JPH03163172A - Modified powder - Google Patents

Abstract

PURPOSE:To obtain a modified powder whose surface activity is killed by bringing a powder having active sites on its surface into contact with a specified silicone compound in the form of a vapor and polymerizing the silicone compound on the entire surface of the powder. CONSTITUTION:A powder having active sites on the surface (e.g. inorganic pigment, a metal oxide, an organic pigment, a silicate mineral, carbon or a metal) is brought into contact with at least one silicone compound of the formula [wherein R<1>, R<2> and R<3> are each a (halogen-substituted) 1-10C hydrocarbon group; R<4>, R<5> and R<6> are each H or a (halogensubstituted) 1-10C hydrocarbon group; a is 0, b is 0 or an integer >=1; and c is 0 or 2, and when c is 0, the sum of a and b is an integer >=3] in the form of a vapor, thereby depositing the silicone compound on the entire surface of the powder and polymerizing the silicone compound by the active sites distributed on the entire surface of the powder to form a uniform thin polymer film. In this way, a modified powder whose surface activity is killed can be obtained. This modified powder neither denatures nor decomposes the coexistent perfume, oil, resin or the like, so that it can be used in many fields.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a modified powder carrying a silicone polymer film on substantially its entire surface. In particular, the present invention relates to a modified powder in which the surface activity of the powder is eliminated by treating the powder with active sites on its surface with a specific silicone compound in vapor form. In this specification, "powder" generally means any object with a particle size of 10 mm or less (sometimes including particles larger than 10 mm). The term "powder" as used herein includes aggregates, shaped bodies, and shaped bodies made of a plurality of the powders. Furthermore, in this specification, the term "active site" refers to a site that can catalyze the polymerization of a silicone compound having a siloxane bond (Si-0-Si) or a Si-H (hydrosilyl) group, such as an acid site. , means a basic point, an acid C1 lower margin point, or a reduction point. The modified powder according to the present invention does not modify or decompose perfumes, oils, or resins coexisting therewith. Therefore, it can be used, for example, in the fields of cosmetics, pharmaceuticals, paints, inks, paints, ornaments, fragrances, magnetic materials, and medical materials without causing problems such as deterioration, odor, and discoloration.

(Prior Art) Conventionally, silicone oil has been frequently used for hydrophobic modification of powder. For example, Japanese Patent Publication No. 41-9890 describes that lubricity is imparted to powders by coating the surface of animal, vegetable, or mineral powders with a silicone resin coating and drying the coating. ing. In Japanese Patent Publication No. 45-2915, a mineral powder such as talc and a silicone compound having a hydrogen atom directly bonded to a silicon atom in the molecular chain are simply attached by mixing in a blender, and then heated and baked to form the powder. It has been given T8 aqueous properties. In addition, in Japanese Patent Publication No. 18999/1989, dimethylbolysiloxane or methylhydrogenpolysiloxane is dissolved in an organic solvent and then contacted and adhered to talc, and then, if necessary, zinc octoate is added as a cross-g polymerization catalyst for methylhydrogenpolysiloxane. Free-flowing properties are imparted to the powder by adding a substance such as the following and baking it. Furthermore, in Japanese Patent Publication No. 49-1769, titanium dioxide is directly coated, emulsified coated, or coated with a solvent solution, and if necessary, an ester compound having a total carbon number of 6 or more is used, and dry baking is performed. We are modifying the dustiness and dispersibility of powder.

Also, JP-A-56-16404, JP-A-55-136
No. 213 and Japanese Unexamined Patent Publication No. 56-29512,
After silicone oil and oil agent are added and a mechanochemical reaction is performed such as stirring and mixing or pulverization to cause γ-combination, baking treatment is performed. Furthermore, JP-A-57-200306 discloses that baking treatment is performed by treating powder with (A) a silane compound, (B) a cyclic polyorganosiloxane, or (C) a linear polyorganosiloxane having a specific structure. without doing
A method of imparting 78 aqueous and fluid properties to a powder is disclosed. In this method, 1 to 10% by weight of the organosilicon compound of the target powder is diluted with a solvent and sprinkled, directly sprinkled, or gaseously sprayed, or directly mixed and stirred to be adsorbed to the powder.
The next method involves water and steam treatment. However, there is no mention of gas phase treatment for the silane compound (A) and the cyclic polyorganosiloxane (B).
Moreover, among the cyclic polyorganosiloxanes (B), trimers having methyl groups are excluded because they are solid and difficult to handle. [Problems to be Solved by the Invention] However, with these methods, it has not been possible to treat most organic materials and anhydrous materials that are sensitive to heat, such as yellow iron oxide and dark blue. For example, the organic pigment Red No. 202 (Resol Rubin BCA) could not be processed because it was dehydrated at 80° C. and the crystal type changed from α type to β type and the color tone changed. In addition, navy blue decomposes when heated and gradually releases cyan gas at temperatures above 150°C. Baking treatment is high at 350℃ for 2 hours.
At low temperatures, the process is carried out at 150°C for 15 to 40 hours; under such conditions, the dark blue color not only changes color but also emits toxic cyan gas, which is extremely dangerous. As described above, conventional baking treatments can only be applied to some stable inorganic pigments, and have the fatal drawback that when organic pigments, which are bright among pigments, are treated, the color tone, which is the life of the pigment, is damaged.

If a catalyst is used to lower the baking temperature, it is true that the process can be carried out at a low temperature, but the catalyst remains and accelerates the deterioration of the silicone resin on the surface, causing significant changes over time and being impractical. there were. In addition, the catalytic action promotes the decomposition of not only the silicone resin on the surface but also other components that coexist, such as oils and fragrances, causing problems such as discoloration and odor, so it should not be used in cosmetics, etc. I couldn't do it.

JP-A-56-16404 describes a silicone treatment method using mechanochemical reactions.

However, since this method utilizes crushing force, the shape of powders that are characterized by a plate-like or spherical shape may change. Additionally, powders such as titanium dioxide, which aggregate when stirred, are difficult to treat alone. In the method described in JP-A-57-200306, the molecular treatment agent is not brought into contact with the powder, but in the form of a liquid or liquid particles. For this reason, trimers, which are solids among cyclic polyorganosiloxanes, are excluded. The amount of processing agent is specified to be 1 to 10% of the powder, but depending on the type of powder, this amount may not be sufficient, and if the powder remains surface active and fragrances etc. coexist. However, there were drawbacks such as poor fragrance stability.

The purpose of the present invention is to maintain the original properties of the powder while
To provide a modified powder that has improved properties (e.g., hydrophobicity, stability) and eliminates the surface activity of the powder (i.e., does not cause alteration or decomposition of other coexisting substances), The object of the present invention is to eliminate the drawbacks of the prior art described above.

[Means to solve the problem]

The above purpose is based on the general formula (RIHSiO)a(R"R'SiO)b(R'R'R
'SiO,)C (1) (where R', R' and R
3 is a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one halogen atom, and R 4, 'RS and R& are each independently a hydrogen atom. or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one halogen atom, a is 0'', b is 0 or an integer of 1 or more, and C is 0 or 2, but if C is 0, the sum of a and b shall be an integer of 3 or more) in vapor form on the surface. The modified powder is made by contacting with a powder having active sites and polymerizing a siliconized metal material on substantially the entire surface of the powder, and carrying a silicone polymer film on substantially the entire surface of the powder. The present invention will be described in detail below.As already mentioned, in the prior art, when treating powder with silicone oil, most of the techniques require heat, catalysts, or crushing power. This is because the silicone oil used is relatively inert and the powder used has no activity.However, many powders have surface activity.
This surface activity of the powder degrades fragrances, oils, medicines, etc. that coexist with the powder. The present inventors reversely utilized this surface activity to polymerize silicone compounds on the powder surface to modify the surface, for example to make it hydrophobic, and to eliminate the surface activity of the powder, thereby improving the stability of coexisting ingredients such as fragrances. We have found an innovative method to do this. The powder modified in the present invention is not particularly limited as long as the powder has surface activity. Typical examples of such powders include inorganic pigments, metal oxides, metal hydroxides, organic pigments, burl luster materials, silicate minerals, porous materials, carbon, metals, etc., which have active sites on their surfaces. Includes biopolymers, mica, and composite powders. These powders are 1
It is possible to process by type or by combining multiple types. Furthermore, it is also possible to process aggregates or shaped bodies of one or more of these powders. These powders are subjected to any conventional treatment (e.g., alkaline cleaning, acid cleaning, plasma treatment) before carrying out the modification treatment according to the present invention (i.e., before contacting with the siliconized apricots). be able to.゛If the powder has many acid sites (for example, kaolinite, iron oxide, manganese violet), it is preferable to perform alkaline washing. This is because, according to the present invention, when the silicone compound is subsequently brought into contact and surface polymerized, a silicone polymer film having a crosslinked structure (described later) is likely to form. Furthermore, the powder treated in the present invention may contain other substances (for example, colorants, UV absorbers, pharmaceuticals, various additives) on or in it. In the present invention, the silicone compound of formula (I) in vapor form and the powder having active sites on the surface are brought into contact at a temperature of 120° C. or lower, preferably 100° C. or lower, preferably 100 non}Ig or lower. More preferably 100
It is carried out in a closed container under pressure below mdg, and the formula (
1) The silicone compound vapor can be deposited in molecular form onto the powder surface. Alternatively, the formula for the form of steam (
The silicone compound of 1) and the powder having active sites on the surface are brought into contact at a temperature of 120° C. or lower, preferably 100° C. or lower, and a mixed gas of the silicone compound of formula (I) and a carrier gas is brought into contact with the powder. This can be done by supplying The silicone compounds of formula (I) are comprised of two groups. The first group corresponds to the case where (-=O in the formula (I), and has the general formula (RJSiO) - (R"R'SiO) b
(I[) [wherein, R'% R'', R'
, a and b have the same meanings as above, but preferably Rl, R2 and R3 are each independently a lower alkyl group or aryl group having 1 to 4 carbon atoms which may be substituted with at least one halogen atom. (for example, a phenyl group), and the sum of a and b is 3 to 7]. Representative examples of this compound are as follows. The above compound (A). (B)
and (C), each can be used alone or in the form of a mixture thereof. In each of the above, n (or a+b) is preferably 3 to 7. As the value of n decreases, the boiling point decreases, so the amount that evaporates and adsorbs onto the powder increases. In particular, 3f and 431 bodies, due to their steric properties,
It is particularly suitable because it polymerizes easily. Furthermore, silicone compounds containing hydrogen atoms have high reactivity and are therefore suitable for surface treatment.

Regarding the treatment amount (or addition amount), the present invention is a gas phase treatment, and the volatilized gaseous molecular silicone compound, such as cyclic organosiloxane, is adsorbed onto the powder and then polymerized by the active sites of the powder. The amount of processing is not fixed,
The end point is when the silicone polymer completely covers the active sites. Of course, complete coverage may not be required depending on the purpose.

Examples of the cyclic silicone compound of formula (n) include dihydrodiene hexamethylcyclotetrasiloxane, trihydrodienepentamethylcyclotetrasiloxane,
To mention tetrahydrogentetramethylcyclotetrasiloxane, dihydrogenoctamethylcyclopentasiloxane, trihydrogenheptamethylcyclopentacycloxane, tetrahydrogenhexamethylcyclopentasiloxane, and pentahydrogenpentamethylcyclopentasiloxane Can be done.

The second group of silicone compounds of the formula (1) corresponds to the case of Cwt 2 in the formula (1), the general formula and b have the same meanings as above, and C is 2, but preferably R I , , R h may be substituted with at least one halogen atom independently of each other, with a carbon number of 1
~4 lower alkyl group or aryl group (for example, phenyl group), and the sum of a and b is 2 to 5]. Representative examples of this compound include compounds represented by the formula (wherein a is 2 to 5). Formula (I[[)
Examples of linear silicone compounds include 1.1,1,
2,3.4.4.4-octamethyltetrasiloxane,
1.1.1,2.3,4.5.5.5-nonamethylbentasiloxane, and 1.1.1.2.3.4,5.6
．． 6.6-Decamethylhexasiloxane may be mentioned. There are two types of silicone polymer film structures that are coated on the powder surface. That is, when polymerization occurs through siloxane bonds (1Si-0-Si-), the resulting silicone polymer is 1-Si-0-S
It has a linear structure containing one t unit and preferably has a weight average molecular weight of 200,000 or more. On the other hand, polymerization occurs in small or trace amounts of H! O or O! S
The following polymerization of the i-H moiety: yields a network structure with yo-10-meng i-0- units. Preferred network polymers are those in which the total St or more is converted into units of 20% of the atoms contained in the silicone polymer in the polymer film. The content of this unit can be determined from the IR absorption of methyl groups in the polymer film. The amount of the silicone compound of formula (1) to be added (processing amount) is not specifically determined, but it is desired in terms of supplying the silicone compound in an amount necessary and sufficient to cover substantially the entire surface of the powder. The amount is determined. In other words, the present invention is based on the addition of processing agents!
It is not a predetermined process, but a process in which the processing agent is supplied in the necessary and sufficient amount and is naturally guided to the end point. Therefore, the amount added or the amount of vapor-deposited polymer film varies depending on the type of powder used. Generally, the amount is o.c. of the powder weight. oos~50%. Regarding these powders, the above-mentioned Japanese Patent Application Laid-Open No. 57-20
The amount of treating agent shown in Publication No. 0306 of 1 to 10% is insufficient, and surface activity remains, resulting in poor fragrance stability. In this way, the present invention can process any powder without excess or deficiency, and this is because the manner in which the processing agent is added is different from that of Tsuborai. Conventional processing methods involve diluting the processing agent in a solvent and spraying it on the raw material powder, directly spraying it, or spraying it in gaseous form. In either case, the molecular processing agent is applied to the powder ← Rather than touching it, it touches the body in the form of liquid or liquid particles.

For this reason, the method described in JP-A No. 57-200306 does not allow cyclic organo. Among siloxanes, trimers, which are solids, are excluded, but in the present invention, they are not added in liquid form, but in molecular form and turned into powder. Even if the original treatment agent is solid, it may be liquid due to contact damage. Also good. Also consider polymerization on the powder surface. and Tokukai. It was excluded in No. 1983-200306. Since trimers are most easily polymerized, processing agents. It is the most important term.
．． That is, the feature of the present invention is that the organosiloxane, for example, the cyclic organosiloxane, has a temperature of 120°C or lower, preferably 10°C.
Powder is left in a low partial pressure state that volatilizes at temperatures below 0°C. This is an energy-saving C treatment method that utilizes the fact that vaporized organosiloxane is adsorbed to the powder in the molecular state and polymerized from surface activation. This is completely different from the method of matching.

In addition, the treatment temperature in the method described in Publication No. 57-200306 is 230 to 3
Although the temperature is 50° C., which is not preferable for the reasons mentioned above, the present invention does not involve heat treatment, so the pigment GS, which has low temperature stability, can also be applied, and its application range is extremely wide.

According to the present invention, a silicone compound of the formula (!) is first vapor-deposited on the surface of a powder, and the siliconized product is polymerized due to the presence of active points distributed over the entire surface of the powder. Therefore, a uniform and thin polymeric film is formed. After the thin layer of silicone polymer is coated, substantially no polymerization occurs thereon. Therefore, the thickness of the silicone polymer coating is generally between 3 and 30 thick. On the other hand, when thermal polymerization occurs, polymerization that forms a thin layer is impossible.

Furthermore, when polymerization is carried out in the presence of a catalyst, it is impossible to uniformly coat only the surface of the powder, since the offsetting mainly occurs around the catalyst.

According to a basic aspect of the present invention, the powder and the silicone compound (e.g., cyclic organosiloxane) are simply placed in separate containers in a sealed room (e.g., below 100°C) with the top open. good.

In this state, the silicone compound vaporizes under the partial pressure at that temperature and maintains an adsorption equilibrium on the powder. If the powder is inactive when the treated powder is taken out of the sealed room, the silicone compound will be desorbed and the powder will return to its original surface, but there will be active sites on the particle surface. In the case of a powder having a polymerization activity, the silicone compound polymerizes on the powder, and as a result, the partial pressure of the silicone compound on the surface of the powder decreases, so that it is volatilized from the silicone compound in the container and supplied. Since surface polymerization occurs in this order, the silicone compound is supplied in the required amount to the system, and there is no waste.

Since the present invention is based on such a simple principle, no special equipment is required. For example, any closed room (for example, a closed room M that can be maintained at a constant temperature), such as a desiccator or a constant temperature bath, can be used. Additionally, a desiccator can be used for small-scale processing. However, ideally, a device that can degas after processing is desirable, and a gas sterilization device is recommended. The object in the closed chamber can be continuously or continuously agitated to make contact between the powder and the silicone compound vapor undesirable.

According to another aspect of the present invention, only the powder is charged in advance in a sealed room at a temperature of 120'C or below, preferably 100'C or below, and a predetermined amount is charged in another sealed room at a temperature of 120'C or below. The silicone compound vapor can be introduced by means of a pipe, for example, into the chamber in which the silicone compound is vaporized under pressure and the powder is charged. Although there are no particular limitations on the pressure of the system, it is preferable to carry out the polymerization under a pressure of 200 mHg or less, preferably 100 mm}Ig or less. For both Mr. B, the processing time is 30 minutes to 15 minutes.
0 hours, after which unpolymerized silicone compounds are removed by degassing to obtain the desired green bottoms. According to another aspect of the invention, the powder may be treated by contacting it with a silicone compound of formula (I) in the form of a gas mixture with a carrier gas (e.g. by supplying it to the powder surface). can.

The silicone compound of formula (1) and the carrier gas are mixed by heating the silicone compound of formula (T), for example, if necessary, until the vapor pressure of the silicone compound becomes LBHg or more, preferably 100 mlg or more, and then a carrier gas stream is added. This can be carried out by introducing (1) into the silicone compound or onto the surface of the silicone compound. The feed rate of the carrier gas flow may be, for example,
It can be appropriately determined depending on the vapor pressure of the silicone compound of formula (r), the type and amount of powder, and the capacity of the processing container. It is preferable to adjust the treatment time so that it can be processed in 30 minutes to 150 hours.

The carrier gas is preferably an inert gas such as nitrogen, argon, helium, etc., but it is also possible to use air or a mixed gas in which water vapor, methanol vapor, or ethanol vapor is mixed in the state of gas molecules in the inert gas.

According to the present invention, a mixed gas containing the silicone compound of formula (I) is brought into contact with the powder to be modified. The mixed gas is expressed by the formula (1
) contains the silicone compound gas as saturated vapor, it is necessary to make the contact/reaction temperature the same as or higher than the temperature of the mixed gas. This is because if the contact/reaction temperature is lower than the temperature of the mixed gas, the silicone compound is likely to condense and the powder will be treated in an aggregated form.

When a powder with many strong active sites on its surface is treated with a mixed gas, the powder tends to become a slurry. In this case, it is preferable to lower the relative pressure to the saturated vapor pressure of the silicone compound by raising the contact/reaction temperature to a temperature higher than the temperature of the supplied mixed gas and by simultaneously supplying a carrier gas that does not contain the silicone compound.

It is also possible to introduce the silicone compound and the carrier gas separately and mix them within the reaction vessel.

As described above, in the present invention, by supplying a mixed gas of a silicone compound and a carrier gas to the powder surface, molecules of the silicone compound are continuously adsorbed to the powder,
Polymerization is carried out using active sites on the surface.

In the present invention, it is particularly preferable to use gas phase treatment for ultrafine powders, porous materials, burl pigments, organic pigments, and the like. When these powders are treated in a gas phase, an ultra-thin film of silicone polymer is formed, and the ultrafine fineness, porosity, burr effect, etc. of the powder can be maintained. In addition, the raw 7i! A metal powder stable against oxidation can be obtained by immediately performing a gas phase treatment.

Note that by adsorbing a pigment or an ultraviolet absorber to the powder before performing the gas phase treatment, it is possible to obtain a powder having those colors and ultraviolet absorbing function. Also, clay tfL'#J
Even with UV absorbers intercalated between the layers, it is unstable when simply placed between the eyebrows and may be removed by solvents, etc. However, according to the present invention, if it is further coated with a silicone polymer, Not detached.

When an ultraviolet absorber is adsorbed onto a powder, new activity may occur; in this case, a polymer is generated on the ultraviolet absorber-adsorbing surface by contacting it with a silicone compound monomer. The ultraviolet absorbers used include 2-hydroxy 4-methoxybenzophenone, 2
, 2'-dihydroxy 4,4'-dimethoxybenzophenone, 2,2'-dihydroxy 4,4'-dimethoxybenzophenone sulfate, 2,2'4,4-tetrahydroxybenzophenone, 2,2'-dihydroxy 4,4'
-dimethoxybenzophenone, 2-hydroxy 4-methoxybenzophenone sulfate, 2-(2-hydroxy-5
'-methylphenyl)penzotriazole, 2-ethylhexyl valadimethylaminobenzoate, amyl valadimethylaminobenzoate, methyl 2,5-diisopropylcinnamate, urocanic acid, and the like.

According to the present invention, as already explained, a wide variety of powders can be modified by coating their surfaces with silicone polymer coatings, as long as they have active sites on their surfaces. Typical examples of such powders are listed and explained below. Inorganic pigments that can be modified by the present invention include, for example, ultramarine, navy blue, manganese bioleft, titanium-coated mica, bismuth oxychloride, iron oxide, iron hydroxide, titanium dioxide, and titanium lower oxidation. Examples include chromium hydroxide, chromium hydroxide, and the like. Among these inorganic pigments, the typical ones modified by the present invention are ultramarine blue and deep blue.

Gunjo is an inorganic pigment that usually exhibits a beautiful blue color with a slight reddish tint. In ancient times, it was made from natural lazuli stone, but nowadays it is almost exclusively manufactured artificially.
Ultramarine is sodium aluminum silicate containing sulfur, and is generally represented by the following compositional formula.

Na (b~q) A16 Si6 0za S n-
41 Ultramarine is a hydrophilic and oleophobic compound, is stable in air up to about 250°C, and has ion exchange ability and catalytic ability. Some of the sulfur in ultramarine is in the active radical form,
Differences in the state of these sulfur radicals and the state of oxidation cause changes in the color tone of ultramarine, and in addition to the reddish blue mentioned above, there are also purple-tinged and green-tinged ones.

Ultramarine blue is used as a blue coloring agent in a wide variety of fields, including building materials, paints, printing inks, paints, paper, textile products, cosmetics, and detergents.Its color is extremely clear and is harmless to humans and animals. It has become important recently.

However, ultramarine blue has serious deficiencies as a colorant. In other words, although ultramarine is generally stable to alkalis,
Extremely sensitive to acids, it gradually decomposes and fades to white while generating hydrogen sulfide under acidic conditions due to the reaction between radical sulfur and acid. Ultramarine blue also generates hydrogen sulfide when subjected to mechanical shearing force or heat during crushing. The hydrogen sulfide generated in this way causes problems such as secondary deterioration of container materials such as aluminium, and odor changes in products in the cosmetics and other fields. In order to overcome these drawbacks, several proposals have been made to improve the stability of ultramarine. For example, there is a method of treating ultramarine blue with sodium silicate and an organic acid to form amorphous silica on the surface (vF Publication No. 54-95632), and a method of forming an acid-resistant polymer coating on the surface of ultramarine blue. (Japanese Unexamined Patent Publication No. 50-27483). Although these conventional methods improve the acid resistance of ultramarine blue to some extent, they are still not sufficient.

In contrast, the ultramarine blue treated with the silicone compound according to the invention is a stable ultramarine blue without the above-mentioned drawbacks.

The stable ultramarine blue according to the present invention is stable against acid, heat, and mechanical shearing force, and does not decompose due to these actions and substantially does not generate hydrogen sulfide. Therefore, it can be used, for example, under acidic conditions. It does not alter the quality of container materials such as aluminum, nor does it cause odor to cosmetics.

In addition to these properties, the ultramarine blue according to the present invention is coated with a silicone polymer film, so it exhibits hydrophobicity and not only suppresses "wetting" to acids, but also enters the oil phase in emulsified systems, so the ultramarine blue is coated with a silicone polymer film. Restrictions on use have been removed and it has become possible to use it for a wide range of purposes.

The stable ultramarine blue modified by the present invention does not decompose other ingredients such as fragrances, so when used in pharmaceuticals and cosmetics, its stability over time is significantly improved. Furthermore, because the silicone polymer film is thin and highly transparent, there is no difference in color tone between stabilized ultramarine and untreated ultramarine.

The stable ultramarine blue according to the present invention has excellent stability because the surface of the ultramarine particles is covered with a silicone polymer film, and the sulfur on the ultramarine surface is not in direct contact with the outside air. Sulfur on the surface of ultramarine blue, that is, surface sulfur, is radical sulfur that exists on the surface of the crystal lattice of ultramarine.This is different from the sulfur (including radical sulfur) that exists inside the crystal lattice, and is free from other substances. It tends to have various types of activity against. This active surface sulfur decomposes under the action of acid, heat, and mechanical shearing force, producing hydrogen sulfide. The surface sulfur is coated with silicone polymer, which stabilizes the ultramarine and prevents it from decomposing even when exposed to acid or heat, suppressing the generation of hydrogen sulfide.

In this case, due to the high transparency of the silicone polymer, there is no difference in color tone between the stabilized ultramarine and the untreated one. The stable ultramarine according to the present invention is a powder, and its particle size is not particularly limited, but it is usually O. 1-200IIm, especially 0
．． 1 to 20 μm, preferably 0.0 μm for blue ones.
3-2 μm, 2-1 for reddish blue ones
It is 0 μm.

The amount of silicone polymer present in the stable ultramarine of the present invention varies depending on the surface area and surface activity of the ultramarine, but is about 0.
．． 1-20% heavy background, preferably 0. 2-2.0% by weight
It is. If it is less than 0.1% by weight, effective stability cannot be imparted to the ultramarine blue, while if it exceeds 20% by weight, bonding between ultramarine blue particles progresses and aggregation occurs, which is disadvantageous. The stable ultramarine according to the present invention can be obtained by coating the surface of the ultramarine particles with a silicone polymer film as described above. It can be made into ultramarine. For example, JP-A-57-17093
The present invention can be applied to a composite powder obtained by using the techniques described in each publication such as No. 1 and JP-A-57-179251, or by simply processing plastic and ultramarine blue in a ball mill to coat the surface with ultramarine blue. .

Since the above-mentioned active sites exist on the surface of the ultramarine powder, the silicone compound of formula (I) deposited on the surface is polymerized at a temperature of, for example, 120°C or lower to form a silicone polymer having a crosslinked network structure. can form a film of

The crosslinking rate can be increased by raising the temperature to about 200°C. Once the active surface is covered with a silicone polymer coating, no further adsorption and polymerization will occur.

The modified ultramarine blue according to the invention is used, for example, as a blue colorant, in particular in the paint, ink, pharmaceutical and cosmetic fields. Prussian blue is a blue inorganic pigment whose main ingredient is ferric ferrocyanide. It is an artificially synthesized pigment that is not found in nature, has good properties, and is used in large quantities as an inexpensive blue.

The chemical structure of dark blue is the general formula: MFe (Fe(CN),) + M= K, N
H4, expressed as Na.

The dark blue crystal has a cubic crystal structure, with Fe”゜ and F
e'° alternately occupy each vertex of the cube, 10 mN groups connect Fe'' and Fe'', and K, NH4, and Na occupy every other center of the cube.

The color is a deep blue unique to navy blue, and it has great tinting power as an inorganic pigment.

It has strong acid resistance but weak alkali resistance, and this property has limited its range of applications.

This alkali resistance can be slightly improved by introducing a nickel salt during production, but this is insufficient.

Heat resistance is also rather weak, decomposing and turning brown when heated, but the heat resistance limit is determined by temperature, time, and atmosphere.

The light resistance is good for dark colors, but becomes weaker when diluted with white pigment to make light colors.

It is also easily reduced and loses its blue color when reduced.

For this reason, if it coexists with substances that are easily oxidized, Prussian blue will act as an oxidizing agent and itself will be reduced and turn brown.

Some products are treated with anionic, cationic, or nonionic surfactants to prevent such effects, but this only improves dispersibility and the like.

As mentioned above, Prussian blue is sensitive to alkalis and has the effect of oxidizing other ingredients, so it cannot be used for concrete or walls.Also, even when used in cosmetics, it deteriorates fragrances, making it difficult to apply and only in small quantities. could only be used.

To fundamentally solve this problem, the dark blue surface should be completely coated with an inert material. However, since Prussian blue decomposes on the alkali side, surface treatment is difficult, and at present, surface treatment is not common.

In contrast, the navy blue treated with the silicone compound according to the present invention is a stable navy blue that does not interact with drugs and does not have a degrading effect on fragrances.

Therefore, when used in pharmaceuticals and cosmetics, the stability over time is significantly improved.

Furthermore, since the silicone polymer (resin) film is thin and highly transparent, there is no difference in color tone between the stabilized navy blue and the untreated one.

In addition to these properties, the navy blue according to the present invention exhibits hydrophobicity because it is coated with a silicone polymer film.
In emulsion systems, the restrictions on the use of Prussian blue because it enters the oil phase have been removed, making it possible to use it in a wide range of applications.

Examples of the stable navy blue according to the present invention include potassium navy blue and ammonium navy blue.

The particle size is not particularly limited, but is 0.01 to 200
pm, especially 0.01 to 100 μm, preferably 0.
05 to 0.1 μm. There is also bead navy blue that is granulated to make it non-scattering, and bead navy blue has a 0. 5-20
It has a particle size of about μm.

The coating amount of the silicone compound in the stable navy blue of the present invention varies depending on the surface area, but is about 0.5 to 40% by weight,
Preferably it is 5 to 30% by weight. If it is less than 0.5% by weight, it is not optimal for imparting effective stability to Prussian blue; on the other hand, if it exceeds 40% by weight, bonding between particles will progress and agglomeration will occur, resulting in poor dispersibility. is not optimal.

The stable navy blue according to the present invention can be expressed by the formula (V
) may be coated with a silicone polymer (resin) represented by the following formula. Therefore, even plastics or mica that have been surface-treated with navy blue can be made into a stable composite by coating with a silicone polymer. Although high temperature heating is not necessary to obtain a powder coated with a silicone polymer film,
The crosslinking rate can be increased by heating to 300°C or less, for example about 140°C. The modified navy blue according to the invention is used, for example, as a coloring agent, inter alia in the field of paints, inks and cosmetics.

Gold, gold metal oxides, and metal hydroxides are used as colorants in the fields of paints, inks, and cosmetics, but they are usually hydrophilic and do not have good dispersibility in oil or solvent systems. I can't say that. In addition, metal oxides and metal hydroxides have catalytic activity, and this catalytic action causes many problems such as deterioration of coexisting oils, fats, fragrances, and discoloration due to interaction with drugs. have.

Conventionally, silicone oil has often been used for surface treatment of metal oxides or metal hydroxides.
In No. 799, a metal or its oxide is treated with a linear or cyclic organopolysiloxane in the vapor phase at a high temperature of 350 to 650'C.

Furthermore, in Japanese Patent Publication No. 49-1769, titanium dioxide powder is directly coated, emulsion coated or solution coated with various alkylbolysiloxanes, optionally combined with an ester compound having a total carbon number of 6 or more, and dried and baked. We are modifying the dustiness and dispersibility of powder. Examples of such heat treatment include JP-A-55-136213, JP-A-56-16404, JP-A-56-29512, and JP-A-57-200306.

In addition to the treatment using heat as mentioned above,
25682 and Japanese Patent No. 1.214,497, there is a treatment method using mechanochemical energy, in which methylhydrodiene polysiloxane and the like are used. In this case, a substance such as zinc octoate is used as a crosslinking polymerization catalyst for methylhydrogenpolysiloxane.

Silicone-treated powder obtained by conventional processing methods does not have a silicone compound coated uniformly on the powder. However, even if the silicone compound coating is incomplete and some of the internal powder surface is exposed, it still shows water repellency.
If it coexists with fragrances, the fragrances will be degraded, and interactions with drugs will not be completely eliminated.

In addition, fine particle powders tend to agglomerate using conventional processing methods, and to date there has been no powder that remains fine particles and does not agglomerate. For this reason, even if the dispersibility was intended to be improved, agglomeration occurred during the process, and in the end, the dispersibility was not improved. The fundamental reason for this is that the silicone compound is supplied in liquid form.

JP-A-57-20, which is considered to be the best among the conventional methods.
In the method described in No. 0306, a silicone compound is sprayed in a gaseous state, but the sprayed mist particles are too large to form a film of several tens of angstroms on micron-sized powder particles, and the particles are separated from each other. The mist particles connected and aggregated, making it impossible to obtain satisfactory results.

In addition, silicone compounds require at least two or more hydrogen atoms in one molecule to form a film, and unless these hydrogen atoms are crosslinked, a stable film cannot be obtained, and the crosslinking rate is important. Regardless, the above-mentioned Japanese Patent Application Publication No. 57-2003
No. 06 has no such description.

As mentioned above, silicone compound coatings obtained by conventional methods have drawbacks such as non-uniform coatings and agglomeration, but they also require the assistance of thermal energy, mechanochemical energy, catalysts, etc. for silicone treatment. It also had the disadvantage of For example, when thermal energy such as baking treatment is applied, a metal hydroxide such as yellow iron oxide dehydrates and turns red, losing its function as a coloring agent. As described above, the conventional baking treatment has the fatal drawback that it can only be applied to some stable metal oxides and cannot treat mixtures all at once.

If a catalyst is used to lower the baking temperature, it is true that the process can be carried out at a low temperature, but the catalyst remains and accelerates the deterioration of the silicone resin on the surface, causing significant changes over time and impractical. there were.

In addition, the action of the catalyst is not limited to the silicone resin on the surface.
It promotes the decomposition of other substances that coexist with it, such as oils and fragrances, causing problems such as deterioration and odor, making it impossible to use it in cosmetics. A silicone treatment method using mechanochemical reactions is
Since no baking treatment is required, it can be applied to pigments with low temperature stability, but when this method is applied, the shape of powders that are plate-like or spherical will change due to the use of crushing force. In addition, it was difficult to treat powders such as titanium dioxide, which aggregate when stirred, alone.

In contrast, the modified metal oxides and metal hydroxides according to the present invention do not interact with drugs and do not have a decomposing effect on fragrances.

Therefore, when used in pharmaceuticals and cosmetics, the stability over time is significantly improved.

In addition, because the silicone polymer (resin) film is thin and highly transparent, there is no difference in color tone between stabilized metal oxides and metal hydroxides compared to untreated ones, and even when they are magnetic, their magnetic properties There is no difference in characteristics.

In addition to these properties, the metal oxides and metal hydroxides of the present invention exhibit hydrophobic properties because they are coated with a silicone polymer film. The restrictions on use of oxides have been removed, making it possible to use them in a wide range of applications. Furthermore, since it is completely covered with a silicone polymer film, it can be used as a column packing material for gas chromatographs, a column packing material for liquid chromatographs, etc.

The stable metal oxides and metal hydroxides according to the present invention include magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum oxide, aluminum hydroxide, silica, iron oxide (α-FezOi, γF
ezO3-. Fe2Qa, Fed), yellow iron oxide (
red iron oxide, black iron oxide, iron hydroxide, titanium oxide (especially titanium dioxide with a particle size of 0.001 to 0.1 μm), lower titanium oxide, zirconium oxide, chromium oxide, chromium hydroxide , manganese oxide, cobalt oxide,
These include nickel oxide, and composite oxides and composite hydroxides made of a combination of two or more of these, such as iron titanate, cobalt titanate, cobalt algonate, and the like.

The particle size is not particularly limited, but is 0.001 μm x
101 m, especially 0.001 to 200 μm, preferably
It is 0.01-10 μm. Even such fine particles are covered with a uniform thin film and do not aggregate.

The coating amount of the silicone compound in the stable metal oxides and metal hydroxides of the present invention varies depending on the surface area, but is about 0. 1-20% by weight, preferably 0.2-5.
It is 0% by weight. If it is less than 0.1%, it is not optimal for imparting effective stability to metal oxides and metal hydroxides, and conversely, if it exceeds 20%, particles will not bond together. As the process progresses, agglomeration occurs, which is not optimal in terms of dispersibility.

The stable metal oxides and metal hydroxides according to the present invention include metal oxides and metal hydroxides having the above formula (I [
) is sufficient as long as it is coated with a silicone polymer (resin). Therefore, even if plastic or mica has been surface-treated with metal oxide or metal hydroxide, it can be made into a stable composite by coating with silicone polymer. Can be done. Polymerization of silicone compounds does not require high temperature heating;
For heating at around ℃, 100x/(x
+y) Only the crosslinking rate increases, but it does not exceed the scope of the present invention. That is, the silicone compound of formula (4) is 1
Powder is left in a low partial pressure state where it vaporizes at a temperature of 0.000 C or below, adsorbed to the powder in its molecular state, and polymerized from the active sites on the surface. Therefore, this method is completely different from the conventional method of spraying a treatment agent and polymerizing it with heat. Japanese Unexamined Patent Publication No. 1983-
In the case of organosiloxane, the treatment temperature in the method described in 200306 is 230 to 350°C, which is not preferable for the reasons mentioned above, but the gas phase treatment can also be applied to metal oxides with low temperature stability. It can be said that the reaction range is wide. The metal oxides and metal hydroxides modified by the present invention are not only used as colorants in the fields of paints, inks, and cosmetics, but also as magnetic materials, ram fillers for gas chromatographs, and liquid chromatographs. It can be widely used as column packing material and catalyst carrier.

BACKGROUND OF THE INVENTION Organic pigments have many applications, such as being used in paints, inks, and cosmetics, and as colorants for plastics and rubber.

In order for organic pigments to break down into paints and inks and exhibit their original performance such as coloring power and clarity, and to produce good coatings and printing films, they must be dispersed in a dispersion medium in a form similar to primary particles. There is.

Conventional surface treatments for organic pigments for the purpose of improving dispersion include rosin treatment and adamant treatment. In these cases, the purpose is to suppress particle growth during production and to improve dispersibility by reducing agglomeration during pigment drying.

On the other hand, in polymer coating, a mixed system of an organic pigment, a polymerizable monomer, and a solvent is dispersed in a ball mill or sand mill, and then a polymerization initiator and catalyst are added to form a polymer on the surface of the pigment particles. In this case, the solvent is selected to dissolve the monomer but not the polymer.

However, although surface-treated organic pigments obtained by conventional processing methods improve pigment dispersibility to some extent, they have the disadvantage that the processing agent is not uniformly coated on the organic pigments, and for this reason, this pigment is not used in products. When blended with pigments, the active sites on the surface of the pigment often interact with other components in the vehicle of the product, causing deterioration of other components.

Furthermore, it is known that pigments such as Red No. 202 undergo crystal transfer and change color due to adsorption and desorption of crystal water. In order to prevent this, it is desirable to have a completely uniform surface treatment that coats the surface with pigment and prevents any moisture from penetrating, but such treatment is currently not possible. The reasons why the treatment agent is not uniformly coated on the organic pigment using conventional methods include problems such as adsorption in the solution and reaction of the reaction initiator, as well as problems such as agglomeration during the filtration and drying steps after treatment. In many cases, this occurred and was uneven.

In contrast, the modified organic pigment of the present invention is stable and does not react with other substances.

The organic pigments used in the present invention include Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 206, and Red No. 2.
No. 07, Red No. 220, Red No. 226, Red No. 227,
Red No. 228, Red No. 230, Red No. 405, Orange 20
No. 3, Orange No. 204, Orange No. 205, Yellow No. 4, Yellow No. 5
No., Yellow No. 205, Yellow No. 401, Blue No. 1, Blue No. 40
Examples include No. 4. Moreover, these organic pigments may be aluminum lake or zirconium lake,
Those organic pigments may be surface-treated, for example, those treated with rosin or the like.

There are no particular restrictions on the particle size of the organic pigment used in the present invention, but the particle size is 0.05 to 200 pm, particularly 0.05 to 3.0 pm.
A thickness of about 0 μm is preferable.

The higher the molecular weight of the silicone polymer that coats the surface, the more complete the coating will be; however, when used in paints, inks, and cosmetics, a molecular weight of 1000 or more is sufficient. If the molecular weight is 200,000 or more, it becomes a complete capsule that cannot be eluted even with a solvent such as chloroform.

The amount of silicone polymer present in the stable material of the present invention is about 0.1-20% by weight, preferably 0.1-20% by weight. 2-5
Weight%. If the amount is less than 0.1% by weight, effective stability cannot be imparted to the organic pigment.

Conventionally, a temperature of about 150°C was required to polymerize a silicone compound on the powder surface, but in the present invention, the temperature at which the organic pigment and silicone compound are allowed to stand is 100°C.
A temperature below 0°C is sufficient. In addition, when processing in a closed system,
If nitrogen substitution is performed, it is safe to introduce a large amount of silicone compound, and if the reaction is performed under reduced pressure, the rate of adsorption will be slightly faster. The modified organic pigment of the present invention can be used in paints, inks,
It can be used as a coloring agent in fields such as cosmetics. Bani Doe & HakuoMica-titanium composite materials, which are made by forming a titanium dioxide layer on the surface of fine flaky mica, have been used in cosmetics, paints, plastics, etc. due to their pearlescent luster and various interference colors. It is widely used as a pigment.

Vacuum deposition is a method for producing it, but as described in DuPont's patent (Japanese Patent Publication No. 43-25644), an aqueous solution of an inorganic acid salt of titanium (for example, titanyl sulfate) is hydrolyzed in the presence of mica, and mica is A common method is to precipitate hydrated titanium dioxide on the surface and then heat it. The mica used is generally Muscovite mica (+nuscovite).
However, in some cases, it is also possible to use biotite, etc. In addition, mica is pulverized with water in advance and the particle size is made uniform using a sieve.

The developed mica-titanium composite material exhibits various interference colors depending on the thickness of the titanium dioxide coating layer on the mica particle surface. The interference color is usually silver when the amount of titanium dioxide is 10 to 26% by weight of the raw wood, but when it is 26 to 40% it is golden,
In the range of 40 to 50%, the color changes to red, blue, and green as the titanium dioxide layer increases, and in the range of 50 to 60%, higher order interference colors are obtained. Although these mica-titanium composite materials have pearlescent luster and various pale interference colors, the external color is always close to white, and no material with a bright external color matching the interference color has been obtained. Conventionally, in order to produce various external colors, colored pigments such as iron oxide, navy blue, chromium oxide, carbon blank, and carbon were added to the raw mica-titanium composite material. The safety, stability, light resistance, acid resistance, alkali resistance, solvent resistance, heat resistance, etc. of these colored mica-titanium composite materials are largely due to the properties of the colored pigments added. Mica titanium composite materials discolor in alkaline solutions, and red mica titanium composite pigments containing carmine discolor and deteriorate when exposed to light.

As mentioned above, mica-titanium composite materials have titanium dioxide and colored pigments on their surfaces, and not only do they deteriorate as described above, but also when added to resins or oils, their catalytic action can cause other problems. It often causes the deterioration of coexisting substances. Some products are coated with silica to prevent this effect, but the coating is not complete and no significant effect has been observed. Chromate treatment is also carried out, but the reality is that it is not used in Japan due to pollution problems and cost.

In contrast, the modified burl luster material of the present invention is stable. The pearl luster materials used in the present invention include mica titanium composite materials, mica iron oxide composite materials, bismuth oxychloride, guanine, and further coated with titanium compounds containing titanium oxynitride and/or lower titanium oxides. Examples include molten mica. The titanium in the mica-titanium composite material may be titanium dioxide, lower titanium oxide, or titanium oxynitride. Further, a mica titanium composite material or bismuth oxychloride may be further mixed with a colored pigment such as iron oxide, navy blue, chromium oxide, carpon black, carmine, or ultramarine blue. The pearl luster material used in the present invention may be used as it is, but if it is used in powder form as a burl luster pigment, the particle size is 0.
Particles with a particle size of about 1 to 200 μm, particularly about 1 to 50 μm, and as flat as possible are preferred because they tend to exhibit beautiful color tone and pearlescent luster.

The higher the molecular weight of the silicone polymer coating the surface of the above-mentioned pearlescent material, the more complete the coating will be, but a molecular weight of 1000 or more is usually sufficient when used for paints, inks, cosmetics, etc. When the molecular weight exceeds 200,000, the capsule becomes a complete capsule that does not shed or elute even when a solvent such as chloroform is used. The amount of silicone polymer present in the stable coated burl gloss material of the present invention ranges from 0.1 to 20% by weight, preferably 0.1 to 20% by weight of the total coated burl gloss material.
It is 2 to 5% by weight. If it exceeds 20%, it will adversely affect the burl gloss, and if it is less than 0.1%, the effect of the present invention will be small.

The coated pearl luster material obtained by the present invention not only has improved stability, but also the powdery burl luster material has good luster, probably due to improved coordination.

The pearlescent material modified according to the present invention is useful as a pigment or colored pearlescent material for, for example, paints, inks, plastics, cosmetics, ornaments, household goods, textile products, or ceramic products.

The modified mica-titanium composite material of the present invention is also expected to be used as a conductive layer or recording layer for recording paper, and as an antistatic material. Among the silicate minerals that have a wide range of industrial uses, phyllosilicate minerals and tectosilicate minerals can be cited. Among these, phyllosilicate minerals are plate-like or flaky-like and have clear cleavage parallel to the bottom surface. It is generally soft, has a relatively low specific gravity, and exhibits flexibility and elasticity on the arm opening. This property has been widely used in cosmetics because it improves usability when used in cosmetics. These characteristics are due to the layered structure of these minerals, which are made up of two-dimensionally expanded SiO4 tetrahedra, which is an important precept element. This tetrahedral layer is another structural unit. AI, FJgs It is combined with a layered group consisting of metal ions such as Fe.

Since the sizes of the unit structures within the tetrahedral and octahedral layers are almost the same, their stacking easily occurs. As a result, a two-layer structure in which two types of layers are stacked one on top of the other, or two
A three-layer structure is created in which an octahedral layer is sandwiched between two tetrahedral layers like a sandwich inch. These composite layers are electrically neutral, and those with negative charges maintain their neutrality by the infiltration of K and Na ions.

However, K compounds with such a structure have a local charge imbalance, which causes them to exhibit activities such as solid acids. Also, Tectosilicate i! Objects have a three-dimensional skeleton or frame consisting of (Si, AI>Oz), and most minerals are aluminosilicate.The reason is that the three-dimensional frame is negatively charged. This is because some of the Si4* ions must be replaced by AI''.

These negatively charged frames are neutralized by containing cations, and depending on the degree of neutralization, active sites are expressed. For the above reasons, when phyllosilicate minerals and tectosilicate minerals are used in cosmetics or paints, they have the negative effect of degrading coexisting fragrances, oils, fats, and resins.

Conventional techniques have focused on dispersion techniques such as dispersion into paints, etc., and there have been no treatment techniques to suppress the catalytic activity on the surface.

In addition, attempts have been made to treat the surface with silicone oil, but it is not possible to completely cover the surface, and the current situation is that it only has the ability to provide ↑Ω water-based properties. Silicone-treated powder obtained by conventional processing methods does not have a silicone compound coated evenly on the powder. However, even if the silicone compound coating is incomplete and some of the internal powder surface is exposed, it still shows {Ω water-based. however,
If it coexists with fragrances, the fragrances will be degraded, and interactions with drugs will not be completely eliminated.

The main reason for this is that the silicone compound is supplied in liquid form.

Among the conventional methods, the one that is considered to be the best is the one described in JP-A-5
No. 7-200306, however, this method has drawbacks as described in connection with metal oxides.

In addition, in the case of silicone treatment, baking may be performed at a temperature of 150°C to 350°C, but in most cases this is done from liquefaction, and solid acids such as phyllosilicate minerals and tectosilicate minerals are used. If a strong substance coexists with silicone oil, ring-opening polymerization will occur, resulting in silicone rubber. As a result, silicate minerals are dispersed in the silicone rubber. If a catalyst is used to lower the baking temperature, it is true that the process can be carried out at a low temperature, but the catalyst remains and accelerates the deterioration of the silicone resin on the surface, causing significant changes over time and impractical. there were. In addition, the catalytic action promotes the decomposition of not only the silicone resin on the surface but also other coexisting substances such as oil and fragrance, causing problems such as deterioration and odor, making it impossible to use it in cosmetics, etc. Ta. The silicone treatment method using mechanochemical ξcal reaction is
Since baking is unnecessary, it can also be applied to pigments with low temperature stability, but when this method is applied, the shape of powders that are plate-shaped or spherical will change due to the use of crushing force. In particular, phyllosilicate minerals are plate-like or flaky, and in order to take advantage of their characteristics, mechanical reactions are not suitable. In contrast, the modified silicate mineral according to the present invention has no interaction with drugs and does not have a decomposing effect on fragrances. Therefore, when used in pharmaceuticals and cosmetics, stability over time is significantly improved.

In addition, since the film of silicone polymer (resin) is thin and highly transparent, there is no difference in color between silicate materials and untreated materials.In addition to these properties, the silicate minerals according to the present invention teeth,
Because it is coated with a silicone polymer, it exhibits hydrophobicity and enters the oil phase in emulsified systems, which removes the limitations of silicate polymers and allows it to be used in a wide range of applications. .

Stable silicates according to the present invention include phyllosilicate minerals (e.g., kaolin, montmorite, argillite, chlorite, serpentine) and tectosilicates (
For example, the zeolite family: paikuchiphyllite, talc, chlorite, chrysotile, antigorite, lizardite, kaolinite, deckite, natalite, yakuchisite, montmorillonite, nontronite, saponite, sauconite, bentonite and sodazeolite. , the sodazeolite family such as mesozeite, scoresite, and thomsonite; the heliosideite group, such as heliodite, fasciolite, and avidite; and the zeolites, such as analzeite, deuterite, ashlarite, chabazite, and gmelinite, etc. is exemplified. These phyllosilicate minerals may contain organic cations between the eyebrows, or may be substituted with alkali metal, alkaline earth metal ions, etc. In tectosilicate as well, metal ions may enter the pores.

The particle size is not particularly limited, but is between 0.01 μm and 10 μm.
n1, especially 0.01 to 100 μm, preferably 0.1 to 30
It is μm.

Stable silicate 112 of the present invention: The amount of silicone polymer coverage in the article varies depending on the surface area, but is about 0.
1-20% by weight, preferably 0. 2-5. O m view%. Less than 0.1% by weight is not optimal for imparting effective stability to silicate minerals;
If it exceeds the weight ratio, particles will continue to bond with each other and cause aggregation, which is not optimal in terms of dispersibility. The stable silicate mineral according to the present invention can be obtained by coating the silicate mineral with a silicone polymer (resin). Therefore, even if the plastic is surface-treated with a silicate mineral, it will be stabilized by the silicone polymer coating. It can be made into a complex.

Polymerization of silicone compounds does not require high temperature heating;
Heating at about 200° C. only increases the crosslinking rate and does not exceed the scope of the present invention.

The modified silicate mineral according to the present invention is an electrical insulator,
In addition to being used as a filler for chemicals, nitrogenous materials, paper, rubber, paint, cosmetics, etc., it can also be used as a catalyst, adsorbent, etc. by changing its surface structure with a silicone polymer film.

Conventionally, in the field of fragrances, etc., formulations such as gel type, liquid type, aerosol type, and impregnated type are known. Porous materials used in the impregnated type include dehydrated mordenite described in JP-A-52-41244, and JP-A-56-5372.
Kaolin group described in Japanese Patent Application Laid-open No. 13342/1983,
JP-A-55-103861, JP-A-53-29943
No., Japanese Patent Application Publication No. 15439/1982, Japanese Patent Application Publication No. 1107/1983.
Silica described in each publication No. 9, Utility Model Publication No. 54-22771,
Alumina, silica alumina, gypsum board, etc. are used. However, these porous substances have quite a few active sites such as acid sites, base sites, oxidation sites, and reduction sites on their outer surfaces and pore surfaces, and when they coexist with fragrances and drugs, they can Some substances may decompose and change in quality, causing odor and deterioration in a short period of time.

For this reason, impregnated type formulations cannot be prepared, the selection of fragrances, etc. is limited, and the products have no choice but to lack elegance in fragrance.

On the other hand, porous materials have a wide range of uses, such as carriers for fragrances and drugs, but since they are used as carriers, it is necessary that they do not decompose or change the quality of fragrances or drugs. Conventionally, surface modification of porous materials has been carried out in various fields, but most of them have used liquid phase treatment. If the material to be modified is a porous material, the pores will be collapsed by the liquid phase treatment, and the treated porous material will no longer have the performance as a porous material.

Therefore, when a porous material is used as a carrier for fragrances or drugs, it is necessary to select a porous material that is inherently inactive. However, in the case of fragrance carriers or drug carriers, it is necessary to impregnate a large amount of fragrances or drugs, so it is necessary to select a porous material that has many pores, and therefore the specific surface area becomes large. . Therefore, even in porous materials with a low active site density, the number of active sites increases overall, making it impossible to completely prevent the deterioration of fragrances and drugs. Therefore, the only way to create a product is to use a limited number of highly stable fragrances and drugs, and the product's characteristics (elegance of fragrance, medicinal efficacy, etc.) could not be fully demonstrated. In order to fundamentally solve the above phenomenon, maintain the characteristics of a porous material, that is, the ability to support a large amount of fragrances and drugs in its pores, and stably support fragrances and drugs. acid sites on the outer surface of the porous material and on the pore surfaces;
A technology is needed to inactivate active sites such as basic sites, oxidation sites, and reduction sites without crushing pores.

On the other hand, a cyclic silicon compound represented by the above formula (wherein RZ, Rj and b have the same meanings as above), a cyclic silicon compound represented by the above formula (R"R3Si
O) b (R'R'R'SiOh) c( rV b
) (wherein R!~R6, b and C have the same meanings as above) is brought into contact with a porous material in the form of vapor, and the porous material is The modified silicone compound of the present invention is prepared by polymerizing the silicone compound on the outer surface and pore surface of a porous material by utilizing its surface activity to form a silicone polymer to cover and eliminate the surface activity. Highly porous materials have high stability against fragrances and drugs, and can be used as excellent carriers. The time for gas phase treatment is generally 1 hour to 72 hours,
Thereafter, unpolymerized silicone compounds are removed by degassing to obtain the desired product.

Porous materials used in the present invention include silicate minerals such as pyrophyllite, talc, chlorite, chrysotile, antigorite, lizardite, kaolinite, deckite, natalite, hallosite, montmorillonite,
Nontronite, saponite, sauconite, bentonite, soda zeolite, mesozeolite, scores zeolite, Thomson zeolite, diabolite, fasciolite, avidite, analzeite, deuterite, ash zeolite, chabazite, gmelin zeolite, muscovite , phlogopite, biotite, sericite, iron mica, red mica, lithian mica, Chinwald mica, soda mica, KAh (AtSSi3)OIOL, KMg(A
I, Sis) OIoFzK (Mgs Fe3) (AI
, Si3)0+oFz, metal oxides such as magnesium oxide, magnesium hydroxide, zinc oxide, calcium oxide, calcium hydroxide, aluminum oxide, aluminum hydroxide, silica, iron oxide (α-FezO3, T F
ezO:+, FP3xOa, Fed), iron hydroxide,
Titanium oxide, lower titanium oxide, zirconium oxide, chromium oxide, chromium hydroxide, manganese oxide, cobalt oxide,
Nickel oxide and combinations of two or more of these silica alumina, iron titanate, cobalt titanate, lithium cobalt titanate, cobalt aluminate, carbonate minerals CaCOz, Mgco, , Fe
CO:+. MnCO= , ZnC01CaM
g(COI)t, Cu(OH)zco:+, C
u+(O}I)z(COs)z, sulfate mineral Ba
SO4. SrSO< , PbSOa + Ca
SO4CaSO4・2}1zo,CaSOn '5H
20. CLl4. SO4. (OH) & IKA13(
OH)6(SQL)2 ,KFf3:+(OH)6(S
O4)z, phosphate mineral YPO4+ (Ce
, La) Pot + Fei (PO4)z8H20,
Cas(Pot)3F, Cas(PO*)ict
, Cas(PO*)sOH, CasCPOa ,
Examples include C(hOH)z (F-Of{), metal nitrides such as titanium nitride, boron nitride, and chromium nitride.

Alternatively, these materials may be granulated or molded, or granulated or molded and then burned. Furthermore, it can be applied to cellulose, fibers, synthetic resins, etc. i.e. porous glass beads, hollow silica or zeolites, or metal oxides, metal nitrides, silicate minerals, carbonate minerals, sulfate minerals or phosphate minerals,
Granulated or shaped products, metal oxides, metal nitrides, silicate minerals, carbonate minerals, sulfate minerals, or phosphate minerals that are granulated or shaped and then fired, Mimetal,
Cellulose, fibers or Hewei resin can be treated.

The treated amount, that is, the amount of silicone polymer adsorbed, reacted, and polymerized, varies depending on the type and surface area of the porous material, but is usually 0.01 to 60% by weight, particularly about 0.01 to 20% by weight, based on the total amount of the treated carrier. %. Further, depending on the intended use of the treated carrier, the active sites may not be completely covered. The particle size is not particularly limited, but is 10 tm or less, preferably 3 μm to 101 l.

The method for treating the porous material is a gas phase method, in which the silicone compound is brought into contact with the porous material in the form of gas molecules.

That is, the silicone compound does not necessarily have to be a gas at room temperature and pressure, and any solid or liquid that can be turned into a gas by heating or the like can be used.

Compounds of formulas (IIIc) and (IVb) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclopentasiloxane, heptamethylcyclobentasiloxane, Hexamethylpentasiloxane,・
Pentamethylsiloxane, octamethyltrisiloxane, 1,1,1,2,3,4,4.4-octamethyltetrasiloxane, 1,1.1.2,3,4,
5.5.5 Mono-nonamethylpentasiloxane and the like.

The manufacturing method of the present invention will be explained in detail below.

The main part of the method of the present invention is that the surface active sites of the porous material come into contact with the gas molecules of the silicone compound,
Basically, any embodiment may be used as long as the gas molecules of the silicone compound diffuse into the outer surface and pores of the porous material.

For example, it can be manufactured using a closed system.

In this case, simply leave the porous material and silicone compound in separate open containers in a closed system. If the porous material had no activity, the silicone compound would not react or polymerize even if it was adsorbed to the porous material, and the silicone compound would be desorbed when taken out from the closed system. Therefore, in this case the porous material is not silicone modified.

When there are active polymerization sites on the surface, the silicone compound adsorbs onto the surface of the porous material, reacts, polymerizes, and is consumed, so the partial pressure of the silicone compound near the surface of the porous material decreases and the silicone compound in the container decreases. is further volatilized and supplied. In this way, the reaction and polymerization proceed one after another, and when the active sites on the surface are completely covered, the polymerization activity disappears, and at that point, the polymerization stops naturally.

Since it is based on such a simple principle, the manufacturing method of the present invention does not require any special equipment. Manufacturing can only be carried out in a closed room. It is more preferable if the closed room can be kept at a constant temperature. A desiccator can also be used for small-scale production. Ideally, a device that can degas after treatment is desirable.

Also, by placing only the porous material in a sealed chamber in advance,
It is also possible to take an embodiment in which the silicone compound is volatilized at a required partial pressure in a separate sealed chamber, and the volatilized silicone compound is introduced into the chamber in which the porous material is placed through a pipe or the like. When processing in such a closed system, vapor pressure can be controlled by temperature, and diffusion can be controlled by pressure.

Therefore, in order to increase the diffusion rate of the silicone compound, the treatment can also be carried out under reduced pressure. In this case 100nHg
The following are preferred.

In addition to the closed system, a method may be used in which the silicone compound is introduced into the porous material using a carrier gas. However, at this time, it is desirable that the vapor pressure of the silicone compound does not exceed saturation near the porous material.

In either embodiment, the treatment time is generally 30 minutes to 72 hours, and then degassed to remove unreacted and unpolymerized silicone to obtain the desired product.

Regarding the compounds of the above (II[c) and (IVb), the smaller the number of b, the lower the boiling point, the faster the rate of volatilization and adsorption to porous substances, and in the case of formula (Ilrc), b-3 ~
7. In the case of formula (IVb), b=2 to 5 is desirable. or,
Hydrogen atoms play an important role in the crosslinking reaction, and two or more hydrogen atoms are desirable in one molecule. An exception is a porous material such as zinc white, in which case silicone modification can be uniformly performed without Si--H groups.

Further, during the reaction, water adhering to the porous material acts as a reaction accelerator; however, if the amount of adhering water is small, steam may be added.

The production method of the present invention is characterized by a gas phase contact reaction, and the volatilized silicone compound is adsorbed onto the surface of a porous material and then undergoes a polymerization reaction through its active sites. In other words, the amount of bioactive substances adsorbed and reacted varies depending on the type and surface area of the porous material. Usually, about 0.01 to 30 weight f in the total amount of silicone-modified porous material
%. Note that, depending on the purpose of use of the silicone-modified porous material, the active sites on the porous material may be completely covered.

The present invention is characterized in that the silicone compound is brought into contact with the porous substance in the form of gas molecules, so not only silicone compounds with low boiling points but also those with high boiling points that are not gaseous at room temperature and pressure can be used under reduced pressure or at high temperatures. It can be used if it is made into a gas. Sublimable substances such as hexamethylcyclotrisiloxane can also be used. In the method of the present invention, it is preferable to select a silicone compound that becomes a polymer with a three-dimensional structure when reacted and polymerized. This is because silicone does not easily desorb even when a silicone-modified porous material is immersed in fragrances, drugs, solvents, etc. RZ,. Silicone compounds in which R3 and the like are methyl groups are easy to handle, but due to restrictions on the polymerization mechanism, only linear polymers can be used.

The dimethyl type is of formula (Iffc) and b
= 3 is desirable, but this material is solid at room temperature and pressure. However, as mentioned above, even such a material can be fully utilized in the present invention. When R3 is a hydrogen atom, it is crosslinked as shown in the following formula, so a network-like polymer can be formed.

In order to obtain a wire-like three-dimensional structure, it is desirable that there be two or more St-H moieties in one molecule of the silicone compound.

The thus crosslinked polymer has crosslinked units [R”
SiOs7z ] x is added. The more X units there are, the more developed the network structure is, which is preferable as a polymeric coating film. In this case, [R”Si03/
z co X [R”HSiO co y [(R”):+
It becomes a film such as SiO+zz] z.

Since the present invention uses active sites on the surface, polymerization occurs only on the surface, and since it uses a gas phase reaction, the active sites can be effectively blocked and the pores are almost completely closed. Saved.

In addition, in coatings using solvents, they will elute when immersed in the same solvent, but in the present invention, the polymer can be polymerized to the extent that it does not elute into the solvent by polymerizing the surface, so there is no such thing as elution.

For example, in order to prevent elution in solvents such as chloroform, the ratio of the number of X units produced by crosslinking reaction to the unreacted y units (x/x+y) should be 20% or more. .

The treated carrier obtained by the present invention does not decompose or change the quality of fragrances or drugs even if they coexist on its outer surface and pore surface, and therefore does not cause problems such as discoloration and odor. It is possible to control the release over a long period of time. Therefore, it can be suitably used in fields such as fragrances, medicines, and toys. Furthermore, since the present invention utilizes a gas phase reaction that takes advantage of the surface activity of porous materials, even porous materials that have been granulated or specially shaped can be processed without changing their shape and maintaining their pores. Can be processed. Therefore, it can be used in fields such as fragrances, medicines, toys, artificial organs, artificial bones, and ceramics.

Carbon Carbon such as activated carbon and carbon black is used as a coloring agent in the fields of paints, inks, and cosmetics, but it is usually hydrophilic and does not have good dispersibility in oil or solvent systems. In addition, lilybon has catalytic activity, and this catalytic action has disadvantages such as degrading coexisting oils, fats, fragrances, and adsorbing drugs.

Conventionally, a method for making a hydrophilic powder hydrophobic is to perform a surface treatment such as alkylating the powder surface, but since carbon is inert, it has been difficult to make it hydrophobic using conventional methods.

Surface treatment using silicone oil is often performed as a method for blocking the surface activity of powders and the like.

Silicone-treated powder obtained by conventional processing methods does not have a uniform coating of silicone compounds on the powder. However, even if the silicone compound coating is incomplete and some of the internal powder surface is exposed, it still exhibits water repellency. However, if they coexist with fragrances, the fragrances will be degraded, and interactions with drugs will not be completely eliminated.

In addition, fine particle powders tend to agglomerate using conventional processing methods, and to date there has been no powder that remains fine particles and does not agglomerate.

The fundamental reason for this is that the silicone compound is supplied in liquid form.

Among the conventional methods, the one that is considered to be the best is the one described in JP-A-5
7-200306, but this method has the same drawbacks as described in connection with metal oxides.

As mentioned above, silicone coatings obtained by conventional methods have drawbacks such as non-uniform coatings and agglomeration, but they also require thermal energy and
It also had the disadvantage of requiring the assistance of mechanochemical energy catalysts.

For example, if a catalyst is used, the treatment can be performed at low temperatures, but the catalyst remains and accelerates the deterioration of the silicone resin on the surface.
Usually, the changes over time were so significant that they were impractical. In addition, the catalytic action promotes the decomposition of not only the silicone resin on the surface but also other coexisting substances such as oil and fragrance, causing problems such as deterioration and odor, making it impossible to use it in cosmetics, etc. Ta. Silicone processing method using mechanochemical reaction is
Because the crushing force is used, the shape of the powder changes. On the other hand, the modified carbon according to the present invention does not interact with drugs, does not exhibit a decomposition effect on perfumes, is highly hydrophobic, and has excellent lipophilicity.

Therefore, when used in pharmaceuticals or cosmetics, stability over time is significantly improved.

In addition to these properties, the modified carbon according to the present invention has
Because it is coated with a silicone polymer film, it exhibits hydrophobicity and enters the oil phase in emulsion systems, etc., which removes the limitations of carbon, making it possible to use it in a wide range of applications.

Furthermore, since it is completely coated with silicone polymer, it can be used as a column packing material for gas chromatographs, a column packing material for liquid chromatographs, etc.

Especially when used as a column packing material for liquid chromatography, carbon itself is stable against acids or alkalis, so eluents with a wide range of pH from acidic to alkaline can be used during chromatography. ．． Chemically bonded resins using silica gel as a carrier, which are currently widely used, cannot be used in alkaline conditions, but when the stable and highly lipophilic carbon of the present invention is used as a filler, alkaline eluents can be used. It is also possible to use

The coating amount of the silicone polymer on the stable and highly lipophilic carbon of the present invention varies depending on the surface area, but is about 0. It is 1 to 50% by weight, preferably 1 to 30% by weight. If it is less than 0.1% by weight, it is not optimal for imparting lipophilic properties that are effective to Liichibong, and if it exceeds 50% by weight, bonding between particles progresses and aggregation occurs. Not optimal in terms of dispersion. Furthermore, the pores of carbon are blocked, making it unsuitable as a filler. The particle size is not particularly limited, but is 0.001 μm to 10 m.

It is sufficient to leave the carbon and silicone compound at a temperature of 100°C or less. In this way, there is no need for high-temperature heating, but
Heating at 100° C. or higher only increases the crosslinking rate and does not exceed the scope of the present invention.

The modified carbon according to the present invention can be used in paints, inks, tires,
It is not only used as a coloring agent in the field of cosmetics, but can also be used in a wide range of applications, such as catalyst carriers, gas chromatograph column fillers, and liquid chromatograph column fillers.

The main metals that can be modified by treatment with the silicone compound according to the present invention include iron, cobalt, nickel, copper, zinc, aluminum, chromium, titanium, zirconium, molybdenum, silver, indium, Mention may be made of tin, antimony, tungsten, platinum, and gold, as well as their alloys. The modified metal powder according to the present invention is stable (ie, does not autooxidize upon contact with oxygen) and has significantly improved dispersibility. Therefore, the modified metal powder described above can be effectively used, for example, in magnetic recording materials.

The particle size of the metal powder is not particularly limited, but is 0.01 μm to 10 m, especially 0.01 μm to
It is preferable to modify the 5n metal powder. Preferably, the silicone polymer coverage is about 0.01 to 20% by weight.

Mica is used in the fields of paints, inks, and cosmetics, and is added as a filler to plastics and rubber, but it is usually hydrophilic and does not have good dispersibility in oil or solvent systems. When kneaded into plastics and rubbers, agglomeration occurs, making it difficult to mix uniformly. For this reason, many surface treatments have been performed on mica. For example, in JP-A No. 56-29512, mica is baked with various 3-lisiloxanes, hydrocarbons, or higher fatty acids, and it is stated that a coating is formed by the reaction between siloxane and fatty acids and the reaction with the mica surface. ing. Also, JP-A-55-136213 and JP-A-5
In No. 6-16404, silicone oil is added to cosmetic raw materials containing mica, and an oil agent is added by baking in the same manner. In JP-A-57-200306, although the treatment of mica is not specifically described, inorganic powders are treated with organic silicon compounds in general to obtain pressed makeup cosmetics.

Except for the treatment using heat as mentioned above,
5682 and Japanese Patent No. 1214497, there are methods of processing using mechanical energy. Silicone-treated mica obtained by conventional processing does not have a uniform coating of a silicone compound on the mica. Since the silicone compound is incompletely coated, a portion of the mica surface is exposed, and if it coexists with fragrances, etc., these will decompose and accelerate deterioration.

The fundamental reason for this is that the silicone compound is supplied in liquid form.

The method described in JP-A-200306, which is considered to be the best among the baking treatment methods, uses gaseous spraying, but even the mist particles sprayed with this method do not reach the mica surface in micron order. It is too large to form a film with a thickness of several tens of angstroms, and the mica particles may become interconnected with each other, resulting in uneven film formation. The reason why the amount of silicone compound added is limited to 1 to 10% relative to mica is that
This is because, as stated in the above-mentioned publication, if the content exceeds 10%, the silicone compound acts not as a surface treatment agent but as a binder, resulting in mica agglomeration. This clearly indicates the above-mentioned situation in which the particle size of the sprayed silicone compound is still too large for the mica. In addition, treatment methods that use mechanochemical energy have the disadvantage that the mica is crushed and loses its original plate shape, resulting in loss of transparency and poor slippage. In contrast, the modified mica according to the present invention is a stable mica without the above-mentioned drawbacks.

Since the stable mica according to the present invention does not decompose other substances such as fragrances, when used in pharmaceuticals and cosmetics, the stability over time is significantly improved.

Furthermore, since the silicone polymer film is thin and highly transparent, the stabilized mica has no difference in color tone from untreated mica.

In addition to these properties, the mica according to the present invention exhibits hydrophobicity because it is coated with a silicone polymer film.
In emulsion systems, etc., it can be blended into the oil phase, and there are fewer restrictions on blending, making it possible to use it in a wide range of applications.

Further, in the present invention, even if the amount of silicone polymer is 10% or more based on the weight of mica, the mica does not become lumpy, and a large amount of coating of about 90% can be performed. As will be described later, if the treatment is carried out in a gas phase, even if a large amount of coating is applied, it has a particularly fluffy feel and has no disadvantages such as stickiness.

Mica that is completely coated with a silicone polymer film does not interact with other components and is hydrophobic, so it can be expected to have a wide range of uses, such as being able to be incorporated into paints, inks, and cosmetics.

The mica that forms the core of the silicone bolimica monomica complex applied to the present invention is a type of mica such as muscovite, phlogopite, biotite, sericite, iron mica, rhodochite, lithian mica, Chinwald mica, and soda mica. is an artificial mica in which the OH group of mica is substituted with F [
For example, KA1z(AI, Si)0+oFz. KMg
z(AI.Sis)0+oFz SK(Mg.Fe
i) (AI, Sis) 0,. Ft ] can be mentioned. These mica may be burned out. There are no particular restrictions on the particle size of the mica used in the present invention, and raw ore can be treated, but the particle size is 0.5 to 200 μm.
, especially those with a diameter of about 0.5 to 40 μm can be processed quickly. The amount of silicone polymer present in the stable mica of the present invention varies depending on the purpose, but when the original shape of the mica is not changed, it is about 0. 1-20% by weight, preferably 0. 2
~5% by weight. 0.1% by weight cannot impart effective stability to mica.

In addition, when obtaining stable mica by folding the mica and making the mica foil thinner as described in detail later, the amount of silicone polymer present is 20 to 95% by weight, especially 20 to 95% by weight.
It is also possible to obtain a composite material with a density of 90%, resulting in a fluffy composite material.

The stable mica according to the present invention only needs to be coated with a silicone polymer, and therefore even mica-coated plastics or paper can be made into stable mica by coating with a silicone polymer. Even if the silicone compound exceeds 10% by weight or more based on the mica, the mica swells and becomes fine powder.

The larger the amount of silicone compound, the more the swelling progresses, and the mica is coated while being inspected. The silicone compound can be used in an amount of up to about 95% by weight based on the mica.

In order to cause polymerization on the surface, heat or a polymerization catalyst was generally used, and conventionally a temperature of about 150°C was required. A temperature of 100°C or less is sufficient.

If the temperature is further raised to, for example, about 200° C., the crosslinking rate increases.

The treatment method described in JP-A-57-200306 uses a step of gaseous spraying and heating, and the treatment is performed with 10% by weight or less of a silicone compound. The particles adhere to the mica surface and polymerize there, so it does not expand. The supply of the silicone compound must be entirely by diffusion in the molecular state.

In particular, when a silicone compound is used in an amount of 20% by weight or more, the arms of the mica open, resulting in fluffy and thin mica. Mica expanded in this way becomes white, and especially when biotite is treated, it becomes significantly whiter than before treatment. Also, fold opening,
Expanded mica is soft and slippery,
Suitable as a raw material for cosmetics.

Furthermore, raw mica ore can also be opened, and if it is crushed after opening, it can be easily powdered, which is a manufacturing advantage.

The modified mica according to the present invention is not only used as a filler in the fields of paints, inks, and cosmetics, but can also be kneaded into rubber and plastics for a wide range of applications such as heat insulation, prevention of radio wave interference, and prevention of mold adhesion.

Due to its high safety, biopolymer powder is used in pharmaceuticals and cosmetics. However, the surface of biopolymer powder is
Since it is covered with hydrophilic groups such as hydroxyl, amino, and carboxyl groups, it does not have good dispersibility in oil-based systems. In addition, dispersibility is relatively good in aqueous and emulsified systems, but when blended for a long time, the conformation of biopolymers changes due to interaction with water, and deterioration occurs due to mold growth.
It has the disadvantage of causing discoloration, discoloration, etc., and problems with stability.

Conventionally, in order to incorporate biopolymer powder into pharmaceuticals and cosmetics, for example, Japanese Patent Application Laid-open Nos. 55-27120 and 1987-70 have been proposed.
As in each publication of No. 435, only a method of refining the powder has been taken, and no essential solution has been reached.

In contrast, the modified biopolymer powder according to the present invention has good dispersion in oil-based systems and emulsified systems, and the silicone polymer and hydrophobic pendant groups on the surface prevent water from penetrating into the interior. Stability is significantly improved. Therefore, when the stable biopolymer powder according to the present invention is used in pharmaceuticals or cosmetics, its stability over time is significantly improved.

The stable biopolymers according to the present invention include hair, animal fur, feathers, horns, hooves, etc., fiproine of silk, animal skin,
Collagen, cellulose, soft cellulose from keys, bones, etc.
Pectin, chitin, condo, leutin, nucleic acids (e.g.
Examples include DNA, RNA), peptidoglucan, and the like.

The particle size is not particularly limited, but may range from 0.01 μm to Lot
It is s. The coating amount of silicone polymer is 0.01 to 4
Preferably it is 0% by weight.

The modified biopolymer according to the present invention can be applied not only to pharmaceuticals and cosmetics, but also to paints, inks, carriers for liquid chromatography, and the like.

The uses of the modified powder according to the present invention will be explained below.

The modified powders according to the invention can be advantageously incorporated, for example as pigments, into any paints, such as solvent-based, powder-based, emulsion-based and water-based paints.

Paints are generally complex, multipart systems consisting of resins, pigments, solvents, plasticizers, and other conventional paint additives. The purpose of incorporating pigments into paints is to (i) improve coloration, hiding power, physical properties (e.g. hardness, strength, adhesion), improved weather resistance, fluorescence, phosphorescence, magnetism, conductivity, and other pigment-specific properties; (ii) Improving coating fluid fluidity and improving workability during painting;
(iii) Preventing the growth and adhesion of rust, mold, and harmful organisms.

In order to obtain such effects, the interactions between pigments, resins, and dispersants are being studied. However, depending on the type of pigment, pigments have various properties, for example from hydrophilic to hydrophobic, which causes undesirable phenomena such as color separation in the same paint.

Because the modified pigment according to the invention has its surface uniformly and substantially completely covered with a silicone polymer film, undesirable color separation does not occur.

Furthermore, since the activity of the pigment surface is blocked by the silicone polymer film, deterioration of the coating film over time can be effectively prevented. Furthermore, since the silicone polymer film on the surface of the modified pigment is transparent and thin, there is virtually no difference in color from that of the untreated pigment, and there is no need to later correct the difference in color due to the modification treatment of the present invention. As paints, it can be used as solution-type paints such as nitrified cotton lacquer, cross-linked paints such as oil-modified alkyd resin paints, melamine resin baking paints, polyamide resin-cured epoxy resin paints, unsaturated polyester resin paints, and the like.

When the modified powder according to the present invention is blended into non-aqueous cosmetics,
↑a It is possible to obtain cosmetics that are highly water-based, have a smooth feel, are less prone to fading, and are highly stable.

Conventionally, in cosmetics, especially makeup cosmetics, a method has been used in which the powder in the formulation is coated with silicone oil, metallic soap silica powder, etc. in order to improve water repellency, smooth feel, and excellent makeup durability. Ta. In particular, coating with silicone oil is widely used, and includes a coating method using an organic solvent, a coating method using a mechanochemical reaction, a coating method that mixes another binder oil and silicone oil and sprays it on the powder, and a coating method that uses a binder oil and silicone oil. A coating method is known in which a baking treatment is performed after mixing mixed oil and powder.

However, the conventional techniques do not necessarily satisfy the requirements of tΩ water resistance, stability, and usability. In other words, conventional silicone coatings do not necessarily have sufficient stability, while metal soap coatings, silicone coatings, etc. do not have sufficient ↑R.
Aqueous is not available.

On the other hand, when the modified powder of the present invention is blended, it is possible to obtain a non-small cosmetic that has sufficient water repellency, high stability, and an excellent feel when used. Powders that are preferably incorporated into cosmetics after being treated according to the present invention are powders that are normally used in non-small cosmetics, such as talc, kaolin, sericite, muscovite, phlogopite, phlogopite, and red mica. Mica, biotite, lithian mica, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate,
Inorganic powders such as calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate, metal tungstate, silica, hydroxyapatite, zeolite, boron nitride, cerax powder, nylon powder, polyethylene powder, penzoguana Organic powders such as Rin powder, tetrafluoroethylene powder, distyrene benzene vinyl polymer powder, microcrystalline cellulose, inorganic white pigments such as titanium oxide and zinc oxide, and inorganic red pigments such as iron oxide (red iron oxide) and iron titanate. pigments, inorganic brown pigments such as gamma iron monoxide, inorganic yellow pigments such as yellow iron oxide and loess, inorganic black pigments such as black iron oxide and carpon black, inorganic pigments such as mango bioleft, cobalt bioleft, etc. Violet pigments, inorganic green pigments such as chromium oxide, chromium hydroxide, cobalt titanate, inorganic blue pigments such as ultramarine blue and navy blue, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, bismuth oxychloride, titanium oxide coated Talc, fish scale foil, colored titanium oxide coated var pigments such as sodo mica, aluminum powder,
Metal powder pigments such as copper powder, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red 220
Organic pigments such as Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401, and Blue No. 404, Red No. 3, Red No. 104
No., Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4,
Organic pigments such as Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1 such as zirconium, barium or aluminum lake, natural pigments such as chlorophyll, β-carotene, etc. are used, but are limited to these. It is not something that will be done.

The molecular weight of the silicone polymer compound coating the surface is 2
It is preferable that it is 00,000 or more. If the molecular weight is less than 200,000, it may be difficult to obtain complete coverage and may not exhibit sufficient water repellency.

The amount of the modified powder according to the present invention is 1 to 100% by weight based on the total amount of the non-small cosmetic.

In addition to the modified powder of the present invention, this cosmetic may contain squalane, liquid paraffin, vaseline, microcrystalline wax, othokerite, ceresin, palmistic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, Cetyl alcohol, hexadecyl alcohol, oleyl alcohol, cetyl-2-ethylhexanoate, 2-ethylhexyl partetate, 2-octyldodecyl bay lystate, 2-octyldodecyl gum ester, neobentylglycol-2-ethylhexanate, isooctyl Various hydrocarbons such as acid triglyceride, 2-octyldodecyl oleate, isoprobyl myristate, isostearic acid triglyceride, coconut oil fatty acid triglyceride, olive oil, avocado oil, ξturow, myristyl lystate, mink oil, lanolin, dimethylborisiloxane, higher fatty acids, oils and fats,
Esters, higher alcohols, waxes, oils such as silicone oil, organic solvents such as acetone, toluene, butyl acetate, ethyl acetate, resins such as alkyd resins and urea resins, plasticizers such as camphor, acetyltributyl citrate, etc. Ultraviolet absorbers, antioxidants, preservatives, surfactants, humectants, fragrances, water, alcohol, thickeners, etc. can be added.

Non-aqueous cosmetics containing the modified powder of the present invention have high water repellency, spread well on the skin, and have little makeup smearing. Moreover, since the coating on the powder surface is strong, dense, and homogeneous, a cosmetic with good stability can be obtained.

For example, fragrances blended into cosmetics are often easily decomposed due to the activity of the powder, often causing odor, etc., but this does not occur with cosmetics containing the modified powder of the present invention.

In addition, since the modified powder of the present invention exhibits excellent dispersibility in powder, oil, or solvent, it can be used in cosmetics with excellent gloss when Burr pigment is used as the powder to be treated. In addition, when titanium oxide is used as the powder to be treated, it is possible to obtain a cosmetic that does not aggregate, has excellent UV protection ability, and has a good makeup effect.

Red No. 202 has two crystal forms, α type and β type, and the β type changes to the α type in the presence of water and changes color. Since the surface of such an organic pigment is completely covered by the silicone coating according to the present invention, it does not change to the α type even in the presence of water, resulting in a stable cosmetic.

Ultramarine blue decomposes with acid and releases hydrogen sulfide, but the coating of the present invention eliminates this problem.

Furthermore, it is also possible to prepare aqueous cosmetics with excellent stability and usability, which contain one or more modified powders according to the present invention, water and/or lower alcohols.

Inorganic and organic powders have traditionally been incorporated into cosmetics as colorants, etc., but in some cases their surfaces are woody, hydrophobic, or have surface activity, making them difficult to use in emulsified cosmetics, etc. When blending powder into cosmetics containing water and/or lower alcohol, measures such as applying hydrophobic or hydrophilic surface treatment or adding a dispersant may be taken. many.

Conventionally, known methods for treating powders mixed in water-based cosmetics include (1) adsorbing surfactants;

■Adsorb fatty acids.

■Cover the surface with alkyl polysiloxane.

■Perform surface crosslinking polymerization with methylhydrogenpolysiloxane.

etc. are known.

However, powders to which surfactants are adsorbed and powders to which fatty acids are adsorbed have not been satisfactory, although adsorbed powders have been desired.

In contrast, by blending the modified powder according to the present invention into water-based cosmetics containing water and/or alcohol, such as emulsified cosmetics, the above problems can be solved, and stability and usability can be improved. You can obtain excellent cosmetics.

The stable powder according to the present invention not only does not have a decomposing effect on the ingredients normally added to water-based cosmetics, especially drugs and fragrances, but also is a powder treated by surface polymerization of methylhydrogenpolysiloxane. As in, hydrogen is not generated even when it comes into contact with water or lower alcohols. Further, since the silicone polymer film is thin and highly transparent, the powder subjected to the surface treatment of the present invention has no difference in color tone from that of the untreated powder, and there is no difference in magnetic properties even when the powder is magnetic.

In addition to these properties, the treated powder of the present invention has high hydrophobicity and has good dispersion in the oil phase due to its woody nature, and is stabilized by being added to the oil phase, dispersed, and then emulsified into the water phase. An oil-in-water type emulsified cosmetic with good usability is added to an oil phase, and after separation, the aqueous phase is emulsified to obtain a stable water-in-oil type emulsified cosmetic with good usability.

Powders that are preferably modified according to the present invention and then incorporated into water-based cosmetics include, for example, silicic acid, silicic anhydride, magnesium silicate, talc, kaolin, mica, synthetic mica,
bentonite, titanium-coated mica, bismuth oxychloride,
Inorganic powders such as zirconium oxide, magnesium oxide, zinc oxide, titanium dioxide, calcium carbonate, magnesium carbonate, iron oxide, ultramarine, navy blue, chromium oxide, chromium hydroxide, zeolite, boron nitride, cera powder, calamine, and carbon black. body, polyamide, polyester, polyethylene, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenolic resin,
Fluorine resins, silicone resins, acrylic acid resins, melamine resins, epoxy resins, polycarbonate resins, divinylbenzene-styrene copolymers, and copolymers made from two or more monomers of the above compounds, celluloid, acetyl cellulose , organic powders such as scales, proteins, hard proteins, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red 228
Organic pigments such as Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227
No., Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow 2
Examples include, but are not limited to, organic pigments such as zirconium, barium or argonium lake of No. 03, Green No. 3, and Blue No. 1. In addition, the particle size of the powder is not particularly limited, but is 0.001 to 2.
00μ, especially 0.001 to 0.00μ. Fine particles of 1 μm can also be used because they are covered with a uniform thin film. The amount of the surface-treated powder used in the present invention to be incorporated into the aqueous cosmetic is 0.01 to 90% by weight, preferably 0.01 to 90% by weight based on the total amount of the cosmetic. The ratio is 1 to 80%.

The content of water and/or lower alcohol is 5 to 90% by weight based on the total amount of the water-based cosmetic.

Since the aqueous cosmetics containing the modified powder according to the present invention are not destabilized by the powder, in addition to the above-mentioned essential ingredients, the aqueous cosmetics commonly used in aqueous cosmetics can be stably blended.

For example, aqueous phase components include propylene glycol, diflopylene glycol, 1,3-butylene glycol, glycerin, maltitol, sorbitol, polyethylene glycol, sodium hyaluronate, pyrrolidone carboxylate, etc., vaseline, lanolin, ceresin, Solid and semi-solid oils such as microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids and higher alcohols, liquid oils such as squalane, liquid paraffin, ester oil, and triglyceride, coloring materials such as inorganic pigments, organic pigments, and dyes. , other powders, surfactants such as cationic active agents, anionic active agents, nonionic active agents, amphoteric active agents, drugs such as vitamin E and vitamin E acetate,
Astringents, antioxidants, preservatives, fragrances, citric acid, sodium citrate, lactic acid, sodium lactate, pHlg regulators such as dibasic sodium phosphate, thickeners such as organically modified montmorillonite, ultraviolet absorbers, etc. They can be blended within a qualitative and quantitative range that does not impair the effects of the invention. The treated powder obtained by the present invention has the following characteristics. ■ Since polymerization occurs on the powder surface without baking, it is effective in terms of energy savings and does not change color.

■ Since no crushing force is used, it is effective in terms of energy conservation, and there is no change or agglomeration of particles. Furthermore, there is no change in color due to crushing force.

■ Processing is easy, there is no waste of processing agent, and the process is uniform due to gas phase processing.

■ Water repellency and surface activity of the treated powder are almost completely blocked.

■ According to the present invention, ultrafine powder (for example, particle size 0.00
5 to 0.05 .mu.m) can be effectively coated with a uniform and thin silicone polymer without desirable agglomeration.

[Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

10g of Zinc white and 5g of hexamethylcyclotrisiloxane
into separate containers and use the gas sterilizer Capocalizer CL-
30B (Fuji Electric Co., Ltd.
d. ), the internal pressure was reduced to 300 mmHg using an asvilator, and the temperature was maintained at 50°C.

After standing overnight, air was introduced to return the pressure to normal pressure, and the mixture was evacuated several times to obtain 10.2 g of treated powder. This treated powder showed significant hydrophobicity.

A log of kaolin was placed as a powder in a 100 d double flask. One neck of the Nilo flask was connected to a 30d bubbler, and the other mouth of the Nilo flask was connected to a trap cooled with dry ice-acetone. After the Niro flask and bubbler were left in a constant temperature bath at 90''C for 3 hours, 5 g of hexamethylcyclotrisiloxane as a treatment agent was poured into the bubbler.

Add 2.0d/n+ nitrogen as carrier gas to the bubbler
It was run for 15 hours at a flow rate of in. Each day, the Niro flask was disconnected from the bubbler and trap and left at 50'C for 3 hours to obtain 35.4 g of treated product.

This treated powder showed significant hydrophobicity, and its ability to decompose linalool had disappeared. However, the treated powder was slightly slurried.

In the main example 2 of the real storm dish, a three-way cock was installed between the Niro flask and the bubbler, and 4. 0ml/m
14.1 g of treated powder was obtained in the same manner as in Example 2 except that the powder was flowed at a flow rate of i.sub.n. This treated powder showed significant hydrophobicity, and the ability to decompose linalool had disappeared.

In Example 2, the powder was muscovite and the treatment agent was 1.3.5-
Tris(3.3.3-}Lifluoropil)-1.3
．． 5-trimethylcyclosiloxane, others are Example 2
In the same manner as above, 10.4 g of treated powder was obtained. This treated powder showed significant hydrophobicity, and the ability to decompose linalool had disappeared.

Claims (1)

[Claims] 1. General formula (R^1HSiO)_m(R^2R^3SiO)_b(
R^4R^5R^6SiO_1_/_2)_c(I)
(In the formula, R^1, R^2 and R^3 are each independently a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one halogen atom, and R^4, R
^5 and R^6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one halogen atom, a is 0, and b is 0 or an integer greater than or equal to 1, and c is 0 or 2; however, if c is 0, the sum of a and b is 3.
) is brought into contact with a powder having active sites on its surface in the form of vapor, and the silicone compound is applied to substantially the entire surface of the powder. A modified powder that is obtained by polymerizing and carries a silicone polymer film on substantially the entire surface.