WO2012124785A1

WO2012124785A1 - Organic-inorganic composite coloring composition and method for producing same

Info

Publication number: WO2012124785A1
Application number: PCT/JP2012/056776
Authority: WO
Inventors: 純男海崎; 隆弘瀧川; 西村　善彦
Original assignee: 国立大学法人大阪大学; ターナー色彩株式会社
Priority date: 2011-03-15
Filing date: 2012-03-15
Publication date: 2012-09-20
Also published as: JPWO2012124785A1

Abstract

[Problem] To provide an organic-inorganic composite coloring composition having superior weather resistance and less color fading after an object to be colored has been colored, and a method for producing the composition. [Solution] An organic-inorganic composite coloring composition comprising a clay mineral and an organic dye is characterized in that the clay mineral is a fibrous clay and in that the coloring composition, having colored an object to be colored, has a color difference ΔE of at most 2 from an exposure time of 500 hours by weather resistance testing as per JIS K5600-7-7.

Description

Inorganic / organic composite coloring composition and method for producing the same

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.

Known blue pigments include phthalocyanine, ultramarine, bitumen, and Maya blue. Among them, 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. In Patent Document 1, 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. By heating the complex of indigo and clay mineral under such heating conditions, a coating composition having a blue fading of 10% or less in one year can be obtained.

Generally, 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. As described above, 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 (ΔE) (for example, 2 or less) and cannot be visually recognized cannot be obtained.

JP 2005-530891 A

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 ΔE 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.

In the invention according to claim 5, 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 inorganic / organic composite coloring composition according to claim 3, wherein the coloring composition is at least one kind of ion.

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 μm 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. for 1 to 24 hours (2A) 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

In the invention according to claim 8, the organic dye is indigo, and 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 method for producing an inorganic / organic composite coloring composition according to claim 6 or 7, further comprising a step of obtaining an inorganic / organic composite coloring composition by washing with water.

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.

In the invention according to claim 13, 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.

According to the first aspect of the present invention, there is provided 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 ΔE 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.

According to the invention of claim 2, 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.

According to the invention of claim 3, since it is an inorganic / organic composite coloring composition containing rare earth element ions, 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.

According to the invention of claim 4, 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. A colored composition.

According to the invention of claim 5, at least one ion selected from trivalent cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium, and divalent europium. Therefore, 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.

According to the invention which concerns on Claim 6, It is a manufacturing method of 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 μm 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. By providing the step of obtaining an object, a colored composition having excellent weather resistance with less fading of the coloring object can be obtained.

According to the invention which concerns on Claim 7, It is a wet manufacturing method of 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.
In the manufacturing method, (1B) after step (1), an ultrasonic wave is applied while stirring the solution containing the reduced organic dye and the fibrous clay so that air is not involved in the solution. 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. As a result, it is possible to improve the dispersibility of the dyes, and to obtain a colored composition with less fading of the coloring object and excellent weather resistance, and the organic dye is oxidized and insolubilized, so that the inorganic / organic composite A body coloring composition can be taken out efficiently.

According to the invention which concerns on Claim 8, 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. By providing the step of obtaining an inorganic / organic composite coloring composition by washing with an alkaline solution, indigo that is not taken into the channel of the fibrous clay and simply adhered can be removed, and thus the coloring object is removed. A blue colored composition with less fading and excellent weather resistance can be obtained.

According to the invention according to claim 9, 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.

According to the invention of claim 10, the organic dye is a quinoline dye, and the crude coloring composition comprising the fibrous clay obtained in the step (2) and the organic dye is used as a reducing agent. By washing with an alkaline solution containing or by soxhlet extraction with ethanol to obtain an inorganic / organic composite coloring composition, an organic dye that is not taken into the channel of the fibrous clay but is simply attached Thus, a yellow colored composition having excellent weather resistance with less fading of the colored object can be obtained.

According to the invention according to claim 11, in the step (1), after the rare earth element ions are incorporated into the fibrous clay by ion exchange, 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.

According to the invention of claim 12, after the lanthanum ions are taken in by ion exchange, 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.

According to the invention of claim 13, at least one ion selected from trivalent cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium, and divalent europium. Is a method for producing an inorganic / organic composite coloring composition in which the fibrous dye containing the ions is ion-exchanged and the organic dye are mixed. A three-primary-colored three-primary-color light-emitting composition that is bright in color and excellent in visibility can be obtained.

According to the invention of claim 14, since 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.

It is an emission spectrum of an inorganic / organic composite coloring composition incorporating trivalent Eu (III) ions.

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.

As 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.
Also, 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. However, it is not preferable to use 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.

As the organic dye, 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). On the other hand, it is soluble in trichloromethane, nitrobenzene and concentrated sulfuric acid even in the state shown in the following formula (Chemical Formula 1).

When the indigo represented by (Chemical Formula 1) is reduced, a reduced leucoin jigo represented by the following formula (Chemical Formula 2) is obtained. 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.
When this 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 δ (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.

When the coloring object is colored with the inorganic / organic composite coloring composition according to the present invention, that is, the composite coloring composition of fibrous clay and organic dye, the color difference ΔE 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 ΔE 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 ΔE in the present invention is based on JIS Z8730.
Moreover, 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.
By ion-exchange of rare earth element ions such as lanthanum, 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 ΔE after coloring of an irradiation time of 500 in a weather resistance test according to JIS K5600-7-7. 2 or less in time.

Next, the method for producing the inorganic / organic composite coloring composition according to the present invention will be described in detail. 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.

As described above, indigo, indirubin, herringdon pink CN, methyl red and quinoline dyes are preferably used as the organic dye. In 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.
Hereinafter, 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.

<Process (1) Micronization and mixing process of fibrous clay and indigo>
Fibrous clay and indigo are pulverized and mixed. The fibrous clay and indigo may be pulverized and mixed, or the fibrous clay and indigo may be mixed and then pulverized.
Fibrous clay and indigo are pulverized to 0.1 to 70 μm. By this pulverization treatment, the contact between the fibrous clay and the indigo is increased, and the indigo is easily dyed on the fibrous clay.

<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.
By ion-exchange of rare earth element ions such as lanthanum, 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. By adjusting the salt concentration described above, the amount of rare earth element ions incorporated into the fibrous clay by ion exchange changes.
In order to efficiently incorporate rare earth element ions into the fibrous clay, it is preferable to use acid pretreated fibrous clay (acid pretreated palygorskite) obtained by removing calcium carbonate, which is an impurity in the fibrous clay, with concentrated hydrochloric acid.

It is preferable to remove calcium carbonate, which is an impurity, from the fibrous clay with concentrated hydrochloric acid. 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: pulverization and mixing of fibrous clay and indigo>
In 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 μm. The mechanical method of pulverization is not limited to the above method.

<Step in wet process (1A) 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).
In the 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.
As 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. On the other hand, if 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.

A well-known thing can be used as a reducing agent. Specifically, sodium hydrosulfite (sodium dithionite) is suitable.
It is preferable to make the aqueous solvent alkaline before adding sodium hydrosulfite to the aqueous solvent. 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. By adjusting the content to 100 to 3000% by weight, 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.

<Step (1) in the wet method: pulverization and mixing of fibrous clay and organic dye>
After obtaining the leuco indigo solution in the above step (1A), 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 μm 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. 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. In addition, 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. By applying ultrasonic waves and stirring, 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.
Although it may be performed without applying an ultrasonic wave and stirring, in that case, leuco coin jig is not efficiently taken into the channel. Furthermore, 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.
Thereby, 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.

<Process (2A) dispersion process>
Before the step (2) heating step described later, it is preferable to disperse the colored product obtained from the step (1) in the form of fibrous clay and indigo in a solvent having a high boiling point, and particularly an organic dye which is easily discolored. It is more preferable when using. Thereby, it can prevent that indigo discolors by the heating of the process (2) mentioned later. As the solvent, a solvent having a boiling point higher than the heating temperature that does not boil by heating is used, and for example, propylene glycol is preferably used in consideration of compatibility with the organic dye to be used.
When using herringdon pink CN as the organic dye, it is preferable to perform this step (2A).

<Process (2) heating process>
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. When the temperature is lower than 120 ° C., indigo attached to the fibrous clay does not get stuck in the channel, and the weather resistance of the coloring composition is deteriorated. On the other hand, if 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.
When the colored material composed of fibrous clay and indigo is dispersed in a high boiling point solvent such as propylene glycol in the step (2A), 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. On the other hand, 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.

As 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.
When the step (2A) dispersion step is not performed, since there are many indigo in a state of being simply attached, this washing step must be performed.

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 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.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the following examples.

Example 1 Production Method 1 for Coloring Composition of Inorganic / Organic Complex by Dry Method
Process (1)
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.

Process (1)
10 g of palygorskite (Atagel # 40, manufactured by Engelhard) was added to 400 g of distilled water, and an ultrasonic wave having a frequency of 37 to 42 kHz was applied at 80 ° C. for 40 minutes while stirring the solution. This solution was mixed with 134.5 g of the leucoin digo solution obtained in the above step (1A) to obtain 544.5 g of a solution containing leuco 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 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.

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.

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 | purified.

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.

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.

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.

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.

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.

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.

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
In Example 6, before step (1C), 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). Under the same conditions except that it was used, 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.

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
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.

Process (1)
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)
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.

Comparative Example 2 Production Method 8 for Coloring Composition of Inorganic / Organic Complex by Dry Method 8
In Example 1, 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. Under the same conditions except that the acid pretreatment palygorskite was used in step (1), 9.0 g of the inorganic / organic composite coloring composition was purified.

Comparative Example 3 Production Method 9 for Coloring Composition with Inorganic / Organic Complex by Dry Method 9
In Example 8, 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
In Example 8, 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.

Comparative Example 5 Production Method 11 for Coloring Composition of Inorganic / Organic Complex by Dry Method 11
Under the same conditions as Example 9 except that the washing in the step (3) was not performed, 9.0 g of the inorganic / organic composite coloring composition was purified.

(Test example)
(Bleed test)
From 7.7 parts by weight of the inorganic / organic composite coloring composition obtained in Example 2 above, 63.5 parts by weight of the pigment dispersion and 28.8 parts by weight of Movinyl 727TXNL (manufactured by Nippon Synthetic Chemical Co., Ltd.) which is an acrylic resin, A primary color paint was prepared, applied and dried, and then a white paint was applied thereon, and a test for confirming the presence or absence of bleeding was performed.
As a comparative example, a similar test was performed on B1000 (manufactured by Mayan Pigments), which is a blue paint.
The results are shown in Table 1. 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 ΔE 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 ΔE of 1.0 or less was accepted. The paint containing the inorganic / organic composite coloring composition of Example 2 passed without clear discoloration.

(Weather 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. In the inorganic / organic composite coloring compositions obtained in Examples 4 and 9, paints were prepared with the same composition.
In the inorganic / organic composite coloring composition used for the weather resistance test described below, a paint was prepared with the same composition.
These paints were applied to a white acrylic plate with a 250 μm 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 ΔE after 300 hours was measured.
In the weather resistance test described below, the color difference ΔE was measured by the same method.
The results are shown in Table 2. The color difference ΔE 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 ΔE 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.

(Weather resistance test 2)
Paints containing the inorganic / organic composite coloring compositions obtained in Examples 1 to 3 above, and, as comparative examples, B1000 (manufactured by Mayan Pigments), RB1000 (manufactured by Mayan Pigments) and Unisperse Blue GS (phthalocyanine) The color difference ΔE after 24, 100, 200, 300, 400, and 500 hours of BASF was measured. Only Example 1 was measured until 600 and 700 hours later.
The results are shown in Table 3. The inorganic / organic composite coloring compositions obtained in Examples 1 and 2 were comparable to phthalocyanine, and the inorganic / organic composite coloring compositions obtained in Examples 1, 2, and 3 were superior to B1000 and RB1000. It showed weather resistance.

(Weather resistance test 3)
24, 100 (124), 200 (224), 300 (324), 400 (424), 500 (524) hours after the coating containing the inorganic / organic composite coloring composition obtained in Examples 5 and 7 above The color difference ΔE was measured.
The results are shown in Table 4. The color difference ΔE of the inorganic / organic composite coloring composition obtained in Example 5 in which lanthanum ions were ion-exchanged was 1.5 or less even after 500 hours, indicating excellent weather resistance. When the La concentration was 1.6% or less, the weather resistance was improved as compared with the La concentration of 0%.

(Weather resistance test 4)
24 of the paint containing the inorganic / organic composite coloring composition obtained in Comparative Examples 1 to 5 and the paint containing the inorganic / organic composite coloring composition obtained in Examples 2, 5, 8, and 9 above. , 100, 200, 300, 400, and 500 hours later, the color difference ΔE was measured.
The results are shown in Table 5. The color difference ΔE of the inorganic / organic composite coloring compositions obtained in Comparative Examples 1 to 5 exceeded 2. Therefore, it turned out that the process (3) washing | cleaning process has contributed greatly to a weather resistance.
For blue, the alkali-washed one of Example 2 showed significantly superior weather resistance compared to no washing and chloroform washing.
As for the red color, the water-washed product of Example 8 showed significantly superior weather resistance compared with no washing and ethanol washing.
For yellow, the color difference ΔE 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. Except for the above, 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.
Thus, it can be seen that the inorganic / organic composite coloring composition in which europium (III) ions are incorporated by ion exchange emits laser excitation light.

In addition, it is as follows when an Example and a comparative example are arranged.

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. Furthermore, by providing three primary colors and three primary colors, it is not only applied to lighting fixtures as white LED phosphors and displays using liquid crystals, but it also provides long afterglow, resulting in unprecedented high weather resistance and It is possible to manufacture a water-resistant and colored phosphorescent color material that can be used outdoors, and a crime prevention / disaster prevention guidance display board and a bulletin board can be manufactured at a lower cost than the existing products.
In addition, 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.

Claims

An inorganic / organic composite coloring composition comprising a clay mineral and an organic dye,
The clay mineral is fibrous clay;
An inorganic / organic composite coloring composition characterized in that a color difference ΔE at an irradiation time of 500 hours according to a weather resistance test according to JIS K5600-7-7 of the coloring composition coloring the coloring object is 2 or less.
The inorganic / organic composite coloring composition 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 inorganic / organic composite coloring composition according to claim 1, comprising rare earth element ions.
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 at least one ion selected from trivalent cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium, and divalent europium. The inorganic / organic composite coloring composition according to claim 3 or 4, characterized in that the composition is colored.
A method for producing an inorganic / organic composite coloring composition comprising a fibrous clay, which is a clay mineral, and an organic dye,
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 μm 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. for 1 to 24 hours (2A) 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
A wet method for producing an inorganic / organic composite coloring composition comprising fibrous clay, which is a clay mineral, and an organic dye,
The method for producing an inorganic / organic composite coloring composition according to claim 6, comprising the following step (1B).
(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,
A step of washing the crude colored composition comprising the fibrous clay obtained in the step (2) and the organic dye with an alkaline solution containing a reducing agent to obtain an inorganic / organic composite colored composition; The method for producing an inorganic / organic composite coloring composition according to claim 6 or 7.
The organic dye comprises at least one selected from the group consisting of indirubin, herringdon pink CN and methyl red;
The crude colored composition composed of the fibrous clay obtained in the step (2) and the organic dye is washed with an alkaline solution containing a reducing agent or washed with Soxhlet extraction with water to be inorganic / organic. 8. The method for producing an inorganic / organic composite coloring composition according to claim 6 or 7, further comprising a step of obtaining the composite coloring composition.
The organic dye is a quinoline dye,
The crude colored composition composed of the fibrous clay obtained in the step (2) and the organic dye is washed with an alkaline solution containing a reducing agent, or washed with Soxhlet extraction with ethanol to be inorganic / organic. 8. The method for producing an inorganic / organic composite coloring composition according to claim 6 or 7, further comprising a step of obtaining the composite coloring composition.
In the step (1), after the rare earth element ions are incorporated into the fibrous clay by ion exchange, the fibrous clay into which the rare earth element ions are incorporated by ion exchange and the organic dye are mixed. The manufacturing method of the inorganic and organic composite coloring composition as described in any one of Claim 6 thru | or 10.
The 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 at least one ion selected from trivalent cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium, and divalent europium. The method for producing an inorganic / organic composite coloring composition according to claim 11 or 12.
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.