WO2012124785A1 - Composition colorante composite organique-inorganique et procédé de production de celle-ci - Google Patents

Composition colorante composite organique-inorganique et procédé de production de celle-ci Download PDF

Info

Publication number
WO2012124785A1
WO2012124785A1 PCT/JP2012/056776 JP2012056776W WO2012124785A1 WO 2012124785 A1 WO2012124785 A1 WO 2012124785A1 JP 2012056776 W JP2012056776 W JP 2012056776W WO 2012124785 A1 WO2012124785 A1 WO 2012124785A1
Authority
WO
WIPO (PCT)
Prior art keywords
inorganic
coloring composition
organic
organic composite
fibrous clay
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/056776
Other languages
English (en)
Japanese (ja)
Inventor
純男 海崎
隆弘 瀧川
西村　善彦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TURNER COLOUR WORKS Ltd
University of Osaka NUC
Original Assignee
TURNER COLOUR WORKS Ltd
Osaka University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TURNER COLOUR WORKS Ltd, Osaka University NUC filed Critical TURNER COLOUR WORKS Ltd
Priority to JP2013504779A priority Critical patent/JPWO2012124785A1/ja
Publication of WO2012124785A1 publication Critical patent/WO2012124785A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26—Aluminium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0002—Grinding; Milling with solid grinding or milling assistants
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0091—Process features in the making of dispersions, e.g. ultrasonics
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0096—Purification; Precipitation; Filtration
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes

Definitions

  • the present invention relates to an inorganic / organic composite coloring composition that is excellent in weather resistance and chemical resistance, and has little fading (discoloration) over time, and a method for producing the same.
  • Maya Blue exhibits the vibrant blue color found in mesoamerican ruins and murals.
  • Maya Blue is a composite of an inorganic compound and an organic compound. Specifically, it is composed of palygorskite which is a clay mineral and indigo which is an organic dye.
  • Palygorskite is a clay mineral having a channel structure.
  • Indigo on the other hand, is a blue-indigo dye.
  • Maya Blue is an inorganic / organic composite coloring material formed by indigo being incorporated into a palygorskite channel.
  • Maya Blue can be obtained by the following method.
  • the indigo is first reduced and mixed with the clay mineral, and then the mixture is exposed to air to oxidize. By passing through this step, an inorganic / organic composite exhibiting a blue color is obtained. Furthermore, the blue coloration is stabilized by heating the inorganic / organic composite.
  • the Maya Blue obtained by the above-mentioned method has a vivid blue color, but is not excellent in weather resistance, and there is a problem that the initial vivid blue color cannot be maintained by fading over time. Similar problems have also been encountered with coloring materials of inorganic / organic composites exhibiting red and yellow.
  • Patent Document 1 describes a coating composition comprising a molecular derivative of indigo and fibrous or layered clay and a method for producing the same.
  • a complex of indigo and clay mineral is heated at a temperature of 100 to 300 ° C. for several hours to 4 days. The coloration is stabilized by performing this heat treatment.
  • a coating composition having a blue fading of 10% or less in one year can be obtained.
  • the color of the coloring object colored by the coloring composition is most often faded at the initial stage after coloring. In other words, it fades exponentially.
  • the technology disclosed in Patent Document 1 cannot prevent such a large initial fading.
  • the color forming composition described in Patent Document 1 has a fading degree of 10% or less in one year. The fading at such a ratio causes a color change that can be visually recognized. That is, with the technique described in Patent Document 1, a color composition having a small color difference ( ⁇ E) (for example, 2 or less) and cannot be visually recognized cannot be obtained.
  • ⁇ E small color difference
  • the present invention has been made to solve the problems of the prior art described above, and provides an inorganic / organic composite coloring composition that has less fading after coloring a coloring object and has excellent weather resistance, and a method for producing the same. It is to provide.
  • the invention according to claim 1 is an inorganic / organic composite coloring composition comprising a clay mineral and an organic dye, wherein the clay mineral is a fibrous clay, and the coloring composition JIS K5600 is colored.
  • the present invention relates to an inorganic / organic composite coloring composition characterized in that a color difference ⁇ E at an irradiation time of 500 hours in a weather resistance test according to -7-7 is 2 or less.
  • the invention according to claim 2 is the inorganic / organic composite according to claim 1, wherein the organic dye comprises at least one selected from the group consisting of indigo, indirubin, herringdon pink CN, methyl red, and quinoline dye.
  • the present invention relates to a coloring composition.
  • the invention according to claim 3 relates to an inorganic / organic composite coloring composition according to claim 1 or 2, characterized in that it contains rare earth element ions.
  • the invention according to claim 4 relates to the inorganic / organic composite coloring composition according to claim 3, wherein the rare earth element ion includes a lanthanum ion.
  • the rare earth element ion is selected from trivalent cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium, and divalent europium.
  • the invention according to claim 6 is a method for producing an inorganic / organic composite coloring composition comprising a fibrous clay, which is a clay mineral, and an organic dye
  • the present invention relates to a method for producing an inorganic / organic composite coloring composition comprising the following steps (1) and (2), and (2A) and / or (3).
  • (1) The step of pulverizing the fibrous clay and the organic dye to 0.1 to 70 ⁇ m and mixing the fibrous clay and the organic dye (2)
  • the fibrous clay obtained in the step (1) The step of heating the colored material comprising the organic dye at 120 to 200 ° C.
  • the colored material comprising the fibrous clay and the organic dye Prior to the step (2), the colored material comprising the fibrous clay and the organic dye is added to the step (2) A step of dispersing in a solvent having a boiling point higher than the heating temperature of (2) (3) The crude colored composition comprising the fibrous clay obtained in the step (2) and the organic dye is washed to obtain an inorganic Step of obtaining an organic composite coloring composition
  • the invention according to claim 7 is a wet manufacturing method of an inorganic / organic composite coloring composition comprising a fibrous clay which is a clay mineral and an organic dye, It has the following process (1B), It is related with the manufacturing method of the inorganic and organic composite coloring composition of Claim 6.
  • (1B) After the step (1), the solution containing the reduced organic dye and the fibrous clay was subjected to the reduction by applying ultrasonic waves while stirring so as not to entrain air in the solution. Step of sufficiently blending the organic dye and the fibrous clay, and then stirring the solution so as to take in air and oxidizing the organic dye with air
  • the organic dye is indigo
  • the crude colored composition comprising the fibrous clay obtained in the step (2) and the organic dye is converted into an alkaline solution containing a reducing agent.
  • the invention according to claim 9 is characterized in that the organic dye comprises at least one selected from the group consisting of indirubin, herringdon pink CN and methyl red, and the fibrous clay obtained in the step (2) and the organic dye.
  • the method comprises a step of washing a crude coloring composition comprising a dye with an alkaline solution containing a reducing agent or washing with a Soxhlet extraction with water to obtain an inorganic / organic composite coloring composition. It relates to a method for producing an inorganic / organic composite coloring composition according to claim 6.
  • the invention according to claim 10 is characterized in that the organic dye is a quinoline dye, and the crude colored composition comprising the fibrous clay obtained in the step (2) and the organic dye contains a reducing agent.
  • the inorganic / organic composite coloring composition according to claim 6, comprising a step of washing with an alkaline solution or washing with Soxhlet extraction with ethanol to obtain an inorganic / organic composite coloring composition. It relates to a manufacturing method.
  • the invention according to claim 11 is characterized in that, in the step (1), the rare earth element ions are incorporated into the fibrous clay by ion exchange, and then the rare earth element ions are incorporated by ion exchange and the organic clay.
  • the present invention relates to a method for producing an inorganic / organic composite coloring composition according to any one of claims 6 to 10, wherein a dye is mixed.
  • the invention according to claim 12 relates to a method for producing an inorganic / organic composite coloring composition according to claim 11, wherein the rare earth element ion includes a lanthanum ion.
  • the rare earth element ion is selected from trivalent cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium, and divalent europium. It is at least 1 type of ion, It is related with the manufacturing method of the inorganic and organic complex coloring composition of Claim 11 or 12.
  • the invention according to claim 14 relates to the method for producing an inorganic / organic composite coloring composition according to any one of claims 7 to 13, wherein the reducing agent is sodium hydrosulfite.
  • an inorganic / organic composite coloring composition comprising a clay mineral and an organic dye, wherein the clay mineral is a fibrous clay, and the coloring composition is a coloring object. Since the color difference ⁇ E at an irradiation time of 500 hours according to a weather resistance test according to JIS K5600-7-7 is 2 or less, it is possible to obtain a colored composition having excellent weather resistance with little color fading.
  • the organic / dye composite coloring composition wherein the organic dye is at least one selected from the group consisting of indigo, indirubin, herringdon pink CN, methyl red, and quinoline dye. Therefore, it can be set as the blue, red, and yellow coloring composition excellent in the weather resistance with few fading of a coloring target object.
  • the surface area and acidity of the inorganic / organic composite coloring composition can be increased, and the weather resistance is improved. It can be set as the outstanding coloring composition.
  • the surface area and acidity of the inorganic / organic composite coloring composition can be increased, and the weather resistance is excellent.
  • a colored composition since it is an inorganic / organic composite coloring composition containing lanthanum ions, the surface area and acidity of the inorganic / organic composite coloring composition can be increased, and the weather resistance is excellent.
  • the coloring composition can be provided with light-emitting properties, and the coloring composition can be colored more vividly. Therefore, the visibility of the colored object can be increased.
  • the inorganic and organic composite coloring composition which consists of the fibrous clay which is a clay mineral, and organic dye, Comprising: (1) Said fibrous clay and said organic dye A step of pulverizing to 0.1 to 70 ⁇ m and mixing the fibrous clay and the organic dye; and (2) a colored material comprising the fibrous clay obtained in the step (1) and the organic dye is 120 to A step of heating at 200 ° C. for 1 to 24 hours; and (3) an inorganic / organic composite coloring composition by washing the crude coloring composition comprising the fibrous clay obtained in the step (2) and the organic dye.
  • a colored composition having excellent weather resistance with less fading of the coloring object can be obtained.
  • the inorganic and organic complex coloring composition which consists of fibrous clay which is a clay mineral, and organic dye, Comprising: (1A) Before the said process (1) The organic dye is dissolved in an aqueous solvent by dispersing the organic dye in an aqueous solvent and reducing the organic dye with a reducing agent to prepare a solution containing the reduced organic dye. The organic dye can be efficiently incorporated into the fibrous clay.
  • the reduced organic dye and the fibrous clay are sufficiently blended, and then the solution is stirred so as to take in air, and the organic dye is air-oxidized.
  • the organic dye is air-oxidized.
  • the said organic dye is indigo, Comprising: The crude coloring composition which consists of the said fibrous clay obtained at the said process (2) and the said organic dye contains a reducing agent.
  • the organic dye comprises at least one selected from the group consisting of indirubin, herringdon pink CN and methyl red, and the fibrous clay obtained in the step (2)
  • An inorganic / organic composite coloring composition obtained by washing the crude coloring composition comprising the organic dye with the alkaline coloring composition by washing with an alkaline solution containing a reducing agent or by Soxhlet extraction with water.
  • the organic dye in a state where it is not taken into the channel of the fibrous clay and is simply attached, thereby eliminating the fading of the coloring object, and thereby providing a red coloring composition with excellent weather resistance. Can be obtained.
  • the organic dye is a quinoline dye
  • the crude coloring composition comprising the fibrous clay obtained in the step (2) and the organic dye is used as a reducing agent.
  • the fibrous clay in which the rare earth element ions are incorporated by ion exchange since it is a manufacturing method of an inorganic / organic composite coloring composition in which the organic dye is mixed, a coloring composition having excellent weather resistance can be obtained because the surface area and acidity of the inorganic / organic composite coloring composition can be increased. Obtainable.
  • the fibrous clay into which the lanthanum ions are taken in by ion exchange and the organic dye are mixed. Since it is a manufacturing method, the surface area and acidity of an inorganic and organic composite coloring composition can be increased, and the coloring composition excellent in the weather resistance can be obtained.
  • a three-primary-colored three-primary-color light-emitting composition that is bright in color and excellent in visibility can be obtained.
  • the reducing agent is a method for producing an inorganic / organic composite coloring composition that is sodium hydrosulfite, the organic dye can be completely reduced and dissolved. Therefore, when the coloring composition is washed, it is possible to remove excess organic dye having poor weather resistance that adheres to the fibrous clay. Therefore, it can be set as the coloring composition with little fading.
  • the inorganic / organic composite coloring composition and the method for producing the same according to the present invention will be described in detail below.
  • the inorganic / organic composite coloring composition according to the present invention comprises a clay mineral that is an inorganic compound and an organic dye that is an organic compound.
  • the clay mineral palygorskite and sepiolite are used.
  • Palygorskite and sepiolite are fibrous clay minerals that grow with unit cells connected in a chain. These clay minerals have a channel structure. The channel is formed in the b-axis direction of the unit cell. Since the above clay mineral has a channel structure, an organic dye described later can be taken into the channel.
  • Palygorskite and sepiolite may be used singly or in combination.
  • clay minerals similar in structure to palygorskite and sepiolite can be used. That is, a fibrous clay mineral having a channel structure can be used.
  • a clay mineral that is not fibrous that is, a layered clay mineral.
  • Specific examples include kaolinite and bentonite.
  • Layered clay minerals can incorporate organic dyes between layers, but lack stability compared to channel structures. For this reason, the organic dye may not be fixed between the layers.
  • indigo, indirubin, herringdon pink CN, methyl red and quinoline dyes are preferably used, but other organic dyes may be used.
  • Indigo is an organic dye exhibiting a blue-blue color and has a structure represented by the following formula (Chemical Formula 1).
  • Indigo has an insoluble property in water, alcohol and ether in the state shown in the following formula (Chemical Formula 1).
  • it is soluble in trichloromethane, nitrobenzene and concentrated sulfuric acid even in the state shown in the following formula (Chemical Formula 1).
  • leucoin digo has a light yellow color and is soluble in water.
  • a solution containing leucoin digo (hereinafter referred to as leucoin digo solution) is colorless and transparent.
  • leucoin jig is oxidized, it returns to indigo and again exhibits a blue-blue color. That is, indigo and roycoin jigo have a reversible relationship.
  • Indirubin, herringdon pink CN and methyl red are used as organic dyes exhibiting red color.
  • Indirubin has the chemical name ⁇ (2,3 ′)-biindolin) -2 ′, 3-dione ((delta (2,3 ′)-Biindoline) -2 ′, 3-dione), CAS. No. Is 479-41-4 and has a structure represented by the following formula (Formula 3).
  • Herringdon Pink CN is an organic pigment generally referred to as Red No. 226. Chemical name 6,6′-Dichloro-4,4′-dimethylthioindigo, CAS No. Is 2379-74-0 and has the structure shown in the following formula (Formula 4).
  • Methyl red is one of the azo dyes and has the chemical name p-dimethylaminoazobenzene-o-carboxylic acid, CAS. No. Is 493-52-7 and has the structure shown in the following formula (Formula 5).
  • a quinoline dye is used as the organic dye exhibiting a yellow color.
  • the quinoline dye is not limited to this, but Disperse Yellow 54 is preferably used.
  • Disperse Yellow 54 has the chemical name 3-Hydroxyquinophthalone, CAS No. Is 12223-85-7 and has the structure shown in the following formula (Formula 6).
  • the inorganic / organic composite coloring composition according to the present invention is composed of the above-described fibrous clay mineral (palygorskite, sepiolite) and an organic dye.
  • Organic dye molecules are incorporated into the palygorskite and sepiolite (fibrous clay) channels.
  • the organic dye molecules incorporated into the fibrous clay are stabilized in the channel by hydrogen bonding or van der Waals force (interaction) with oxygen constituting the fibrous clay.
  • the color difference ⁇ E after coloring is an accelerated weathering tester for xenon lamps. Is measured according to JIS K5600-7-7, and the irradiation time is 500 or less and is 2 or less.
  • the complex coloring composition of the above-described fibrous clay and organic dye has a color difference ⁇ E exceeding 2 by a known technique. That is, fading starts after coloring, and it becomes difficult to maintain the original color of the colored composition.
  • the color difference ⁇ E in the present invention is based on JIS Z8730.
  • the inorganic / organic composite coloring composition according to the present invention is obtained by a method for producing an inorganic / organic composite coloring composition described later.
  • the rare earth element ions are selected from lanthanide ions.
  • the rare earth element ions contained in the inorganic / organic composite coloring composition according to the present invention include lanthanum ions and / or trivalent cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, It is at least one ion selected from thulium and ytterbium, and divalent europium.
  • the surface area and acidity of the inorganic / organic composite coloring composition can be increased.
  • Trivalent cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium, and divalent europium ions can impart luminescence to the colored composition.
  • the inorganic / organic composite coloring composition containing the rare earth element ion described above has a color difference ⁇ E after coloring of an irradiation time of 500 in a weather resistance test according to JIS K5600-7-7. 2 or less in time.
  • the inorganic / organic composite coloring composition according to the present invention is produced by a dry method and a wet method using a fibrous clay (palygorskite, sepiolite) and an organic dye.
  • indigo, indirubin, herringdon pink CN, methyl red and quinoline dyes are preferably used as the organic dye.
  • the manufacturing method of the blue-red-yellow primary color inorganic / organic composite coloring composition described below the manufacturing method when indigo is used as the organic dye is described, but the manufacturing method is the same when other organic dyes are used. It is.
  • the method for producing an inorganic / organic composite coloring composition according to the present invention mainly comprises (1) pulverization and mixing of fibrous clay and indigo, (2) heating step, and (3) washing step.
  • the steps (1) to (3) will be described in the order of the steps common to the dry method and the wet method, the step based on the dry method, and the step based on the wet method.
  • Step (1C) Step of incorporating rare earth element ions When taking in rare earth element ions, a compound containing rare earth element ions is added. By doing so, rare earth element ions are ion-exchanged with magnesium ions of the fibrous clay.
  • the rare earth element ions added in the present invention are lanthanum ions and / or trivalent cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium, and divalent europium. At least one ion selected.
  • the surface area and acidity of the inorganic / organic composite coloring composition can be increased.
  • Trivalent cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium, and divalent europium ions can impart luminescence to the colored composition.
  • the rare earth element ions to be added are added in the form of a salt such as nitrate. Specifically, lanthanum nitrate hexahydrate, neodymium nitrate hexahydrate, and europium nitrate hexahydrate.
  • a salt such as nitrate.
  • the salt concentration described above the amount of rare earth element ions incorporated into the fibrous clay by ion exchange changes.
  • acid pretreated fibrous clay obtained by removing calcium carbonate, which is an impurity in the fibrous clay, with concentrated hydrochloric acid.
  • the fibrous clay It is preferable to remove calcium carbonate, which is an impurity, from the fibrous clay with concentrated hydrochloric acid.
  • this acid pretreated fibrous clay When this acid pretreated fibrous clay is used, rare earth element ions can be efficiently incorporated.
  • the fibrous clay incorporating the rare earth element ions is preferably filtered and washed with water. Thereby, the rare earth element ion which is not taken in by the fibrous clay can be removed.
  • Step (1) in the dry method fibrous clay and indigo are mixed by a mechanical method using, for example, a mixer, and the fibrous clay and indigo are mixed by a mechanical method using a dry pulverizer such as a ball mill. Finely pulverize to 0.1 to 70 ⁇ m.
  • the mechanical method of pulverization is not limited to the above method.
  • Step of reducing indigo The manufacturing method by the wet method includes a step (step (1A)) of preparing a leucoin digo solution by dispersing indigo in a solvent and reducing indigo with a reducing agent before the step (1).
  • step (1A) first, indigo is dispersed in an aqueous solvent, and the indigo is reduced with a reducing agent. Indigo does not dissolve in water as it is (see (Chemical Formula 1) above). However, in the state of leucoin digo (see above (Chemical Formula 2)) obtained by reducing indigo, it becomes soluble in water. Therefore, first, indigo is reduced with a reducing agent.
  • a predetermined amount of indigo is added to an aqueous solvent and dispersed.
  • an aqueous solvent in which indigo is dispersed it is preferable to use water.
  • the water used for the aqueous solvent is preferably purified water such as pure water or ultrapure water. By using purified water, the amount of impurities in the final inorganic / organic composite coloring composition can be reduced.
  • Indigo is in a dispersed state without being dissolved in an aqueous solvent.
  • a reducing agent is added to the dispersion medium in which the indigo is dispersed.
  • the amount of indigo added is preferably 3 to 10 parts by weight with respect to 100 parts by weight of clay mineral described later. When added in the above range, indigo is taken into the structure of the fibrous clay without excess or deficiency, and a vividly colored coloring composition can be obtained.
  • the amount of indigo is less than 3 parts by weight, there is a possibility that sufficient color development cannot be obtained because the amount of dye incorporated into the fibrous clay becomes too small. Moreover, when it exceeds 10 weight part, the dye which is not taken in in fibrous clay will arise.
  • the excess indigo that is not taken up adheres to the surface of the fibrous clay. This indigo adhering to the surface of the fibrous clay is not preferable because it becomes one of the causes of color change (fading) after coloring the coloring object, as will be described later.
  • sodium hydrosulfite sodium dithionite
  • Sodium hydrosulfite has the property of being acidic and decomposing. By making the aqueous solvent alkaline, it is possible to prevent the decomposition of sodium hydrosulfite. Therefore, indigo can be reliably reduced.
  • the addition amount of the reducing agent is preferably 100 to 3000% by weight with respect to indigo.
  • indigo can be completely reduced and dissolved in the solvent. If it is less than 100% by weight, the reduction of indigo becomes insufficient, and there is a possibility that indigo will remain without being reduced (see (Chemical Formula 1)). Therefore, there is a possibility that indigo that is not taken into the fibrous clay is generated. On the other hand, if it exceeds 3000% by weight, no further effect can be expected.
  • fibrous clay is added to the leuco indigo solution.
  • the fibrous clay is preferably dispersed in water and then added to the solution. However, the fibrous clay may be added directly, or the leucoin digo solution may be added to a solution containing clay minerals.
  • Indigo reduced in the step (1A) is dissolved in an aqueous solvent. That is, the dye is present in the aqueous solvent in the form of leucoin digo.
  • the aqueous solvent (leucoin digo solution) containing leucoin digo is light yellow.
  • the fibrous clay added to the leucoin digo solution is the aforementioned palygorskite and sepiolite. Since these fibrous clays are described in the description of the inorganic / organic composite coloring composition according to the present invention, they are omitted here.
  • the fibrous clay is preferably pulverized to a particle size in the range of 0.1 to 70 ⁇ m and added to the leucoin digo solution. Micronization can be performed by a mechanical method similar to the dry method or by application of ultrasonic waves. By setting the particle size of the fibrous clay in the above range, the contact area with the leuco coin jig in the solution can be increased.
  • Step (1B) ultrasonic application and stirring step in wet method An ultrasonic wave is applied to the solution containing leuco indigo and fibrous clay obtained in the above step.
  • ultrasonic waves By applying ultrasonic waves to the above solution, leuco indigo is more efficiently taken into the channel of the fibrous clay. Cavitation occurs when ultrasonic waves are applied to the solution. Therefore, the dispersibility of fibrous clay improves and the contact with leucoin digo and fibrous clay increases.
  • roy coin jig is inserted into the fibrous clay channel by pressure by cavitation. That is, it can be prevented from adhering to the surface without being taken into the channel of the fibrous clay. Therefore, weather resistance can be improved.
  • the frequency of the ultrasonic wave applied to the leuco indigo and the fibrous clay is preferably 28 to 100 kHz, and more preferably 30 to 40 kHz. If it is less than 28 kHz, the dispersion of the fibrous clay may be insufficient. On the other hand, even if it exceeds 100 kHz, the dispersion of fibrous clay and the insertion of leuco digo into the channel cannot be further promoted.
  • the application time of the ultrasonic wave is desirably 10 minutes or more, and more preferably 60 minutes or more. If it is less than 10 minutes, the dispersion of the fibrous clay may be insufficient.
  • the application of ultrasonic waves is performed while stirring the leuco indigo solution to which fibrous clay is added so that air is not involved in the solution.
  • leuco indigo is easily taken into the channel of fibrous clay.
  • the reason why the air is stirred so as not to get caught in the solution is to prevent the leucoin digo from being oxidized before being taken into the fibrous clay.
  • leuco coin jig is not efficiently taken into the channel.
  • it is not taken up by the channel and only adheres to the surface of the clay mineral. This is not preferable because it causes discoloration after coloring the coloring object.
  • the solution is then agitated to entrain air and oxidized by exposing the leuco digo to air.
  • the leucoin jigs present in the channel of the fibrous clay are oxidized and become indigo (see (Chemical Formula 1)) again.
  • the dye that is oxidized to indigo has a blue-blue color. Therefore, it looks as if the fibrous clay itself is colored indigo blue.
  • the colored material composed of fibrous clay and indigo obtained in the above step (1) is heated and dried.
  • the heating temperature is preferably 120 to 200 ° C, and more preferably 150 to 180 ° C.
  • indigo attached to the fibrous clay does not get stuck in the channel, and the weather resistance of the coloring composition is deteriorated.
  • the temperature exceeds 200 ° C., the discoloration of indigo may increase, which is not preferable. It is preferable to heat in the above temperature range for 1 to 24 hours. Indigo can be stabilized by heating under such conditions.
  • the solvent is removed and dried.
  • This solvent can be removed using aspirator suction filtration or a centrifuge, but the removal method is not limited thereto.
  • Step (3) Cleaning step> The crude colored composition composed of fibrous clay and indigo obtained by heating in the above step (2) is washed with a solution containing a reducing agent. That is, in the step (3), indigo that is simply attached is removed without being taken into the channel of the fibrous clay. By using a reducing agent, indigo attached to the fibrous clay is reduced to leucoin digo and can be dissolved. Leucoin digo is dissolved and removed in a solution containing a reducing agent.
  • Indigo that is simply attached without being taken into the channel of fibrous clay causes discoloration.
  • Indigo taken into the channel is stabilized in the fibrous clay (channel) by interactions such as hydrogen bonds and van der Waals forces.
  • the indigo adhering to the surface of the fibrous clay is not stabilized and is only physically adsorbed with the fibrous clay mineral, and is the interaction (hydrogen bond or van der Waals force) weak? Few.
  • Such indigo is decomposed or oxidized by, for example, ultraviolet rays or acids. If it does so, since it will not be indigo which exhibits a blue indigo color, the change of the color of a coloring target object will become large apparently. By removing the excess indigo, the cause of color change (fading) can be eliminated.
  • the reducing agent it is preferable to use the same reducing agent as in the above step (1A). That is, sodium hydrosulfite (sodium dithionite) is suitable. By using sodium hydrosulfite, indigo can be reduced to leucoin digo and easily removed (dissolved). As described above, by passing through this step (3), the crude coloring composition can be purified, and an inorganic / organic composite coloring composition having excellent weather resistance and less fading can be obtained.
  • this washing step must be performed.
  • red dye indirubin When one or more selected from the group consisting of red dye indirubin, herringdon pink CN, and methyl red is used as the organic dye, it is washed with an alkaline solution containing a reducing agent, or washed with Soxhlet extraction with water
  • a quinoline dye which is a yellow dye
  • Soxhlet extraction with ethanol When a quinoline dye, which is a yellow dye, is used as the organic dye, it is preferably washed with an alkaline solution containing a reducing agent or by Soxhlet extraction with ethanol. Thereby, excess organic dye can be removed and the cause of a color change (fading) can be removed.
  • Example 1 Production Method 1 for Coloring Composition of Inorganic / Organic Complex by Dry Method Process
  • Indigo (Dystar Indigo Gr, manufactured by Dystar Japan) 0.5 g was added to 10 g of palygorskite (Atagel # 40, manufactured by Engelhard) and mixed with a mixer. The mixture was pulverized using a ball mill and pulverized, and then mixed well with a mixer.
  • Process (2) The colored product composed of palygorskite and indigo obtained in the above step (1) was heated at 170 ° C. for 6 hours to obtain 10 g of a crude colored composition composed of palygorskite and indigo.
  • Step (3) The crude coloring composition composed of palygorskite and indigo obtained in the above step (2) is washed with a solution composed of 1.5 g of sodium hydrosulfite, 10 g of 2M aqueous sodium hydroxide solution and 100 g of distilled water, and colored with an inorganic / organic complex. 9.0 g of the composition was purified. In addition, the amount of indigo loss before and after washing was reduced by about 30% from the result of CHN analysis.
  • Example 2 Production Method 1 of Inorganic / Organic Complex Coloring Composition by Wet Method Step (1A) 0.5 g of Indigo (Dystar Indigo Gr, manufactured by Dystar Japan) was added to 22.5 g of distilled water, and 10 g of 2M aqueous sodium hydroxide solution was added to this solution. Next, a solution composed of 100 g of distilled water and 1.5 g of sodium hydrosulfite as a reducing agent was added with the air shut off to reduce indigo to obtain 134.5 g of leucoin digo solution.
  • Indigo Dystar Indigo Gr, manufactured by Dystar Japan
  • Step (1B) After incubating the solution obtained in the above step (1) at 50 ° C. for 40 minutes, an ultrasonic wave having a frequency of 37 to 42 kHz was applied to the solution for 30 minutes while stirring the solution so that air was not involved in the solution. Then, the mixture was stirred for 60 minutes so that air was taken into the solution, and leucoin digo was oxidized and insolubilized.
  • Process (2) The solution containing the colored product composed of palygorskite and indigo obtained in the above step (1B) was suction filtered, washed with water, dried at 50 ° C. to obtain a powder, and the powder was heated at 170 ° C. for 6 hours.
  • Step (3) The crude coloring composition consisting of palygorskite and indigo obtained in the above step (2) was washed with a solution consisting of 1.5 g of sodium hydrosulfite, 10 g of 2M aqueous sodium hydroxide solution and 100 g of distilled water at 50 ° C. for 40 minutes, 8.7 g of the inorganic / organic composite coloring composition was purified. In addition, the amount of indigo loss before and after washing was reduced by about 30% from the result of CHN analysis.
  • Example 3 Method 2 for producing an inorganic / organic composite coloring composition by a dry method Process (1) 0.5 g of Indigo (Dystar Indigo Gr, manufactured by Dystar Japan) was added to 10 g of sepiolite (Pangel AD, manufactured by TOLSA) and mixed with a mixer. The mixture was pulverized using a ball mill and pulverized, and then mixed well with a mixer.
  • Indigo Dystar Indigo Gr, manufactured by Dystar Japan
  • Pangel AD sepiolite
  • Process (2) The colored product composed of sepiolite and indigo obtained in the above step (1) was heated at 170 ° C. for 6 hours to obtain 10 g of a crude colored composition composed of sepiolite and indigo.
  • Step (3) The crude colored composition composed of sepiolite and indigo obtained in the above step (2) is washed with a solution composed of 1.5 g of sodium hydrosulfite, 10 g of 2M aqueous sodium hydroxide solution and 100 g of distilled water, and colored with an inorganic / organic complex. 9 g of the composition was purified.
  • Example 4 Method 3 for producing inorganic / organic composite coloring composition by dry method Process (1) To 10 g of palygorskite (Zemex 601-P, manufactured by Zemex), 0.5 g of Herringdon Pink CN (Red 226, manufactured by Kasei Kasei) was added and mixed with a mixer. The mixture was pulverized using a ball mill and pulverized, and then mixed well with a mixer.
  • palygorskite Zemex 601-P, manufactured by Zemex
  • Herringdon Pink CN Red 226, manufactured by Kasei Kasei
  • Step (2A) 10 g of a colored product composed of palygorskite and herringdon pink CN obtained in the above step (1) was added to 100 g of propylene glycol and dispersed.
  • Process (2) The propylene glycol solution containing the colored product composed of palygorskite and herringdon pink CN obtained in the above step (2A) is heated at 170 ° C. for 6 hours, filtered with suction, washed with water, dried at 50 ° C. 9.6 g of a crude coloring composition comprising palygorskite and red 226 was obtained.
  • Step (3) The crude colored composition composed of palygorskite and herringdon pink CN obtained in the above step (2) was washed with a solution composed of 1.5 g of sodium hydrosulfite, 10 g of 2M aqueous sodium hydroxide solution and 100 g of distilled water, and inorganic and organic The complex coloring composition 8.0g was refine
  • Example 5 Method 2 for producing an inorganic / organic composite coloring composition by a wet method Step (1A) 0.5 g of Indigo (Dystar Indigo Gr, manufactured by Dystar Japan) was added to 22.5 g of distilled water, and 10 g of 2M aqueous sodium hydroxide solution was added to this solution. Next, a solution consisting of 100 g of distilled water and 1.5 g of sodium hydrosulfite was added as a reducing agent to reduce indigo to obtain 134.5 g of leucoin digo solution.
  • Indigo Dystar Indigo Gr, manufactured by Dystar Japan
  • Step (1C) 10 g of palygorskite (Atagel # 40, manufactured by Engelhard) was added to 115 g of distilled water, and a solution consisting of 285 g of distilled water and 0.52 g of lanthanum nitrate hexahydrate was added to this solution. The solution was stirred at 80 ° C. for 4 hours.
  • palygorskite Atagel # 40, manufactured by Engelhard
  • Process (1) The solution obtained in the step (1C) and 134.5 g of the leucoin digo solution obtained in the step (1A) were mixed to obtain 545 g of a solution containing indigo and palygorskite.
  • Step (1B) After incubating the solution obtained in the above step (1) at 50 ° C. for 40 minutes, an ultrasonic wave having a frequency of 37 to 42 kHz was applied to the solution for 30 minutes while stirring the solution so as not to entrain air in the solution. Then, stirring was performed so that air was taken into the solution for 60 minutes, and leuco digo was oxidized and insolubilized.
  • Process (2) The solution containing the colored product composed of palygorskite and indigo obtained in the above step (1B) was suction filtered, washed with water, dried at 50 ° C. to obtain a powder, and the powder was heated at 170 ° C. for 6 hours.
  • Step (3) The crude coloring composition consisting of palygorskite and indigo obtained in the above step (2) was washed with a solution consisting of 1.5 g of sodium hydrosulfite, 10 g of 2M aqueous sodium hydroxide solution and 100 g of distilled water at 50 ° C. for 40 minutes, 9.0 g of the inorganic / organic composite coloring composition was purified.
  • Example 6 Method 3 of Manufacturing Inorganic / Organic Complex Colored Composition by Wet Method Step (1A) 0.5 g of Indigo (Dystar Indigo Gr, manufactured by Dystar Japan) was added to 22.5 g of distilled water, and 10 g of 2M aqueous sodium hydroxide solution was added to this solution. Next, a solution consisting of 100 g of distilled water and 1.5 g of sodium hydrosulfite was added as a reducing agent to reduce indigo to obtain 134.5 g of leucoin digo solution.
  • Indigo Dystar Indigo Gr, manufactured by Dystar Japan
  • Step (1C) 10 g of palygorskite (Atagel # 40, manufactured by Engelhard) was added to 115 g of distilled water, and a solution consisting of 285 g of distilled water and 0.52 g of lanthanum nitrate hexahydrate was stirred at 80 ° C. for 4 hours. In exchange, lanthanum ions were incorporated into the palygorskite. This solution was filtered, and the palygorskite was thoroughly washed with water and dried.
  • palygorskite Atagel # 40, manufactured by Engelhard
  • Process (1) The palygorskite obtained in the step (1C) and 134.5 g of the leucoin digo solution obtained in the step (1A) were mixed to obtain 545 g of a slurry solution.
  • Step (1B) After incubating the solution obtained in the above step (1) at 50 ° C. for 40 minutes, an ultrasonic wave having a frequency of 37 to 42 kHz was applied to the solution for 30 minutes while stirring the solution so as not to entrain air in the solution. Then, stirring was performed so that air was taken into the solution for 60 minutes, and indigo was oxidized and insolubilized.
  • Process (2) The solution containing the colored product composed of palygorskite and indigo obtained in the above step (1B) was suction filtered, washed with water, dried at 50 ° C. to obtain a powder, and the powder was heated at 170 ° C. for 6 hours.
  • Step (3) The crude coloring composition consisting of palygorskite and indigo obtained in the above step (2) was washed with a solution consisting of 1.5 g of sodium hydrosulfite, 10 g of 2M aqueous sodium hydroxide solution and 100 g of distilled water at 50 ° C. for 40 minutes, 9.0 g of the inorganic / organic composite coloring composition was purified. In addition, the amount of indigo loss before and after washing was reduced by about 30% from the result of CHN analysis.
  • Example 7 Method 4 for producing inorganic / organic composite coloring composition by dry method 4
  • calcium carbonate which is an impurity in palygorskite (Atagel # 40, manufactured by Engelhard) is removed with concentrated hydrochloric acid, and this acid pretreated palygorskite is used in step (1).
  • cerium nitrate hexahydrate was used in place of lanthanum nitrate hexahydrate, and there was no step (1A), 9.0 g of the inorganic / organic composite coloring composition was used. Purified.
  • Example 8 Method 5 for producing inorganic / organic composite coloring composition by dry method 5 Process (1) 0.5 g of methyl red (Johnson Matthey Company) 0.5 g was added to 10 g of palygorskite (Atagel # 50, manufactured by Engelhard) and mixed with a mixer. The mixture was pulverized using a ball mill and pulverized, and then mixed well with a mixer.
  • palygorskite Atagel # 50, manufactured by Engelhard
  • Process (2) The colored product composed of palygorskite and methyl red obtained in the above step (1) was heated at 170 ° C. for 6 hours.
  • Step (3) The crude colored composition composed of palygorskite and methyl red obtained in the above step (2) was washed by Soxhlet extraction with water to purify 9.0 g of the inorganic / organic composite colored composition. The amount of methyl red lost before and after washing was reduced by about 50% from the result of CHN analysis.
  • Example 9 Production Method 6 for Coloring Composition of Inorganic / Organic Complex by Dry Method 6
  • 10 g of palygorskite (Atagel # 40, manufactured by Engelhard) was added to 115 g of distilled water, and a solution consisting of 285 g of distilled water and 0.52 g of lanthanum nitrate hexahydrate was stirred at 80 ° C. for 4 hours. In exchange, lanthanum ions were incorporated into the palygorskite. This solution was filtered, and the palygorskite was thoroughly washed with water and dried.
  • Disperse Yellow 54 (Arimoto Chemical Co., Ltd.) 0.5 g was added to 10 g of the palygorskite (Atagel # 50, manufactured by Engelhard Co., Ltd.) obtained in the step (1C), and mixed with a mixer. The mixture was pulverized using a ball mill and pulverized, and then mixed well with a mixer.
  • Process (2) The colored product composed of palygorskite and disperse yellow 54 obtained in the above step (1) was heated at 170 ° C. for 6 hours.
  • Step (3) The crude colored composition composed of palygorskite and disperse yellow 54 obtained in the above step (2) was washed by Soxhlet extraction with ethanol to purify 9.0 g of the inorganic / organic composite colored composition. Incidentally, the amount of 54 disperse yellow reduced before and after washing was reduced by about 30% from the result of CHN analysis.
  • Comparative Example 1 Method 7 for producing inorganic / organic composite coloring composition by dry method 7 Under the same conditions as Example 1 except that the washing in the step (3) was not performed, 9.0 g of the inorganic / organic composite coloring composition was purified.
  • Example 2 Production Method 8 for Coloring Composition of Inorganic / Organic Complex by Dry Method 8
  • the washing in step (3) was performed with chloroform, and before step (1), calcium carbonate which is an impurity in palygorskite (Atagel # 40) was removed with concentrated hydrochloric acid.
  • the acid pretreatment palygorskite was used in step (1), 9.0 g of the inorganic / organic composite coloring composition was purified.
  • Example 8 Comparative Example 3 Production Method 9 for Coloring Composition with Inorganic / Organic Complex by Dry Method 9
  • the washing in step (3) was performed by Soxhlet extraction with ethanol, and before step (1), calcium carbonate which is an impurity in the palygorskite (Atagel # 40) was removed with concentrated hydrochloric acid. Then, 9.0 g of the inorganic / organic composite coloring composition was purified under the same conditions except that this acid pretreated palygorskite was used in step (1).
  • Comparative Example 4 Method 10 for Manufacturing Inorganic / Organic Complex Colored Composition by Dry Method the washing in step (3) was not performed, and before step (1), calcium carbonate, which is an impurity in the palygorskite (Atagel # 40), was removed with concentrated hydrochloric acid. Under the same conditions except that the treated palygorskite was used in the step (1), 9.0 g of the inorganic / organic composite coloring composition was purified.
  • the color difference due to bleed was measured by measuring the color difference of the paint surface dyed by bleed with respect to the color of the white paint alone. A larger color difference indicates a larger bleed. If the color difference ⁇ E is 1.0 or less, there is almost no change in color and it can be determined that there is no bleeding. Therefore, a color difference ⁇ E of 1.0 or less was accepted.
  • the paint containing the inorganic / organic composite coloring composition of Example 2 passed without clear discoloration.
  • Weight resistance test 1 1.71 parts by weight of the inorganic / organic composite coloring composition obtained in Example 1 above, 0.17 parts by weight of 10% Emulgen A-500 aqueous solution (manufactured by Kao Corporation), BYK028 (manufactured by Big Chemie Japan Co., Ltd.) ) 0.03 parts by weight, Movinyl 727 (made by Nippon Synthetic Chemical Co., Ltd.) 6.41 parts by weight, Cs-12 (made by Chisso Chemical Co., Ltd.) 0.45 parts by weight, and Big Art White (made by Turner Color Co., Ltd.) ) A paint was prepared from 91.23 parts by weight.
  • paints were prepared with the same composition.
  • a paint was prepared with the same composition. These paints were applied to a white acrylic plate with a 250 ⁇ m applicator, dried, and then subjected to a weather resistance test according to JIS K5600-7-7 using an accelerated weather resistance tester of a xenon lamp. The color difference ⁇ E after 300 hours was measured. In the weather resistance test described below, the color difference ⁇ E was measured by the same method. The results are shown in Table 2.
  • the color difference ⁇ E of the inorganic / organic composite coloring compositions obtained in Examples 1 and 4 was 2.0 or less even after 300 hours, and showed excellent weather resistance.
  • the color difference ⁇ E of the inorganic / organic composite coloring composition obtained in Example 9 also showed excellent weather resistance equivalent to that in Examples 1 and 4 at 100 hr.
  • the water-washed product of Example 8 showed significantly superior weather resistance compared with no washing and ethanol washing.
  • the color difference ⁇ E after 500 hours was 2 or less even without washing, but when compared with after 100 hours, better weather resistance was obtained with the washing step.
  • FIG. 1 shows that Example 5 did not have a washing step, Disperse Yellow 54 and indirubin were used instead of indigo, and Europium nitrate hexahydrate was used instead of lanthanum nitrate hexahydrate.
  • the inorganic / organic composite coloring composition produced under the same conditions and the one obtained by incorporating europium (III) ions into Atagel # 40 were excited by 457.9 nm, 5 mW, exposure time 10 ⁇ It is the emission spectrum measured in 30 sec. The sharp peak at 16000-17400 cm-1 is the 4f-4f emission characteristic of europium (III) ions.
  • the inorganic / organic composite coloring composition in which europium (III) ions are incorporated by ion exchange emits laser excitation light.
  • the blue / yellow / yellow primary inorganic / organic composite coloring composition based on the same palygorskite clay according to the present invention enables expression of various colors, excellent weather resistance, hydrophilicity / lipophilicity, and high dispersibility -A basic colorant with low sedimentation and easy handling at high concentrations. Therefore, taking advantage of the safety of this coloring material, unique and various colors, etc., it is suitably used for products such as paints, stationery, and cosmetics.
  • the method for producing an inorganic / organic composite coloring composition according to the present invention is suitably used for producing a coloring composition with little fading over time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Coloring (AREA)

Abstract

La présente invention concerne une composition colorante composite organique-inorganique présentant une résistance supérieure aux intempéries et une faible atténuation de la couleur une fois qu'un objet à colorer a été coloré, et un procédé de production de la composition. La composition colorante composite organique-inorganique de l'invention, comprenant une argile minérale et un colorant organique, est caractérisée en ce que l'argile minérale est une argile fibreuse, et en ce que la composition colorante ayant coloré un objet à colorer présente une différence de couleur ΔE d'au plus 2 après une durée d'exposition de 500 heures à un test de résistance aux intempéries selon la norme JIS K5600-7-7.
PCT/JP2012/056776 2011-03-15 2012-03-15 Composition colorante composite organique-inorganique et procédé de production de celle-ci Ceased WO2012124785A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013504779A JPWO2012124785A1 (ja) 2011-03-15 2012-03-15 無機・有機複合体着色組成物及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011056986 2011-03-15
JP2011-056986 2011-03-15

Publications (1)

Publication Number Publication Date
WO2012124785A1 true WO2012124785A1 (fr) 2012-09-20

Family

ID=46830849

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/056776 Ceased WO2012124785A1 (fr) 2011-03-15 2012-03-15 Composition colorante composite organique-inorganique et procédé de production de celle-ci

Country Status (2)

Country Link
JP (1) JPWO2012124785A1 (fr)
WO (1) WO2012124785A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2023053982A1 (fr) * 2021-09-28 2023-04-06
WO2023053980A1 (fr) * 2021-09-28 2023-04-06 Dic株式会社 Composition de colorant insoluble dans l'eau
WO2023053981A1 (fr) * 2021-09-28 2023-04-06 Dic株式会社 Composition de pigment insoluble dans l'eau et insoluble dans les huiles
JPWO2023053983A1 (fr) * 2021-09-28 2023-04-06

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008097837A2 (fr) * 2007-02-02 2008-08-14 Board Of Regents, The University Of Texas System Complexes organiques/inorganiques sous forme de compositions de couleurs
WO2009092103A1 (fr) * 2008-01-17 2009-07-23 Mayan Pigments, Inc. Compositions de pigments hybrides organiques-inorganiques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008097837A2 (fr) * 2007-02-02 2008-08-14 Board Of Regents, The University Of Texas System Complexes organiques/inorganiques sous forme de compositions de couleurs
WO2009092103A1 (fr) * 2008-01-17 2009-07-23 Mayan Pigments, Inc. Compositions de pigments hybrides organiques-inorganiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DOMENECH, ANTONIO ET AL.: "Evidence of topological indigo/dehydroindigo isomers in Maya Blue-like complexes prepared from palygorskite and sepiolite", JOURNAL OF PHYSICAL CHEMISTRY C, vol. 113, no. 28, 2009, pages 12118 - 12131 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2023053982A1 (fr) * 2021-09-28 2023-04-06
WO2023053980A1 (fr) * 2021-09-28 2023-04-06 Dic株式会社 Composition de colorant insoluble dans l'eau
WO2023053981A1 (fr) * 2021-09-28 2023-04-06 Dic株式会社 Composition de pigment insoluble dans l'eau et insoluble dans les huiles
JPWO2023053980A1 (fr) * 2021-09-28 2023-04-06
JPWO2023053983A1 (fr) * 2021-09-28 2023-04-06
JPWO2023053981A1 (fr) * 2021-09-28 2023-04-06
JP7552926B2 (ja) 2021-09-28 2024-09-18 Dic株式会社 非水溶性、非油溶性色素組成物
JP7552924B2 (ja) 2021-09-28 2024-09-18 Dic株式会社 非水溶性色素組成物
JP7552927B2 (ja) 2021-09-28 2024-09-18 Dic株式会社 非水溶性色素組成物
JP7552925B2 (ja) 2021-09-28 2024-09-18 Dic株式会社 非水溶性、非油溶性色素組成物

Also Published As

Publication number Publication date
JPWO2012124785A1 (ja) 2014-07-24

Similar Documents

Publication Publication Date Title
DE2012152C3 (de) Verfahren zur Herstellung von Pigmentfarbstoffgemischen aus Disazofarbstoffen und deren Verwendung
EP0374655B1 (fr) Film ou feuille polarisant contenant des colorants de stilbène
CN104357931B (zh) 一种荧光沙柳再生纤维素纤维及其制备方法
DE112007000656B4 (de) Leuchtstoff, Verfahren zur Herstellung desselben und lichtemittierende Vorrichtungen unter Verwendung desselben
JP2018035035A (ja) 炭素量子ドットの製造方法及びその方法で得られる炭素量子ドット
Li et al. Design and assembly of AIE-active fluorescent organic nanoparticles for anti-counterfeiting fluorescent hydrogels and inks
WO2012124785A1 (fr) Composition colorante composite organique-inorganique et procédé de production de celle-ci
DE102009026746A1 (de) Sprühgetrocknete Farbstoffkomposite, Verfahren zu ihrer Herstellung und ihre Verwendung
TWI472581B (zh) Triarylmethane and rosy red pigment compositions, and the use of such pigment dispersions
CN110157412B (zh) 一种长寿命室温磷光材料及其制备方法
CN102702853B (zh) 一种水性荧光增强防伪油墨的制备方法
CN104357934B (zh) 一种荧光Lyocell纤维及其制备方法
Al-Senani et al. Preparation of multifunctional and mechanically-reliable smart wood infiltrated with cellulose nanocrystal-reinforced polyvinyl alcohol nanocomposite
Al-Senani et al. Development of smart adhesive using lanthanide-doped phosphor and carboxymethyl cellulose-reinforced gum Arabic
Dong et al. Maya blue pigments derived from clay minerals
CN106243835A (zh) 一种水性稀土配合物复合微球荧光油墨及其制备工艺
CN101407652A (zh) 一种紫外光固化发光涂料的制备方法
JP2003082256A (ja) ベンツイミダゾロン系混晶顔料
CN109233807A (zh) 一种稀土复合发光水凝胶材料及其制备方法与应用
JP4759966B2 (ja) モノアゾレーキ顔料組成物の製造方法
CN108485656B (zh) 一种x射线成像材料
Al‐Qahtani et al. Development of glass nanofiber and lanthanide phosphor–embedded natural polymer nanocomposite coating for ultraviolet filtering smart windows and optical data encryption
CN114591728B (zh) 一种防伪颜料及其制备方法和应用
CN112775433B (zh) 一种酶合成荧光金纳米簇的制备方法
CN112759980A (zh) 一种环保型防伪油墨及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12758297

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2013504779

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12758297

Country of ref document: EP

Kind code of ref document: A1