, has polarity, and has a boiling point higher than that of the non-polar solvent. An inorganic solvent such as water may be used, or an organic solvent may be used. Examples of the water include pure water, ultrapure water, tap water, well water, mineral spring water, mineral water, hot spring water, spring water, fresh water, and seawater.

Examples of the organic solvent include protic polar solvents and aprotic polar solvents. Examples of the protic polar solvent include alcohol solvents, carboxylic acid solvents, phenol solvents, and the like. Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, methoxymethanol, methoxyethanol, methoxypropanol, methoxybutanol, ethylene glycol, or propylene glycol. Examples of the carboxylic acid solvent include formic acid, acetic acid, propionic acid, and butyric acid. Examples of the phenolic solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylinol, 3,4 -xylenol or 3,5-xylenol.

Examples of the aprotic polar solvent include one or more selected from amide solvents, lactone solvents, sulfoxide solvents, nitrile solvents, organic phosphorus solvents and cellosolve solvents. Examples of the amide solvent include N,N-dimethylacetamide, N-methyl-pyrrolidone, 2-pyrrolidone, N-methylcaprolactam, N,N-dimethylformamide, N,N-diethylformamide, N,N-diethyl acetamide, N-methylpropionamide, methylimidazolidinone, and the like. Examples of the lactone solvent include β-lactones such as β-propiolactone and β-butyrolactone; -lactones, δ-lactones such as δ-valerolactone, and ε-lactones such as ε-caprolactone. Examples of the sulfoxide solvent include dimethylsulfoxide, diethylsulfoxide, methylphenylsulfoxide, tetramethylenesulfoxide, and the like. Examples of the nitrile solvent include benzonitrile, acetonitrile, propionitrile, butyronitrile and adiponitrile. Examples of the organic phosphorus solvent include tetramethylphosphoricamide, hexamethylphosphoricamide, and the like. Examples of the cellosolve solvent include ethyl cellosolve acetate and methyl cellosolve acetate.

In the present invention, the polar solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and most preferably an amide solvent.

The boiling point of the polar solvent is not particularly limited as long as it is higher than the boiling point of the non-polar solvent. Most preferably it is 300°C. Here, the boiling point means the boiling point under atmospheric pressure. The difference in boiling points between the polar solvent and the non-polar solvent is not particularly limited, but in the present invention, the boiling point difference is preferably 30° C. or higher, since film formation can be performed more stably, and 50° C. is preferable. It is more preferably 70° C. or higher, and most preferably 70° C. or higher.

The mixing ratio of the polar solvent in the raw material solution is not particularly limited, but is preferably 0.0001 mol % to 90 mol %, more preferably 0.001 mol % to 50 mol %. The blending ratio of the non-polar solvent in the raw material solution is not particularly limited, but is preferably 0.01 mol % to 99 mol %, more preferably 1 mol % to 95 mol %. In the present invention, it is preferable that the volume ratio of the nonpolar solvent and the polar solvent is 5:1 to 1:1, since a raw material solution more suitable for atomization or dropletization can be obtained. , more preferably 4:1 to 2:1, most preferably 4:1 to 7:3.

The solvent is not particularly limited as long as it contains the nonpolar solvent and the polar solvent in the above ratio, and may further contain other solvents. The other solvent is not particularly limited, and may be a solvent other than the polar solvent or the nonpolar solvent, may be an organic solvent, or may be an inorganic solvent. Examples of the organic solvent include alcohols, esters, ethers and the like. Examples of the inorganic solvent include water, and more specific examples include pure water, ultrapure water, tap water, well water, mineral spring water, mineral water, hot spring water, spring water, fresh water, and seawater.

The raw material solution may further contain an additive. The additive is not particularly limited as long as it does not interfere with the object of the present invention, and may be an acid, a base, a solvent, or the like, and may be a known additive. It may be an inorganic material or an organic material. Examples of the acid include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, carbonic acid, formic acid, benzoic acid, chlorous acid, hypochlorous acid, sulfurous acid, Sulfurous acid, nitrous acid, hyponitrous acid, phosphorous acid, protonic acid such as hypophosphorous acid, or mixtures thereof. Examples of the base include sodium hydroxide, potassium hydroxide, calcium hydroxide, and mixtures thereof. The solvent is not particularly limited as long as it does not interfere with the object of the present invention, and may be an organic solvent other than the non-polar solvent or the polar solvent, or may be an inorganic solvent. A mixed solvent of an organic solvent and an inorganic solvent may be used. Examples of the organic solvent include alcohols, esters, ethers and the like. Examples of the inorganic solvent include water, and more specific examples include pure water, ultrapure water, tap water, well water, mineral spring water, mineral water, hot spring water, spring water, fresh water, and seawater.

The raw material solution is obtained, for example, by mixing the coloring agent, the polar solvent, and the non-polar solvent. The mixing means is not particularly limited, and may be a known mixing means. More specifically, for example, it can be obtained by dissolving or dispersing the coloring agent in the polar solvent and the non-polar solvent.

In the present invention, a carrier gas is supplied to the mist or the droplets, and then the mist or the droplets are transported to the substrate using the carrier gas, thereby coloring the substrate more uniformly and favorably. preferred because it can The carrier gas is not particularly limited as long as it does not interfere with the object of the present invention. Suitable examples include oxygen, ozone, inert gases such as nitrogen and argon, and reducing gases such as hydrogen gas and forming gas. mentioned. In addition, although one type of carrier gas may be used, two or more types may be used, and a diluted gas with a reduced flow rate (for example, a 10-fold diluted gas, etc.) may be further used as a second carrier gas. good too. In addition, the carrier gas may be supplied at two or more locations instead of at one location. Although the flow rate of the carrier gas is not particularly limited, it is preferably 0.01 to 20 L/min, more preferably 1 to 10 L/min. In the case of diluent gas, the flow rate of diluent gas is preferably 0.001 to 2 L/min, more preferably 0.1 to 1 L/min.

The thermal reaction is not particularly limited as long as the mist or liquid droplets react with heat, and the reaction conditions and the like are not particularly limited as long as the object of the present invention is not hindered. In this step, the thermal reaction is usually carried out at a temperature of 300° C. or less, but in the present invention, the thermal reaction is carried out at a temperature lower than the boiling point of the polar solvent so as to color the substrate more uniformly. It is preferable because The lower limit is not particularly limited as long as the object of the present invention is not hindered, but 100° C. or higher is preferable, and 120° C. or higher is more preferable. In addition, the thermal reaction may be carried out under vacuum, under a non-oxygen atmosphere, under a reducing gas atmosphere, or under an oxygen atmosphere as long as the object of the present invention is not hindered. It is preferably carried out under atmosphere. Also, the reaction may be carried out under atmospheric pressure, increased pressure or reduced pressure, but in the present invention, it is preferably carried out under atmospheric pressure. Note that the film thickness can be set by adjusting the film formation time.

Further, in the present invention, an annealing treatment may be performed after the film formation. Annealing treatment temperature is not particularly limited as long as the object of the present invention is not impaired. The annealing treatment time is usually 1 minute to 48 hours, preferably 10 minutes to 24 hours, more preferably 30 minutes to 12 hours. Annealing may be performed in any atmosphere as long as it does not interfere with the object of the present invention, preferably in a non-oxygen atmosphere, more preferably in a nitrogen atmosphere.

In the present invention, the film may be formed directly on the substrate, or may be formed via another layer such as a buffer layer (buffer layer) or stress relaxation layer. Methods for forming other layers such as a buffer layer (buffer layer) and a stress relaxation layer are not particularly limited, and known methods may be used. In the present invention, the mist CVD method is preferred.

By forming the film as described above, the substrate can be uniformly and favorably colored in an industrially advantageous manner.

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these.

(Example 1)
1. Film Forming Apparatus A film forming apparatus 1 used in this example will be described with reference to FIG. The film forming apparatus 1 includes a carrier gas source 2a for supplying a carrier gas, a flow control valve 3a for adjusting the flow rate of the carrier gas sent from the carrier gas source 2a, and a carrier gas (dilution) for supplying the carrier gas (dilution). dilution) supply source 2b, flow control valve 3b for adjusting the flow rate of carrier gas (dilution) sent from carrier gas (dilution) supply means 2b, mist generation source 4 containing raw material solution 4a, water 5a, an ultrasonic transducer 6 attached to the bottom surface of the container 5, a hot plate 8, a substrate 10 placed on the hot plate 8, and from the mist source 4 to the vicinity of the substrate 10. and a supply pipe 9 that connects the

2. Preparation of Raw Material Solution C60 fullerene was mixed with mesitylene (1,3,5-trimethylbenzene) and 2-pyrrolidone to obtain a raw material solution. The mixing ratio of mesitylene and 2-pyrrolidone in the solution was 3:1 (volume ratio), and the concentration of C60 fullerene in the solution was 1.4×10 ⁻³ mol/L.

3. Preparing for film formation 2 above. The raw material solution 4 a obtained in 1. was accommodated in the mist generation source 4 . Next, as the substrate 10, a glass/ITO substrate (20 mm.times.25 mm) was placed on the hot plate 8, and the hot plate 8 was operated to raise the temperature of the substrate 10 to 210.degree. Next, the flow control valves 3a and 3b are opened to set the flow rate of the carrier gas supplied from the carrier gas supply source 2a to 2.0 L/min, and the carrier gas (dilution) supplied from the carrier gas (dilution) 2b. The flow rate was adjusted to 4.0 L/min. Nitrogen was used as a carrier gas.

4. Formation of Colored Film Next, the ultrasonic oscillator 6 is vibrated at 2.4 MHz, and the vibration is propagated through the water 5a to the raw material solution 4a, thereby atomizing the raw material solution 4a to generate mist 4b. rice field. A carrier gas is supplied to the mist 4b, and the carrier gas conveys the mist 4b through the supply pipe 9 to the substrate 10, where the mist 4b near the substrate 10 at 210° C. under atmospheric pressure. thermally reacted to form a fullerene film on the substrate 10 . The film thickness of the obtained fullerene film was about 50 nm.

5. Evaluation 4 above. The color of the fullerene film obtained in 1. was yellow, and the substrate was uniformly and well colored while maintaining transparency. Also, the obtained fullerene film was subjected to ultraviolet-visible absorption measurement. The results are shown in FIG. As can be seen from FIG. 2, the obtained fullerene film had an absorption peak between wavelengths of 300 nm and 400 nm.

(Example 2)
A fullerene film was formed in the same manner as in Example 1, except that the film formation temperature was set to 180.degree. The color of the obtained fullerene film was yellow, and the substrate was uniformly and well colored while maintaining transparency. Further, the obtained fullerene film was subjected to UV-visible absorption measurement in the same manner as in Example 1. The results are shown in FIG. As can be seen from FIG. 2, the fullerene film obtained in Example 2 had an absorption peak between wavelengths of 300 nm and 400 nm.

(Examples 3-4)
As Examples 3 and 4, fullerene films were formed in the same manner as in Example 1 except that the film formation temperature in Example 1 was set to 150° C. and 120° C., respectively. The color of the obtained fullerene film was yellow, and the substrate was uniformly and well colored while maintaining transparency. Further, when the obtained fullerene film was subjected to ultraviolet-visible absorption measurement in the same manner as in Example 1, the obtained fullerene film had an absorption peak between wavelengths of 300 nm and 400 nm.

(Examples 5-8)
As Examples 5 to 8, fullerenes were prepared in the same manner as in Examples 1 to 4, respectively, except that the mixing ratio of mesitylene and 2-pyrrolidone in Examples 1 to 4 was 4:1 (volume ratio). A film was deposited. The color of the obtained fullerene film was yellow, and the substrate was uniformly and well colored while maintaining transparency. In addition, when UV-visible absorption measurement was performed on each of the obtained fullerene films in the same manner as in Example 1, all of the obtained fullerene films had an absorption peak in the wavelength range of 300 nm to 400 nm. rice field.

(Examples 9-12)
As Examples 9 to 12, fullerenes were prepared in the same manner as in Examples 1 to 4, respectively, except that the mixing ratio of mesitylene and 2-pyrrolidone in Examples 1 to 4 was 7:3 (volume ratio). A film was deposited. The color of the obtained fullerene film was yellow, and the substrate was uniformly and well colored while maintaining transparency. In addition, when UV-visible absorption measurement was performed on each of the obtained fullerene films in the same manner as in Example 1, all of the obtained fullerene films had an absorption peak in the wavelength range of 300 nm to 400 nm. rice field.

(Comparative example 1)
A film was formed in the same manner as in Example 1, except that only mesitylene was used as a solvent. As a result, the film formation rate was 1/10 or less of that in Example 1, and uneven coloring was observed.

(Comparative example 2)
A film was formed in the same manner as in Example 1, except that only 2-pyrrolidone was used as a solvent. However, the C60 fullerene was hardly soluble in the solvent, and it was difficult to atomize, so it was impossible to form a film.

The coloring method of the present invention is industrially advantageous and can uniformly and satisfactorily color a substrate without using a resin as a binder. , substrates, etc., and can be used in a wide variety of fields.

REFERENCE SIGNS LIST 1 film forming apparatus 2a carrier gas source 2b carrier gas (dilution) source 3a flow control valve 3b flow control valve 4 mist generation source 4a raw material solution 4b mist 5 container 5a water 6 ultrasonic vibrator 7 nozzle 8 hot plate 9 supply pipe 10 substrate

Claims (7)

A method for coloring a substrate by forming a colored film on the substrate using a mist or droplets of a raw material solution containing at least a coloring agent and a solvent, wherein the solvent is a nonpolar solvent and the nonpolar A polar solvent having a higher boiling point than the solvent is contained so that the volume ratio of the non-polar solvent and the polar solvent is 4:1 to 7:3, the colorant is a polycyclic pigment, and the composition is A coloring method, wherein the film is formed by thermally reacting the mist or the droplets on the substrate. The coloring method according to claim 1, wherein the polar solvent is an aprotic polar solvent. The coloring method according to claim 1 or 2, wherein the nonpolar solvent is represented by the following formula (1).

(Wherein, R ¹ to R ⁶ are each the same or different and represent a hydrogen atom or a hydrocarbon group optionally having a substituent, and any two groups selected from R ¹ to R ⁶ are bonded may form a ring.) The coloring method according to any one of claims 1 to 3, wherein the boiling point difference between the nonpolar solvent and the polar solvent is 50°C or more. The coloring method according to any one of claims 1 to 4, wherein the thermal reaction is performed at a temperature below the boiling point of the polar solvent. 6. The thermal reaction according to any one of claims 1 to 5, wherein the thermal reaction is carried out after supplying a carrier gas to the mist or the droplets, and then transporting the mist or the droplets to the substrate using the carrier gas. coloring method. The coloring method according to any one of claims 1 to 6, wherein the mist or the droplets are obtained using ultrasonic vibration.

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