JPH0154381B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a modified powder that carries 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 refers to a particle size of 10
Refers to any object smaller than 1 mm (sometimes including objects larger than 10 mm). The term "powder" as used herein includes aggregates, molded 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, It means a basic point, an oxidation point, or a reduction point. The modified powder according to the 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, Tokuko Sho 41-9890
The publication describes that the surface of animal, vegetable, or mineral powders is coated with a silicone resin coating material, and the powders are imparted with lubricity by drying and baking. 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, etc., and then the powder is heated and baked. It imparts water repellency to some types. In addition, in Japanese Patent Publication No. 18999, dimethylpolysiloxane or methylhydrodienepolysiloxane is dissolved in an organic solvent and then contacted and adhered to talc, and then, if necessary, zinc octoate is added as a crosslinking polymerization catalyst for methylhydrodienepolysiloxane. By adding such substances and baking them, free-flowing properties are imparted to the powder. Furthermore, in Japanese Patent Publication No. 49-1769, titanium dioxide is directly coated with various alkylpolysiloxanes, emulsion coated or coated with a solvent solution, an ester compound having a total carbon number of 6 or more is used as needed, and dry baking is performed. We are improving the dustiness and dispersibility of powder. Also, JP-A-56-16404, JP-A-55-
136213 and JP-A-56-29512,
After silicone oil and oil agent are added and mixed by a mechanochemical reaction such as stirring or pulverization, a baking treatment is performed. Furthermore, JP-A No. 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 with a specific structure. A method is disclosed for imparting water repellency and fluidity to powder without carrying out such steps. This method uses 1 to 10 of the target powder.
This is a method in which % by weight of the above organosilicon compound is diluted in a solvent and sprinkled, directly sprinkled, or atomized in gaseous form, or directly mixed and stirred to be adsorbed onto the powder, and then treated with water and steam. However, there is no description that the silane compound (A) and the cyclic polyorganosiloxane (B) are subjected to gas phase treatment, and in addition, among the cyclic polyorganosiloxanes (B), the trimer having a methyl group is excluded because it is a solid and difficult to handle. [Problems to be Solved by the Invention] However, with these methods, most organic pigments and even inorganic pigments that are sensitive to heat such as yellow iron oxide and dark blue cannot be treated. For example, the organic pigment Red No. 202 (Resol Rubin BCA) could not be processed because it was dehydrated at 80°C and its crystal form changed from α type to β type, and the color tone also changed. In addition, when heated, navy blue decomposes and gradually releases cyan gas at temperatures above 150°C. Baking treatment is carried out at 350℃ for 2 hours for high temperatures, and for 15 to 40 hours at 150℃ for low temperatures.
Under these conditions, the dark blue 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. It was hot. In addition, the action of the catalyst promotes the decomposition of not only the silicone resin on the surface but also other coexisting components such as oil and fragrance, causing problems such as deterioration and odor, making it particularly unsuitable for use in cosmetics. Nakatsuta. JP-A-56-16404 describes a silicone treatment method using mechanochemical reactions. However, this method uses crushing force, so
If the powder is characterized by a plate-like or spherical shape, the shape will change. Furthermore, it has been difficult to treat powders such as titanium dioxide that aggregate when stirred alone. In the method described in JP-A-57-200306,
Rather than bringing a molecular treatment agent into contact with the powder,
The powder is brought into contact with the powder in the form of a liquid or liquid particles. For this reason, trimers, which are solids among the 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 surface activity may remain in the powder, allowing fragrances to coexist. In this case, there were disadvantages such as poor fragrance stability. The purpose of the present invention is to maintain the original properties of the powder, have improved properties (e.g. hydrophobicity, stability), and eliminate the surface activity of the powder (i.e. The object of the present invention is to provide a modified powder (which does not cause deterioration or decomposition of components), and to eliminate the drawbacks of the prior art described above. [Means for solving the problem] The above purpose is to solve the general formula (R ¹ HSi0) _a (R ² R ³ Si0) _b (R ⁴ R ⁵ R ⁶ Si0 _1/2 ) _c (
) (wherein R ¹ , R ² and R ³ 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, However, R ¹ , R ² and R ³ are not hydrogen atoms at the same time, 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 an integer of 0 or 1 or more, b is an integer of 0 or 1 or more, and c is 0 or 2,
However, if c is 0, the sum of a and b shall be an integer of 3 or more). This can be achieved by using a modified powder that carries a silicone polymer film on substantially the entire surface of the powder, which is made by contacting the powder with a silicone compound and polymerizing the silicone compound on substantially the entire surface of the powder. . The present invention will be explained in detail below. As already mentioned, most conventional techniques require heat, catalysts, or crushing power when treating powder with silicone oil. This is because it is assumed that the silicone oil used is relatively inert and that the powder used is not active. However, many powders have surface activity. This surface activity of the powder degrades perfumes, 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 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, pearlescent materials, silicate minerals, porous materials, carbon, metals, and biomaterials that have active sites on their surfaces. Includes polymers, mica and composite powders. These powders may be treated with one type or in combination of multiple types. Furthermore, it is also possible to process aggregate molded bodies or shaped bodies of one or more of these powders. These powders can be subjected to any conventional treatment (eg, alkaline cleaning, acid cleaning, plasma treatment) before carrying out the modification treatment according to the present invention (ie, before contacting with the silicone compound). When 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 easily formed.
Furthermore, the powder treated according to the invention may contain other substances on or in it (eg, colorants, UV absorbers, pharmaceuticals, various additives). In the present invention, the silicone compound of the formula () in vapor form is brought into contact with the powder having active sites on its surface at a temperature of 120°C or lower, preferably 100°C or lower, preferably 100mmHg or lower, and more preferably 100mmHg or lower. 100
Performed in a closed container under pressure of mmHg or less,
The vapor of the silicone compound of formula () can be deposited in molecular form onto the powder surface. Alternatively, the silicone compound of formula () in the form of vapor and a powder having active sites on its surface may be brought into contact with the silicone compound of formula () and a carrier gas at a temperature of 120°C or lower, preferably 100°C or lower. This can be done by supplying a mixed gas of The silicone compounds of the formula () are comprised of two groups. The first group is c=
0, and the general formula (R ¹ HSi0) _a (R ² R ³ Si0) _b () [In the formula, R ¹ , R ² , R ³ , a and b have the same meanings as above, Preferably, R ¹ , R ² and R ³ are each independently a lower alkyl group having 1 to 4 carbon atoms or an aryl group (e.g. phenyl group) which may be substituted with at least one halogen atom, and a and The sum with b is 3 to 7.] This is a cyclic silicone compound represented by: Representative examples of this compound are as follows. The aforementioned compounds (A), (B) and (C) can be used individually or in the form of a mixture thereof. In each of the above formulas, n (or a+b) is preferably 3-7. As the value of n decreases, the boiling point decreases, so the amount that evaporates and adsorbs onto the powder increases. In particular, trimers and tetramers are particularly suitable because they are easily polymerized due to their steric properties. 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 treatment is not fixed, and the end point is when the silicone polymer completely covers the active sites. Of course, depending on the purpose, complete coverage may not be required. Examples of cyclic silicone compounds of formula () include dihydrodienehexamethylcyclotetrasiloxane, trihydrodienepentamethylcyclotetrasiloxane, tetrahydrodienetetramethylcyclotetrasiloxane, dihydrodieneoctamethylcyclopentasiloxane, and trihydrodieneoctamethylcyclopentasiloxane. Mention may be made of dieneheptamethylcyclopentacycloxane, tetrahydrogenhexamethylcyclopentasiloxane, and pentahydrodienepentamethylcyclopentasiloxane. The second group of silicone compounds of the formula () corresponds to the case where c=2 in the formula (), and has the general formula (R ¹ HSi0) _a (R ² R ³ Si0) _b (R ⁴ R ⁵ R ⁶ Si0 _1/2 ) _c (
) [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , a and b have the same meanings as above, and c is 2, but preferably R ¹ to R ⁶ are mutually is a lower alkyl group or aryl group (e.g. phenyl group) having 1 to 4 carbon atoms which may be independently substituted with at least one halogen atom, and the sum of a and b is 2 to 5. It is a linear silicone compound represented by: A typical example of this compound is the formula (In the formula, a is 2 to 5.) Compounds represented by the following can be mentioned. Examples of linear silicone compounds of formula () include 1,1,1,2,3,4,4,4-octamethyltetrasiloxane, 1,1,1,2,3,
4,5,5,5-nonamethylpentasiloxane,
and 1,1,1,2,3,4,6,6,6-decamethylhexasiloxane. There are two types of silicone polymer film structures that are coated on the powder surface. That is, when polymerization occurs through siloxane bonds (-Si-O-Si-), the resulting silicone polymer is -Si-
It has a linear structure containing O--Si- units, and preferably has a weight average molecular weight of 200,000 or more. On the other hand, polymerization involves small or trace amounts of H ₂ 0 or O ₂
The following polymerization of the Si--H moiety occurs when the dehydrogenation reaction of the hydrosilyl bond (Si--H) occurs in the presence of: derived from. The silicone polymer will include a network structure with units. A preferable network polymer has 20% or more of the total Si atoms in the polymer film. It is converted into units. The content of this unit is
It can be determined from the IR absorption of methyl groups in the polymer film. The amount of the silicone compound of formula () 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, in the present invention, the amount of the processing agent to be added is not determined in advance, but the processing agent is supplied in a 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 0.005~50% of the powder weight
It is. Regarding these powders, please refer to the above-mentioned Japanese Unexamined Patent Application Publication No. 1983
The amount of processing agent of 1 to 10% shown in Japanese Patent Publication No. 200306 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 method of adding the processing agent is different from conventional methods.
Conventional processing methods involve diluting the processing agent in a solvent and spraying, direct spraying, or gaseous spraying on the raw material powder; in either case, the molecular processing agent comes into contact with the powder. Instead of contacting the powder in the form of a liquid or liquid particles. For this reason, in the method described in JP-A-57-200306, the trimer, which is a solid among the cyclic organosiloxanes, is excluded, but in the present invention, the trimer is not added in a liquid state but in molecular form, so that the original substance is brought into contact with the powder. The processing agent may be solid or liquid. Furthermore, considering polymerization on the powder surface, the trimer excluded in JP-A-57-200306 is the most easily polymerized and is therefore the most suitable as a processing agent. That is, the feature of the present invention is that the powder is left in a low partial pressure state where the organosiloxane, for example, a cyclic organosiloxane, is volatilized at a temperature of 120°C or lower, preferably 100°C or lower, and the vaporized organosiloxane is converted into a molecular state. This is an energy-saving treatment method that utilizes adsorption to powder and polymerization from the active sites on the surface, and is completely different from the conventional method of spraying a treatment agent and polymerizing it with heat. Furthermore, the treatment temperature in the method described in JP-A-57-200306 is 230 to 350°C in the case of cyclic organosiloxane.
While this is not preferred for the reasons mentioned above, the present invention does not involve heat treatment, so it can be applied to pigments with low temperature stability, and its range of applications 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 silicone compound is polymerized due to the presence of active sites distributed over the entire surface of the powder. Therefore, a uniform and thin polymer film is formed. After the thin layer of silicone polymer is formed, substantially no polymerization occurs thereon. Therefore, the thickness of the silicone polymer coating is generally between 3 Å and 30 Å. 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, the polymerization mainly occurs around the catalyst, making it impossible to uniformly coat only the surface of the powder. According to a basic embodiment of the invention (e.g. 100°C
Simply place the powder and the silicone compound (for example, cyclic organosiloxane) in separate containers in a closed room (see below) and leave the top open. 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 removed from a 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 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 that can be kept at a constant temperature)
For example, a desiccator or a constant temperature bath can be used. Moreover, a desiccator can be used for small-scale processing. However, ideally, a device that can degas after treatment is desirable, and a gas sterilization device is preferably used. The powder in the closed chamber can be continuously or intermittently 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 lower, preferably 100°C or lower, and then heated at a predetermined partial pressure in another sealed room at a temperature of 120°C or lower. The silicone compound can be vaporized and the silicone compound vapor introduced, for example by pipe, into the chamber containing the powder. There are no particular restrictions on the pressure in the above system, but polymerization is controlled at 200 mmHg or less, preferably 100 mmHg.
Preferably, the reaction is carried out under the following pressures: In either embodiment, the processing time is from 30 minutes to 150 hours, after which unpolymerized silicone compounds are removed by degassing to yield the desired product. According to another aspect of the invention, the powder is treated by contacting it with a silicone compound of formula () in the form of a gas mixture with a carrier gas (e.g. by feeding it onto the powder surface). Can be done. When mixing the silicone compound of formula () with the carrier gas, the vapor pressure of the silicone compound is 1 mm.
Hg or higher, preferably 100 mm Hg or higher, for example by optionally heating the silicone compound of formula () and subsequently introducing a carrier gas stream into or onto the surface of the silicone compound of formula (). It can be implemented. The feed rate of the carrier gas stream can be suitably determined, for example, by the vapor pressure of the silicone compound of formula (), the type and amount of powder, and the capacity of the processing vessel. It is preferable to adjust the process 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 a silicone compound of formula () is brought into contact with a powder to be modified. Since the silicone compound of mixed gas formula (2) is contained 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, the contact/reaction temperature is preferably higher than the temperature of the supplied mixed gas, and a carrier gas containing no silicone compound is simultaneously supplied to lower the relative pressure to the saturated vapor pressure of 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, and active points on the surface are utilized. Polymerization is carried out by In the present invention, it is particularly preferable to use gas phase treatment for ultrafine powders, porous materials, pearl pigments, organic pigments, and the like. When these powders are treated in a gas phase, an ultra-thin film of silicone polymer is formed.
The ultra-fineness, porosity, pearl effect, etc. of the powder can be maintained. Further, by subjecting a metal that is easily oxidized to a vapor phase treatment immediately after its generation, a metal powder that is stable against oxidation can be obtained. 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. In addition, with regard to clay minerals with intercalated ultraviolet absorbers between the layers, if they are simply placed between the layers, they are unstable and may come off with solvents, etc., but according to the present invention, they can be further coated with silicone polymer. If you do this, it won't come off. 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)benzotriazole, 2-ethylhexyl paradimethylaminobenzoate, amyl paradimethylaminobenzoate, 2,
Examples include methyl 5-diisopropylcinnamate and urocanic acid. 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. can. Representative examples of such powder will be described below. Inorganic pigments Inorganic pigments that can be modified by the present invention include, for example, ultramarine, navy blue, manganese violet, titanium-coated mica, bismuth oxychloride,
Examples include iron oxide, iron hydroxide, titanium dioxide, lower titanium oxides, and chromium hydroxide. Among these inorganic pigments, the typical ones modified by the present invention are ultramarine blue and deep blue. Ultramarine blue has been used as a blue coloring agent in many fields, but it has serious deficiencies as a coloring agent. That is, ultramarine blue is extremely sensitive to acids, and under acidic conditions, it gradually decomposes and fades while generating hydrogen sulfide, becoming white. Also,
Ultramarine blue also generates hydrogen sulfide when subjected to mechanical shearing force such as crushing or heat. On the other hand, the ultramarine blue treated with the silicone compound according to the present invention is stable against acid, heat, and mechanical shearing forces, and does not decompose due to these actions and substantially does not generate hydrogen sulfide. Even if this product is used, for example, under acidic conditions, it will not change the quality of container materials such as aluminum, nor will 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. Since the stable ultramarine blue modified by the present invention does not decompose other components such as fragrances, when used in pharmaceuticals and cosmetics, the stability over time is significantly improved. Furthermore, because the silicone polymer film is thin and highly transparent, there is no difference in color 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 ultramarine surface,
In other words, surface sulfur refers to radical sulfur that exists on the surface of the ultramarine crystal lattice, and this refers to the sulfur (including radical sulfur) that exists inside the crystal lattice.
Unlike other substances, they tend to have various types of activity towards other substances. This active surface sulfur decomposes under the action of acid, heat, and mechanical shearing force, generating 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 is usually 0.1 to 200 μm,
In particular, it is 0.1 to 20 μm, preferably 0.3 to 2 μm for blue ones, and 2 to 10 μm for reddish blue ones. 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 approximately 0.1 to 20% by weight, preferably 0.2 to 2.0% by weight.
Weight%. 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, the 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. Therefore, even if the surface of plastic or metal oxide is treated with ultramarine, it will be stabilized by the silicone polymer coating. It can be made into ultramarine. For example, JP-A-57-170931 and JP-A-57-
The present invention can be applied to a composite powder obtained by using the techniques described in each publication of No. 179251 or by simply treating plastic and ultramarine blue with a ball mill to coat the surface with ultramarine blue. Since the active sites described above exist on the surface of the ultramarine powder, the silicone compound of formula () deposited on the surface is polymerized at a temperature of, for example, 120°C or lower, and
A film of silicone polymer with a crosslinked network structure can be formed. The crosslinking rate can be increased by increasing the temperature to about 200°C. When the active surface is covered with a silicone polymer coating,
No more adsorption or polymerization occurs. The modified ultramarine blue according to the invention is used, for example, as a blue colorant, inter alia in the paint, ink, pharmaceutical and cosmetic fields. Dark blue has low alkali resistance and somewhat low heat resistance. It is also easily reduced and loses its blue color when reduced. 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 color 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, which removes the restrictions on its use in navy blue and allows it to be used 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~
200μm, especially 0.01~100μm, preferably 0.05~
It is 0.1 μm. There is also bead navy blue that is granulated to make it non-scattering, and bead navy blue has a particle size of about 0.5 to 20 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 5-30% by weight. 0.5
If it is less than 40% by weight, it is not optimal in terms of imparting effective stability to Prussian blue, and conversely, if it exceeds 40% by weight, bonding between particles will progress and agglomeration will occur, which is not optimal in terms of dispersibility. do not have. The stable navy blue according to the present invention may be coated with a silicone polymer (resin) represented by the formula (V), for example, and therefore, even if it is a plastic or mica whose surface is treated with navy blue, The silicone polymer coating allows for a stable composite. Although there is no need for high temperature heating to obtain a powder coated with a silicone polymer film,
The crosslinking rate can be increased by heating to a temperature of 140° C. or lower, 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. Metal oxides and metal hydroxides Metal oxides and metal hydroxides are used in paints, inks,
Although it is used as a coloring agent in the field of cosmetics, it is usually hydrophilic and its dispersibility in oil or solvent systems is not good. In addition, metal oxides and metal hydroxides have catalytic activity, and this catalytic action can cause many problems such as deterioration of coexisting oils, fats, fragrances, and discoloration due to interaction with chemicals. It has points. In contrast, the modified metal oxides and metal hydroxides according to the present invention do not interact with drugs,
Furthermore, it does not show any decomposition 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 and untreated ones, and even when they are magnetic, their magnetic properties There is no difference. 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 the 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 chromatography, a column packing material for liquid chromatography, 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-Fe ₂ 0 ₃ , γ - Fe ₂ 0 ₃ , Fe ₃ 0 ₄ , Fe0), yellow iron oxide (especially rod-shaped ones), red iron oxide, black iron oxide, iron hydroxide, titanium oxide (especially particle size 0.001~
0.1 μm titanium dioxide), lower titanium oxide, zirconium oxide, chromium oxide, chromium hydroxide, manganese oxide, cobalt oxide, nickel oxide, and composite oxides and composite hydroxides made of combinations of two or more of these. , iron titanate, cobalt titanate, cobalt aluminate, etc. The particle size is not particularly limited, but is 0.001 μm.
~10mm, especially 0.001~200μm, preferably 0.01~
It is 10μm. Even such fine particles are covered with a uniform thin film and do not aggregate. The amount of silicone compound coated in the stable metal oxides and metal hydroxides of the present invention varies depending on the surface area, but is preferably about 0.1 to 20% by weight.
It is 0.2-5.0% by weight. If it is less than 0.1% by weight,
It is not optimal for imparting effective stability to metal oxides and metal hydroxides; on the other hand, if it exceeds 20% by weight, bonding between particles will progress and agglomeration will occur, which is optimal in terms of dispersibility. isn't it. The stable metal oxides and metal hydroxides according to the present invention may be obtained by coating the metal oxides and metal hydroxides with, for example, a silicone polymer (resin) represented by the above formula (). Even plastics and mica surface-treated with oxides or metal hydroxides can be made into stable composites by coating with silicone polymers. Polymerization of silicone compounds does not require high temperature heating;
100 _x / (x +
y) The crosslinking rate increases, but does not exceed the scope of the present invention. In other words, the powder is left in a low partial pressure state where the silicone compound of formula () vaporizes at a temperature of 100°C or less, and the powder is adsorbed in the molecular state and polymerized from the active sites on the surface. do. Therefore, this method is completely different from the conventional method of spraying a processing agent and polymerizing it with heat. In the case of organosiloxane, the treatment temperature in the method described in JP-A-57-200306 is 230 to 350°C, which is not preferable for the reasons mentioned above, whereas the gas phase treatment described above treats metal oxides with low temperature stability. It can be said that the reaction range is wide. The metal oxides and metal hydroxides modified according to the present invention are not only used as colorants in the fields of paints, inks, and cosmetics, but also as magnetic materials, column packing materials for gas chromatography, and liquids. It can be widely used as column packing material for chromatography, catalyst carrier, etc. Organic Pigment The modified organic pigment of the present invention is stable and does not react with other coexisting components. The organic pigment used in the present invention includes red 3
No., Red No. 104, Red No. 106, Red No. 201, Red No. 202
No., Red No. 204, Red No. 205, Red No. 206, Red No. 207
No., Red No. 220, Red No. 226, Red No. 227, Red No. 228
No., Red No. 230, Red No. 405, Orange No. 203, Orange No. 204
No., Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow 205
No. 401, Yellow No. 1, Blue No. 404, etc. Further, these organic pigments may be aluminum lake or zirconium lake, or those organic pigments may be surface-treated, for example, treated with rosin or the like. The particle size of the organic pigment used in the present invention is not particularly limited, but a particle size of about 0.05 to 200 μm, particularly about 0.05 to 3.0 μm is preferable. The higher the molecular weight of the silicone polymer that coats the surface, the more complete the coating, but a molecular weight of 1000 or more is usually sufficient when used in paints, inks, and cosmetics. Those with a molecular weight of 200,000 or more form a complete capsule that cannot be eluted even with solvents such as chloroform. The amount of silicone polymer present in the stable organic pigments of the present invention is about 0.1-20% by weight, preferably
It is 0.2 to 5% by 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 the silicone compound on the powder surface, but in the present invention, it is sufficient to leave the organic pigment and the silicone compound at a temperature of 100°C or less. Also,
When processing in a closed system, it is safe to introduce a large amount of silicone compound if nitrogen substitution is performed, and if the reaction is carried out under reduced pressure, the rate of adsorption will be slightly faster. The modified organic pigment of the present invention can be used as a coloring agent in the fields of paints, inks, cosmetics, etc. Pearlescent Materials The pearlescent materials used in the present invention include mica titanium composite materials, mica iron oxide composite materials, bismuth oxyrochloride, guanine, and titanium oxynitride and/or titanium containing lower titanium oxide. Examples include mica coated with a compound. 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, carbon black, carmine, or ultramarine blue. The pearlescent material used in the present invention may be used as it is, but when used as a pearlescent pigment in powder form, particles with a particle size of 0.1 to 200 μm, particularly 1 to 50 μm, and as flat a particle shape as possible are preferred for beautiful color tone and pearlescent luster. This is preferable because it is easy to demonstrate. 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 in which the film components do not fall off or elute even when a solvent such as chloroform is used. The amount of silicone polymer present in the stable coated pearlescent material of the present invention is about 0.1 to 20% by weight, preferably 0.2 to 5% by weight of the total coated pearlescent material.
Weight%. If it exceeds 20%, it will have an adverse effect on pearl luster, and if it is less than 0.1%, the effect of the present invention will be small. The coated pearlescent material obtained by the present invention not only has improved stability, but also has good luster in the case of powdered pearlescent material, probably due to improved orientation. The pearlescent material modified by the present invention is
For example, it is useful as a pigment or a colored pearlescent material for paints, inks, plastics, cosmetics, ornaments, household goods, textile products, or ceramic products. Further, the modified mica titanium composite material according to the present invention is expected to be used as a conductive layer or recording layer for recording paper, and as an antistatic material. Silicate Mineral The modified silicate mineral according to the present invention has no interaction with coexisting 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 between silicate minerals and untreated ones. In addition to these properties, the silicate mineral according to the present invention exhibits hydrophobicity because it is coated with a silicone polymer, and because it enters the oil phase in emulsion systems, restrictions on the use of silicate minerals are removed. This made it possible to use it for a wide range of purposes. Stable silicate minerals according to the invention are phyllosilicate minerals (e.g. kaolin family, montmorillonite family, argillaceous mica family, chlorite family, serpentine) and tectosilicate minerals (e.g. zeolite family); fluorite, talc, chlorite, chrysotile, antigorite, lizardite, kaolinite, detsuite, nacrite, hallosite,
Montmorillonite, nontronite, saponite, sauconite, bentonite and sodazeolite, mesozoite scoresite, sodazeolite group such as Thomsonite zeolite, heliosideite group such as helioside, bundlezite, xiozoite, analzite, deuterozite, Examples include zeolites such as ash zeolite, chabazite, gmelin zeolite, and the like. These phyllosilicate minerals may have organic cations intercalated between the layers, or may contain alkali metals,
It may be substituted with an alkaline earth metal ion or the like. In tectosilicate as well, metal ions may enter the pores. The particle size is not particularly limited, but it is 0.01 μm ~
10 mm, especially 0.01-100 μm, preferably 0.1-30 μm. The amount of silicone polymer coverage in the stable silicate mineral of the present invention varies depending on the surface area, but is about 0.1-20% by weight, preferably 0.2-5.0% by weight.
It is. Less than 0.1% by weight is not optimal for imparting effective stability to silicate minerals;
On the other hand, if it exceeds 20% by weight, bonding between particles will progress and agglomeration will occur, 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). It can be a stable complex. Although high-temperature heating is not necessary for polymerization of silicone compounds, heating at about 200°C will only increase the crosslinking rate and will not exceed the scope of the present invention. The modified silicate mineral according to the present invention can be used in electrical insulators, fillers for medicine, nitrogen materials, paper, rubber, paint, cosmetics, etc., and can also be used to change the surface structure with a silicone polymer film. Therefore, it can also be used as a catalyst, adsorbent, etc. Porous Material The modified porous material according to the present invention has the formula (wherein R ² , R ₃ and b have the same meanings as above) or a cyclic silicone compound represented by the above formula (R ² R ₃ CSi0) _b (R ⁴ R ⁵ R ₆ Si0 ₁ ) _c ( b) At least one linear silicone compound represented by (wherein R ² to R ⁶ , b and c have the same meanings as above)
A seed is brought into contact with the porous material in the form of a vapor, and the surface activity of the porous material is used to polymerize the silicone compound on the outer surface of the porous material and on the pore surfaces to form a silicone polymer. The modified porous material of the present invention prepared by coating and eliminating the above-mentioned surface activity has high stability against fragrances and drugs, and can be used as an excellent carrier. The time for the gas phase treatment is generally from 1 hour to 72 hours, and then the desired product is obtained by degassing and removing unpolymerized silicone compounds. Porous materials used in the present invention include silicate minerals such as pyrophyllite, talc, chlorite, chrysotile, antigorite, lizardite, kaolinite, detsuite, nacrite, hallosite, montmorillonite, nontronite,
Saponite, sauconite, bentonite, soda zeolite, mesozeolite, scores zeolite, Thomson zeolite,
Heolite, stiltite, xardite, analzite, deuterite,
Boschite, chabazite, gmelinite, muscovite, phlogopite, biotite, sericite, iron mica, rhodotite, lithian mica, Chinwald mica, soda mica, KAl ₂ (Al, Si ₃ ) 0 ₁₀ F ₂ , KMg(Al, _Si3 ) _{010F2 ,}
K (Mg, Fe ₃ ) (Al, Si ₃ ) 0 ₁₀ F ₂ is a metal oxide. Magnesium oxide, magnesium hydroxide, zinc oxide, calcium oxide, calcium hydroxide, aluminum oxide, aluminum hydroxide, silica, iron oxide (α-Fe ₂ 0 ₃ , γ-Fe ₂ 0 ₃ , Fe ₃ 0 ₄ , Fe0) , 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 CaC0 ₃ , MgC0 _{3 , FeC0 3 ,} MnC0 ₃ , ZnC0 ₃ ,
CaMg (C0 ₃ ) ₂ , Cu (0H) ₂ CO ₃ , Cu ₃ (0H) ₂ (C0 ₃ ) ₂ ,
Sulfate minerals BaS0 ₄ , SrS0 ₄ , PbS0 ₄ ,
CaS0 ₄ , CaS0 ₄ , 2H ₂ 0, CaS0 ₄ , 5H ₂ 0, CuS0 ₄
(OH) ₆ , , KAl ₃ (0H) ₆ (S0 ₄ ) ₂ , KFe ₃ (0H) ₆
(S0 ₄ ) ₂ , phosphate mineral YP0 ₄ , (Ce, La)
P0 ₄ , Fe ₃ (P0 ₄ ) ₂・8H ₂ 0, Ca ₅ (P0 ₄ ) ₃ F, Ca ₅
(P0 ₄ ) ₃ Cl, Ca ₅ (P0 ₄ ) ₃ 0H, Ca ₅ (P0 ₄ , C0 ₃ 0H) ₃
(F, 0H), metal nitrides such as titanium nitride, boron nitride, and chromium nitride. Also, granulated or molded products,
Alternatively, it may be granulated or molded and then fired. Furthermore, it can be applied to cellulose, fibers, synthetic resins, etc. That is, porous glass beads, hollow silica or zeolite, or granulated or molded metal oxides, metal nitrides, silicate minerals, carbonate minerals, sulfate minerals or phosphate minerals, metal oxides. , metal nitrides, silicate minerals, carbonate minerals, sulfate minerals, or phosphate minerals, which are granulated or molded and then fired, can be used to treat metals, cellulose, fibers, or synthetic resins. . 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% of the total amount of the treated carrier.
~60% by weight, especially about 0.01-20% by weight. Furthermore, 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 mm or less, preferably 3 μm to 10 mm. 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. 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 the fields of fragrances, medicines, toys, etc. Furthermore, since the present invention utilizes a gas phase reaction that takes advantage of the surface activity of porous materials, even if the porous material is granulated or specially molded, it can maintain its pores without changing its shape. Processing can be done while the
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. Furthermore, carbon has catalytic activity, and this catalytic action has disadvantages such as degrading coexisting oils, fats, fragrances, and adsorbing drugs. In contrast, the modified carbon according to the present invention
Carbon does not interact with drugs, does not decompose fragrances, is highly hydrophobic, and has excellent lipophilic properties. 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 exhibits hydrophobicity because it is coated with a silicone polymer film, and because it enters the oil phase in emulsification systems, restrictions on the use of carbon are removed. It has become 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 chromatography, a column packing material for liquid chromatography, 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 are used during chromatography. be able to. 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 amount of silicone polymer coated on the stable and highly lipophilic carbon of the present invention varies depending on the surface area, but is approximately 0.1 to 50% by weight, preferably 1 to 50% by weight.
It is 30% by weight. If it is less than 0.1% by weight, it is not optimal for imparting effective lipophilicity to carbon, and if it exceeds 50% by weight, the bond between particles will progress and agglomeration will occur, resulting in poor dispersibility. is not optimal. Furthermore, the pores of carbon become clogged, making it unsuitable as a filler. The particle size is
Although not particularly limited, it is 0.001 μm to 10 mm. The temperature at which carbon and silicone compounds are left is 100
A temperature below ℃ is sufficient. Thus, although there is no need for high-temperature heating, 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,
It is not only used as a coloring agent in the fields of tires and cosmetics, but can also be used in a wide range of applications, including as a catalyst carrier, a column packing material for gas chromatography, and a column packing material for liquid chromatography. Metals According to the present invention, metals that can be modified by treatment with the silicone compound include iron, cobalt, nickel, copper, zinc, aluminum, chromium, titanium, zirconium, molybdenum, silver, Mention may be made of indium, tin, antimony, tungsten, platinum, and gold, as well as alloys thereof. 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 mm, particularly 0.01 μm to 5 mm.
It is preferable to modify the metal powder. Preferably, the silicone polymer coverage is about 0.01 to 20% by weight. Mica 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 or rubber, agglomeration occurs, making it difficult to mix uniformly. The modified mica according to the invention is a stable mica. Since the stable mica according to the present invention does not decompose other components such as fragrances, when used in pharmaceuticals and cosmetics, the stability over time is significantly improved. Furthermore, because the silicone polymer film is thin and highly transparent, the stabilized mica has no difference in color from untreated mica. In addition to these properties, the mica according to the present invention has
Because it is coated with a silicone polymer film, it exhibits hydrophobicity and can be incorporated into the oil phase in emulsion systems, with fewer restrictions on formulation and 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 form into lumps, and a large amount of coverage of about 90% can be achieved. As will be described later, when treated in a gas phase, even when coated in large quantities, it has a particularly fluffy feel and has no drawbacks such as stickiness. Mica that is completely coated with a silicone polymer film does not interact with other ingredients 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 core mica of the silicone polymer mica composite applied to the present invention is muscovite, phlogopite, biotite,
Micas such as sericite, iron mica, red mica, lithian mica, Chinwald mica, and soda mica are artificial micas in which the OH group of mica is substituted with F [e.g., KAl ₂ (Al,
Si ₃ ) 0 ₁₀ F ₂ , KMg ₃ (Al, Si ₃ ) 0 ₁₀ F ₂ , K (Mg,
Fe ₃ ) (Al, Si ₃ ) 0 ₁₀ F ₂ ]. These mica may be calcined. 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
~200μm, especially 0.5~40μm, can be processed quickly. The amount of silicone polymer present in the stable mica of the present invention varies depending on the purpose, but is about 0.1 to 20% by weight, preferably 0.2 to 5% by weight when the original shape of the mica is not changed. 0.1% by weight cannot impart effective stability to mica. Additionally, when processing the mica to cleave the mica and make the mica foil thinner to obtain stable mica as detailed below, the amount of silicone polymer present is between 20 and 95% by weight, especially between 20 and 90% by weight. can also be obtained as a fluffy composite. 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 stable 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 a fine powder. The larger the amount of silicone compound, the more the swelling progresses, and the mica is covered while being cleaved. It is possible to use up to about 95% by weight of the silicone compound based on the mica. Conventionally, in order to cause polymerization on the surface, heat or a polymerization catalyst was used, and a temperature of about 150°C was required, but according to the above method, the combination of mica and cyclic silicone compound The storage temperature is
A temperature below 100℃ is sufficient. If the temperature is further raised to, for example, about 200°C, the crosslinking rate will increase. In the treatment method described in JP-A-57-200306,
It uses a process of gas spraying and heating, and is treated with less than 10% by weight of a silicone compound.
In this method, particles of the silicone compound sprayed adhere to the mica surface and polymerize there, so that no expansion occurs. 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, cleavage of mica occurs, 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. In addition, cleaved and expanded mica is soft and slippery, making it suitable as a raw material for cosmetics. Furthermore, raw mica ore can also be cleaved, and if it is pulverized after cleavage, it has the advantage of being easily pulverized into powder. 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 plastic for a wide range of applications, such as heat insulation, prevention of radio wave interference, and prevention of mold adhesion. Biopolymers Biopolymer powders are highly safe and are used in pharmaceuticals and cosmetics. However, since the surface of biopolymer powder is covered with hydrophilic groups such as hydroxyl groups, amino groups, and carboxyl groups, dispersibility in oily systems is not good. In addition, dispersibility is relatively good in aqueous and emulsified systems, but if blended for a long time, the conformation of the biopolymer changes due to interaction with water, and deterioration occurs due to mold growth.
It has the disadvantage of causing discoloration, breath change, 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 1972
- No. 70435 As in each publication, only the method of making the powder finer 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. Stable biopolymers according to the present invention include kechitin from hair, animal hair, feathers, horns, hooves, etc., fibroin from silk, collagen from animal skin, tendons, bones, etc., cellulose, hemicellulose, pectin, chitin, condom, leutin, nucleic acids (e.g. DNA, RNA),
Examples include peptidoglucan. The particle size is not particularly limited, but is 0.01 μm to 10
mm. Silicone polymer coverage is from 0.01 to
Preferably it is 40% 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. Applications Applications of the modified powder according to the present invention will be explained below. Paint The modified powder according to the present invention can be used as a pigment, for example.
It can be advantageously incorporated into any paint, such as solvent-based, powder-based, emulsion-based, and water-based paints. Paints are generally complex multicomponent systems consisting of resins, pigments, solvents, plasticizers, and other conventional paint additives. The purposes of adding pigments to paints are (i) coloration, hiding power, physical properties (e.g. hardness, strength, adhesion), improved weather resistance, fluorescence, phosphorescence,
imparting magnetism, conductivity, and other pigment-specific properties to the paint film; (ii) improving coating fluidity and improving workability during painting; and (iii) preventing rust.
It may prevent the growth and adhesion of mold and harmful organisms. In order to obtain such effects, the interactions between pigments, resins, and dispersants are being studied. However, pigments have various properties depending on the type, for example from hydrophilic to hydrophobic, and this 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 for solution-type paints such as nitrified cotton lacquer, bridge-type paints such as oil-modified alkyd resin paints, melamine resin baking paints, polyamide resin-cured epoxy resin paints, and unsaturated polyester resin paints. Non-Aqueous Cosmetics When the modified powder according to the present invention is blended into non-aqueous cosmetics, it is possible to obtain highly water-repellent cosmetics that have a smooth feel, are less prone to makeup fading, and are highly stable. Powders that are preferably incorporated into cosmetics after being treated according to the present invention are powders that are normally used in non-aqueous cosmetics, such as talc, kaolin, sericite, muscovite, synthetic mica, phlogopite, and red mica. mica,
Biotite, lithian mica, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate, metal tungstate, silica, Inorganic powders such as hydroxyapatite, zeolite, boron nitride, ceramic powder, nylon powder, polyethylene powder, benzoguanamine powder, tetrafluoroethylene powder, distyrene benzene pinhole polymer powder, organic powders such as microcrystalline cellulose, titanium oxide, Inorganic white pigments such as zinc oxide, inorganic red pigments such as iron oxide (red iron oxide), iron titanate, inorganic brown pigments such as γ-iron oxide, yellow iron oxide, inorganic yellow pigments such as ocher, black iron oxide , inorganic black pigments such as carbon black, inorganic purple pigments such as mango violet and cobalt violet, inorganic green pigments such as chromium oxide, chromium hydroxide, and cobalt titanate, inorganic blue pigments such as ultramarine blue and navy blue, Pearl pigments such as titanium oxide coated mica, titanium oxide coated bismuth oxychloride, bismuth oxychloride, titanium oxide coated talc, fish scale foil, colored titanium oxide coated mica, metal powder pigments such as aluminum powder, cut pearl powder, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220,
Red No. 226, Red No. 228, Red No. 405, Orange No. 203,
Organic pigments such as Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 404, Red No. 3, Red No. 104, Red 106
No., Red No. 227, Red No. 230, Red No. 401, Red No. 505
No., Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow 202
Organic pigments such as zirconium, barium or aluminum lake of No. 203, yellow No. 203, green No. 3 and blue No. 1, natural pigments such as chlorophyll, β-carotene, etc. are used, but are not limited thereto. The molecular weight of the silicone polymer compound coating the surface is preferably 200,000 or more. molecular weight
If it is less than 200,000, it is 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-aqueous cosmetic. In addition to the modified powder of the present invention, this cosmetic may contain squalane, liquid paraffin, vaseline,
Microcrystalline wax, ozokerite,
Ceresin, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, cetyl alcohol, hexadecyl alcohol, oleyl alcohol, cetyl-2-ethylhexanoate, 2-ethylhexyl partetate, 2-octyldodecyl myristate, 2 -Octyldodecyl gum ester, neopentyl glycol-2-
Ethylhexanate, isooctyl triglyceride, 2-octyl dodecyl oleate, isopropyl myristate, isostearic triglyceride, coconut oil fatty acid triglyceride, olive oil, avocado oil, beeswax, myristyl myristate, mink oil, lanolin, dimethylpolysiloxane, etc. Hydrocarbons, higher fatty acids, fats and oils, 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, camphor, citric acid. Plasticizers such as acetyltributyl acid, ultraviolet absorbers, antioxidants, preservatives, surfactants, humectants, fragrances,
Water, alcohol, thickeners, etc. can be added. The non-aqueous cosmetic containing the modified powder of the present invention is
It has high water repellency and spreads easily on the skin, causing less 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, the modified powder of the present invention exhibits excellent dispersibility in powder, oil, or solvent, so when pearl pigment is used as the powder to be treated, it can be used in cosmetics with excellent gloss. 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 make-up effect. Red No. 202 has two crystal forms, α-form and β-form, and the β-form changes to the α-form in the presence of water, changing its 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. Water-based cosmetics 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 excellent stability and usability can be achieved. You can obtain cosmetics with 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 has a powder treated by surface polymerization of methylhydrodiene polysiloxane. Unlike the body, hydrogen is not evolved when it comes into contact with water or lower alcohols. In addition, since the silicone polymer film is thin and highly transparent, powders subjected to the surface treatment of the present invention have no difference in color tone from untreated powders, and there is no difference in magnetic properties of powders that are magnetic. . In addition to these properties, the treated powder of the present invention has high hydrophobicity and inherently has good dispersion in the oil phase, and can be stabilized by being added to the oil phase, dispersed, and then emulsified into the aqueous phase. An oil-in-water type emulsified cosmetic with good usability can also be obtained by adding it to an oil phase, dispersing it, and then emulsifying the aqueous phase 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 silicic acid, silicic anhydride, magnesium silicate, talc, kaolin, mica, synthetic mica, bentonite, and titanium-coated mica. , bismuth oxychloride, zirconium oxide,
Inorganic powders such as magnesium oxide, zinc oxide, titanium dioxide, calcium carbonate, magnesium carbonate, iron oxide, ultramarine blue, navy blue, chromium oxide, chromium hydroxide, zeolite, boron nitride, ceramic powder, calamine and carbon black, polyamide, polyester , polyethylene, polypropylene, polystyrene, polyurethane, vinyl resin,
Urea resin, phenolic resin, fluororesin, silicone resin, acrylic acid resin, melamine resin, epoxy resin, polycarbonate resin, divinylbenzene-styrene copolymer, and a copolymer consisting of two or more monomers of the above compounds. , organic powders such as celluloid, acetyl cellulose, polysaccharides, proteins, and hard proteins, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405 , organic pigments such as 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,
Red No. 230, Red No. 401, Red No. 505, Orange No. 205,
Examples include, but are not limited to, organic pigments such as Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1 zirconium, barium or aluminum lake. In addition, there is no particular limit to the particle size of the powder, but it is 0.001
The particle size ranges from 200μ to 200μ, and in particular, fine particles from 0.001 to 0.1μC can be used by being covered with a uniform thin film. The amount of the surface-treated powder used in the present invention contained in the water-based cosmetic is 0.01 to 90% by weight based on the total amount of the cosmetic.
Preferably it is 0.1 to 80% by weight. 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, ingredients normally used in aqueous cosmetics can be stably blended. For example, as water phase components, moisturizers such as propylene glycol, diflopylene glycol, 1,3-butylene glycol, glycerin, maltitol, sorbitol, polyethylene glycol, sodium hyaluronate, pyrrolidone carboxylate, petrolatum, lanolin, ceresin, micro Solid products such as crystalline wax, carnauba wax, candelilla wax, higher fatty acids, higher alcohols, etc.
Semi-solid oils, squalane, liquid paraffin, ester oils, liquid oils such as triglycerides, inorganic pigments, organic pigments, colorants such as dyes, other powders, cationic activators, anionic activators, nonionic activators agents, surfactants such as amphoteric surfactants, drugs such as vitamin E and vitamin E acetate, astringents, antioxidants, preservatives, fragrances, citric acid, sodium citrate, lactic acid, sodium lactate, dibasic sodium phosphate PH adjusters such as, thickeners such as organically modified montmorillonite, ultraviolet absorbers, etc., can be incorporated within a qualitative and quantitative range that does not impair the effects of the present invention. [Effects of the Invention] The treated powder obtained by the present invention has the following characteristics. Because 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.
Also, there is no change in color due to crushing force. Processing is simple, there is no waste of processing agent, and the process is uniform due to gas phase processing. The water repellency and surface activity of the treated powder are almost completely blocked. According to the present invention, ultrafine powder (e.g. particle size
0.005-0.05 μm) can be effectively coated with a uniform and thin silicone polymer without undesirable agglomeration. [Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1.1 10g and 20g of yellow iron oxide in a 200ml beaker
5 g of tetramethyltetrahydrodienecyclotetrasiloxane in a ml sample tube was placed in a desiccator and left at 50°C. After 1 day, remove from the desiccator and leave at 50℃ for 3 hours.
10.185g of treated product was obtained. Comparative Example 1.1 25 g of a hexane solution containing 0.185 g of tetramethyltetrahydrodienecyclotetrasiloxane was added to 10 g of yellow iron oxide, stirred thoroughly, and then evaporated to dryness. After that, when it was baked at 250℃, it turned red. Comparative Example 1.2 Yellow iron oxide 10g and calcium hydroxide 0.019g
was placed in a ball mill and mixed and ground for 30 minutes. Thereafter, 0.185 g of hydrogen methylpolysiloxane (molecular weight -2600) was added, and mixing and grinding was performed for an additional 30 minutes. Next, add 0.076g of myristic acid and 30
A treated product was obtained by mixing and grinding for a minute. Color measurement, water repellency,
The specific volume and decomposition behavior of linalool in a microreactor were measured. (Color measurement) A sample was filled into a cell for powder measurement, and measured in the range of 380 nm to 780 nm using a Hitachi Color Analyzer Model 607. The respective spectral curves are shown in Figure 1. As is clear from the spectral curves, the untreated powder and the powder of Example 1.1 are quite similar, and it can be seen that the patterns of Comparative Example 1.1 and Comparative Example 1.2 are different. In addition, the color measurement results are displayed in L, a, b,
Table 1.1 shows the calculated color difference ΔE. It can be seen that the color difference ΔE of Example 1.1 is significantly smaller than that of each comparative example. (Water repellency) 5 ml of ion-exchanged water was placed in a 10 ml sample tube, and 0.1 g of powder was added and shaken. Judgment was made as follows. ×... Dispersed in the water. △...Water repellent, but some of it was dispersed in water. 〇...It was water repellent and floated to the surface of the water. The results are shown in Table 1.1. The untreated yellow iron oxide was well dispersed in water. Example 1.1 and Comparative Example 1.2 had water repellency and floated on water, but Comparative Example 1.1
However, the treatment was not complete and some of it was dispersed into the water. (Specific volume) Put 5g of powder into a test tube for tapping specific volume,
Tapping was performed 200 times to determine the specific volume. The results are shown in Table 1.1. It can be seen that in Comparative Example 1.2, the specific volume was reduced due to agglomeration due to the use of a ball mill. Some aggregation also occurred in Comparative Example 1.1, but this seems to be due to the evaporation of the solvent. On the other hand, in Example 1.1, since the gas phase treatment is performed, aggregation does not occur and the specific volume is the same as that of the untreated sample.

[Table] (Decomposition of linalool using a microreactor) 20 mg of powder was fixed with quartz wool in a Pyrex glass tube with an inner diameter of 4 mm, and the decomposition of linalool (a type of aroma component) was measured at a reaction temperature of 180°C.
The amount of linalool injected was 0.3μ, and the carrier gas was nitrogen at a flow rate of 50ml/min. The analysis was performed using Shimadzu GC-7A, and the column was 5% FFAP/chromosorb w 80/100 3mm x 3m.
and increase the column temperature from 80℃ (4min).
The temperature was raised to 220°C (heating rate: 5°C/min). FIG. 2 is a gas chromatogram pattern of linalool decomposition of untreated yellow iron oxide. In Figure 2, a is the peak of linalool,
Each peak is a peak of linalool decomposition product. FIG. 3 is a gas chromatogram pattern of linalool decomposition in Example 1.1. It can be seen that the decomposition products of , have decreased compared to the untreated product, and the linalool degrading activity has disappeared. Fourth
The figure shows the linalool decomposition pattern of Comparative Example 1.1.
There is no linalool peak, only decomposition products. In other words, the decomposition activity of the powder of Comparative Example 1.1 was increased compared to that of the untreated powder, indicating that the fragrance stability was worsened. FIG. 5 shows the linalool decomposition pattern of Comparative Example 1.2. The activity is weaker than in Comparative Example 1.1, and unreacted linalool remains, but the activity is stronger than that of the untreated product. As described above, in Comparative Examples 1.1 and 1.2, the linalool decomposition activity is stronger and the flavor stability is worse than in the untreated product, but in Example 1.1, the linalool decomposition activity is weaker and the flavor stability is improved. ing. For the linalool decomposition activity in Table 1.1, the untreated product is marked as △ (standard), the one that is stronger than the untreated one is marked as ×, and the one that is weaker is marked as ○. Judging from Table 1.1 comprehensively, it can be seen that Example 1.1 remains water repellent with almost the same color and specific volume as the untreated sample. Furthermore, the fragrance stability has been improved, and it is considered to be an extremely excellent treated powder when blended into cosmetics and the like. Example 1.2 100g yellow No. 5 aluminum lake and trimethyltrihydrodienecyclotrisiloxane
Put 500g into a separate container and charge it into a gas sterilizer Capokalyzer CL-30B (Fuji Electric Co.Ltd.), and use an aspirator to reduce the internal pressure to 100mmHg.
The pressure was reduced to 30°C and the temperature was maintained at 30°C. After 6 hours, air was introduced to return the pressure to normal pressure, and the pressure was evacuated several times to obtain 128 g of treated powder. This treated powder exhibited significant hydrophobicity and lost its ability to decompose linalool. Example 1.3 10 g of Prussian blue and 10 g of tetramethyltetrahydrodienecyclotetrasiloxane were placed in separate containers in a desiccator and left at 100° C. for 6 hours. Thereafter, it was dried at 100° C. for 2 hours to obtain 13.3 g of treated powder. This treated powder showed significant hydrophobization, and the ability to decompose linalool had disappeared. Also,
The navy blue did not decompose during this treatment and there was no cyan odor. Example 1.4 10 g of zinc white and 5 g of hexamethylcyclotrisiloxane were placed in separate containers and charged into a gas sterilizer capocalizer CL-30B (Fuji Electric Co. Ltd.), and the internal pressure was increased to 300 mm using an aspirator.
The pressure was reduced to Hg and the temperature was maintained at 50°C. After leaving it for one night, after putting air in it and returning it to normal pressure,
After evacuation several times, 10.2 g of treated powder was obtained. This treated powder showed significant hydrophobicity. Example 1. 5. 20 kg of titanium dioxide was placed in a rotating double cone type reaction tank (made of stainless steel, with a heat insulation jacket) having a volume of 100 ml. On the other hand, 400 g of tetramethyltetrahydrogencyclotetrasiloxane was placed in a stock solution supply tank (made of stainless steel, equipped with a heat insulating jacket) that was directly connected to this reaction tank through a stainless steel pipe. Next, vacuum pump the system.
The pressure was reduced to 100 mmHg. A circulating pump supplies the heat medium heated to 90℃ from the heat medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank, and the temperature of the system is raised to 90℃.
It was kept at ℃. The reaction tank was rotated three times using a timer after being allowed to stand still for 10 minutes, and the operation of mixing and stirring titanium dioxide in the reaction tank was repeated for 10 hours. Thereafter, N ₂ gas was introduced into the system to return it to normal pressure, and 20.3 kg of treated powder was taken out. This treated powder exhibited good fluidity without any agglomeration seen in untreated titanium dioxide, exhibited significant hydrophobicity, and had lost its ability to decompose linalool. Example 2.1 Yellow iron oxide as a powder in a 100 ml two neck flask
I put 10g. One neck of the two-necked flask was connected to a 30 ml bubbler, and the other neck of the two-necked flask was connected to a trap cooled with dry ice-acetone. Two-necked flask and bubbler at 90℃
After leaving it in a constant temperature bath for 3 hours, 5 g of tetramethyltetrahydrodienecyclotetrasiloxane was poured into the bubbler as a treatment agent. Nitrogen was flowed through the bubbler as a carrier gas at a flow rate of 2.0 ml/min for 15 hours. Disconnect each neck of the two-necked flask from the bubbler and trap and leave it at 50℃ for 3 hours.
10.2g of treated product was obtained. Regarding the yellow iron oxide of Example 2.1, colorimetry, water repellency, specific volume, and decomposition behavior of linalool in a microreactor were measured in the same manner as in Example 1.1. The results are shown in Table 2.1.

[Table] Example 2.2 35.4 g of treated powder was obtained in the same manner as in Example 2.1 except that kaolin was used as the powder and hexamethylcyclotrisiloxane was used as the processing agent. This treated powder showed significant hydrophobicity, and its ability to decompose linalool had disappeared. However, the treated powder was slightly slurried. Example 2.3 In Example 2.1, a three-way cap was installed between the two-necked flask and the bubbler, and nitrogen was supplied at 4.0 ml/min.
14.1 g of treated powder was obtained in the same manner as in Example 2.2 except that the powder was flowed at a flow rate of . This treated powder showed significant hydrophobicity, and the ability to decompose linalool had disappeared. Example 2.4 In Example 2.1, the powder was muscovite, the treatment agent was 1,
10.4 g of powder treated in the same manner as in Example 2.1 except that 3,5-tris(3,3,3-trifluoropropyl)-1,3,5 trimethylcyclosiloxane was used.
I got it. This treated powder showed significant hydrophobicity, and the ability to decompose linalool had disappeared. Example 2.5 20 kg of titanium dioxide was placed in a rotating double cone reactor (made of stainless steel, equipped with a thermal jacket) having a volume of 100 ml. The temperature of the reaction tank and the processing liquid supply tank (made of stainless steel, with a heat insulating jacket) with a capacity of 10 that is directly connected to it is determined by using a circulating pump to supply a heat medium heated to 90°C from the heat medium heating tank to each heat insulating jacket. to 90℃. One portion of 1,3,5,7-tetramethylcyclotetrasiloxane was added to the treatment liquid supply tank, and nitrogen gas was supplied to the treatment liquid supply tank at 2/min to bubble the treatment liquid. Note that the reaction tank is equipped with a condenser from which nitrogen gas is released and unreacted processing agent can be recovered. In addition, the reaction tank was rotated for 1 minute at 10 minute intervals, and the operation of mixing titanium dioxide in the reaction tank was repeated for 10 minutes.
Repeatedly for several hours, 20.3 kg of treated powder was collected. This material had no agglomeration seen in untreated titanium dioxide, exhibited good fluidity, and also exhibited significant hydrophobicity, and the ability to decompose linalool had disappeared. Example 3.1 100 g of ultramarine powder and 20 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers and left in a closed system at room temperature. After 96 hours, the ultramarine was taken out and its weight was measured, and 100.78 g of treated ultramarine was obtained.Furthermore, when it was left in a dryer at 50°C for 24 hours, 100.32 g of final treated ultramarine was obtained. Example 3.2 A mixed solution of 1 g of tetrahydrotetramethylcyclotetrasiloxane and 1 g of pentahydropentamethylcyclopentasiloxane and 10 g of ultramarine powder were placed in separate containers and allowed to stand at 90° C. in a closed system.
After 24 hours, remove the ultramarine and place it in a dryer at 90℃.
When left for 24 hours, 10.13 g of final treated ultramarine was obtained. Regarding the ultramarine blues of Examples 3.1 and 3.2, (1) Measurement of crosslinking rate, (2) Measurement of chloroform elution of silicone polymer, (3) Measurement of hydrogen sulfide by hydrogen sulfide detection method, (4)
Hydrogen sulfide was measured using the silver plate blackening test method, and (5) linalool decomposition was measured using a microreactor. (1) Measurement of crosslinking rate In the present invention, the silicone polymer [RSiO _3/2 ] _x [RHSiO] _y coated on the ultramarine surface is 100x/(x
+y) indicates the Si--H group crosslinking rate, which can be measured using a Fourier transform infrared spectrophotometer. Mix 100mg of sample and 900mg of KBr powder uniformly,
It was packed in a diffuse reflection spectrum measurement cell and measured under the following conditions. Resolution: 1 cm ^-1 Number of integrations: 100 Wavenumber range: 1300 to 1200 cm ^-1 Next, the obtained spectrum is subjected to Kubelkamung function conversion using the included computer software, and then peak division is performed using the decomposition method. I went there. Spectrum after peak splitting is 1261cm ^-1 and 1272cm
^-1 , and the peak at 1261 cm ^-1 is assigned to the methyl group of [RHSiO] _y , and the peak at 1272 cm ^-1
Since the peak is attributed to the methyl group of [RSiO _3/2 ] _x , the crosslinking rate of the silicone polymer can be determined by the following formula. Crosslinking rate of silicone polymer = ○/x/○/x+○/y
×100: Peak height of 1272 cm ^-1 : Peak height of 1261 cm ^-1 (2) Chloroform elution measurement of silicone polymer Disperse 20 g of sample in 100 ml of chloroform, filter, and concentrate the filtrate with an evaporator. Molecular weight was measured by Schon chromatography. The equipment is Japan Analytical
Measurement was carried out using Industry Co. Ltd LC-08 and three columns, B4H and B3H x 2. The solvent was chloroform (1.07ml/min).
RI was used as a detector. Molecular weight was estimated from a standard polyethylene calibration curve. After filtration, the ultramarine blue was dried at 80°C for 24 hours and tested for water repellency. (3) Hydrogen sulfide measurement using hydrogen sulfide detection method Attach a 50ml dropping funnel and a simple gas detection tube that can detect hydrogen sulfide to a 200ml three-necked round-bottomed flask with a magnetic stirrer, connect the detection tube to a water pump, and measure the amount of hydrogen sulfide generated. Hydrogen sulfide gas was always drawn in at a constant pressure. The scale was printed directly on the gas detection tube, and hydrogen sulfide of 0.1 to 2.0% could be read directly. Measurement was performed using this measuring device in the following manner. Put 0.5g of ultramarine into a three-neck round bottom flask and add 5ml of this.
was uniformly dispersed in ion-exchanged water. Next, 5 ml of 1N hydrochloric acid was added at once through the funnel, and the mixture was stirred with a magnetic stirrer. Ultramarine blue was decomposed by the acid, and the amount (%) of hydrogen sulfide generated was read using a detection tube. (4) Hydrogen sulfide measurement using silver plate blackening test method Ultramarine blue and silver plate were heated at 80℃ for 2 days in a sealed container.
The degree of blackening of the silver plate due to hydrogen sulfide generated during that time was observed with the naked eye. (5) Decomposition measurement of linalool using a microreactor 20 mg of powder was fixed with quartz wool in a Pyrex glass tube with an inner diameter of 4 mm, and the decomposition of linalool, one of the aroma components, was measured at a reaction temperature of 180°C. The amount of linalool injected was 0.3 μ, the carrier gas was nitrogen,
The flow rate was 50ml/min. The analysis was performed with Shima Ritsu GC-7A. Column: 5% FFAP/chromosorb w80/100 3mm x 3m
column temperature from 80℃ (4min) to 220℃
(The temperature increase rate was 5° C./min). (6) Measurement of water repellency Pour 5 ml of ion exchange water into a 10 ml sample tube,
Further, 0.1 g of sample was added and shaken. After shaking, it was left to stand for 24 hours and it was determined whether the ultramarine blue dispersed in the water or floated on the surface. (Results and evaluation regarding Example 3.1) (1) From the results of the infrared absorption spectrum, 100x/(x
+y)=44. Therefore, it can be seen that 44% of the structure of [CH ₃ SiO _3/2 ] _x [(CH ₃ )HSIO] _y is cross-linked with x, forming a considerable network structure. (2) Gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment revealed that silicone polymers do not elute in chloroform. This indicates that the silicone polymer on the ultramarine surface has become polymerized to the extent that it cannot be dissolved in chloroform. In a similar gel permeation experiment, silicone polymers with a molecular weight of less than 200,000 were eluted in chloroform, suggesting that the silicone polymer polymerized on the ultramarine surface had a molecular weight of 200,000 or more. This result is
This agrees well with the above result of 100x/(x+y)=44, indicating that the network-structured silicone polymer tightly coats the ultramarine surface. (3) According to the results of the hydrogen sulfide detection method, untreated ultramarine rapidly generates hydrogen sulfide, reaching 1.0% or more in 10 minutes, but the ultramarine obtained in Example 3.1 hardly generates hydrogen sulfide. . As described above, the ultramarine blue obtained in Example 3.1 has extremely excellent acid resistance. (4) In the silver plate blackening test, the ultramarine blue obtained in Example 3.1 remained unchanged, but the untreated ultramarine blue was completely blackened. According to this result, Example
It can be seen that the ultramarine blue obtained in 3.1 has extremely excellent heat resistance. (5) According to the results of linalool decomposition measurement using a microreactor, in untreated ultramarine, linalool decomposes and many decomposition products are generated, but Example 3.1
Linalool is hardly decomposed in the ultramarine obtained. From this result, the ultramarine obtained in Example 3.1 is not only resistant to acids and heat and does not release hydrogen sulfide, but also has no effect of decomposing fragrance components, and is superior in that it does not cause odor even when coexisting with fragrances. It is an ultramarine color. (6) According to the water repellency measurement results, the untreated ultramarine was well dispersed in water and showed no water repellency at all, whereas the ultramarine of Example 3.1 exhibited water repellency and floated on water. Furthermore, it was confirmed that the ultramarine blue after chloroform elution also had water repellency. This means that the silicone polymer on the ultramarine surface is not eluted by chloroform and is coated on the surface.
Moreover, it shows that the surface condition has hardly changed. The table below shows the results regarding the ultramarine blue obtained in Examples 3.1 and 3.2. The ultramarine blue obtained in Example 3.2 was also stable like the ultramarine blue obtained in Example 3.1.

[Table] Example 3.3 5 kg of ultramarine blue was placed in a rotating double cone type reaction tank (made of stainless steel, with a heat-insulating jacket) having a capacity of 100 ml. A stock solution supply tank (made of stainless steel, with heat insulating jacket) is directly connected to this reaction tank with a stainless steel tube. 500 g of silicone compound was added, and the pressure of the system was reduced to 20 mmHg using a vacuum pump. The temperature of the system was maintained at 90°C by supplying a heating medium heated to 90°C from a heating medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump. The reaction tank was allowed to stand still for 10 minutes using a timer and then rotated three times, and this rotation was repeated for 5 hours. Thereafter, nitrogen gas was introduced into the system to return it to normal pressure, and 5.3 kg of silicone polymer-coated ultramarine was obtained. For example 3.3 and untreated,
[R ²¹ SiO] _x [R ²² R ²³ SiO] _y [R ²⁴ R ²⁵ R ²⁶ SiO] x of _z ,
y ratio, chloroform elution, water repellency, linalool decomposition, etc. were measured. (1) Measurement of crosslinking rate Silicone polymer coated on the ultramarine surface in the present invention [R ²¹ SiO _3/2 ] _x [R ²² R ²³ SiO] _y [R ²⁴ R ²⁵ R ²⁶ SiO _2/1 ] _z
In the case where R ²² is H, the crosslinking rate can be measured using a Fourier transform infrared spectrophotometer.
The crosslinking is [(R ²³ )HSiO] _y unit Si-H comrades are Si-
This shows that it becomes O-Si. That is,
[R ³¹ SiO _3/2 ] Since it is _x unit, x/
All you have to do is measure the value of (x+y),
[R ³⁴ R ³⁵ R ³⁶ SiO _1/2 ] The _z unit does not participate in the reaction. For the measurement, 100 mg of the sample and 900 mg of KBr powder were uniformly mixed, placed in a diffuse reflection spectrum measurement cell, and performed under the following conditions. Resolution: 1 cm ^-1 Number of integrations: 100 Wavenumber range: 1300 to 1200 cm ^-1 Next, the obtained spectrum is subjected to Kubelkamunk function conversion using the included computer software, and then peak division is performed using the decomposition method. I went there. Spectrum after peak splitting is 1261cm ^-1 and 1272cm
^-1 peak is maintained, and the peak at 1261 cm ^-1 is assigned to the methyl group of [R ²² R ²³ SiO] _y , and the peak at 1272 cm ^-1 is assigned to the methyl group of [R ²¹ SiO _3/2 ] _x . From this, the crosslinking rate of the silicone polymer can be determined using the following formula. Crosslinking rate of silicone polymer = x / ^x + ^y × 100
After filtration, the filtrate was concentrated using an evaporator, and then the molecular weight was measured using gel permeation chromatography. The equipment is Japan Analytical
Measurement was carried out using Industry Co. Ltd LC-08 with three columns, B4H and B3H x 2. The solvent was chloroform (1.07ml/min).
RI was used as a detector. The molecular weight was measured using a standard polystyrene calibration curve. (3) Measurement of water repellency Pour 5 ml of ion exchange water into a 10 ml sample tube,
Further, 0.1 g of sample was added and shaken. After shaking, it was left for 24 hours to determine whether the sample dispersed in the water or floated on the surface. The judgment is as follows. ×... Dispersed in the water. △...Water repellent, but some of it was dispersed in water. 〇...It was water repellent and floated to the surface of the water. (4) Linalool decomposition measurement using a microreactor A 20 mg sample was fixed with quartz wool in a Pyrex glass tube with an inner diameter of 4 mm, and the decomposition of linalool, one of the aroma components, was measured at a reaction temperature of 180°C. The amount of linalool injected was 0.3 μ, the carrier gas was nitrogen,
The flow rate was 50ml/min. The analysis was performed with Shima Ritsu GC-7A. The column is 5% FFAP/chromosorb w 80/100 3mm×
3m, column temperature from 80℃ (4min)
The temperature was raised to 220°C (heating rate: 5°C/min). As a result of this measurement, the untreated one was marked as △ (standard), the one whose activity was stronger than that of the untreated one was marked as ×, and the one whose activity was weaker was marked as ○. (5) Hydrogen sulfide measurement using the hydrogen sulfide detection method Attach a 50ml dropping funnel and a simple gas detection tube that can detect hydrogen sulfide to a 200ml three-necked round bottom flask with a magnetic stirrer, connect the detection tube to a water pump, and measure the amount of hydrogen sulfide generated. Hydrogen sulfide gas was always drawn in at a constant pressure. The scale was printed directly on the gas detection tube, and hydrogen sulfide of 0.1 to 2.0% could be read directly. Measurement was performed using this measuring device in the following manner. 0.5 g of ultramarine blue was placed in a three-necked round-bottomed flask and uniformly dispersed in 5 ml of ion-exchanged water. Next, 5 ml of 1N hydrochloric acid was added at once through the funnel, and the mixture was stirred with a magnetic stirrer. The amount (%) of hydrogen sulfide produced by the acid as ultramarine blue was read using a detection tube. (6) Hydrogen sulfide measurement using silver plate blackening test method Ultramarine and silver plates were heated in a sealed container for 2 days at 80°C.
The silver plate was left to stand at ℃, and the degree of blackening of the silver plate due to hydrogen sulfide generated during that time was observed with the naked eye. (Results and evaluation regarding Example 3.3) (1) From the results of the infrared absorption spectrum, it was found that 100x/(x+y)=80 in the gas phase treatment of Example 3.3. Two-fifths of the silicone adsorbed in the gas phase are terminal groups (x+y):z=3:2. These terminal groups do not participate in the reaction, and crosslinking means that y units become x units, and at a crosslinking rate of 80%, x:y:z=48:12:40. The more x units there are, the more developed the network structure is, and the better the film is formed. In the case of Example 3.3, 42% was crosslinked, and more than two-thirds of Si--H in the initially supplied silicone monomer was crosslinked, so the network structure was maintained. From the above results, the structure of the silicone polymer in Example 3.3 is [CH ₃ SiO _3/2 ] _x [CH ₃ (H)SiO] _y
[(CH ₃ ) ₃ SiO _1/2 ] _z , and x:y:z=48:
It is 12:40. (2) As a result of gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment, it was found that the silicone polymer did not elute in chloroform. This shows that in Example 3.3, the silicone polymer is polymerized and
This indicates that it is no longer eluted in chloroform. In a similar gel permeation experiment, the molecular weight
Since a silicone polymer with a molecular weight of less than 200,000 is eluted in chloroform, the silicone polymer of Example 3.3 is considered to have a molecular weight of 200,000 or more. This result agrees well with the crosslinking rate {100x/(x+y)}=80 and the development of a network structure. (3) Showing the results of water repellency and linalool decomposition measurements.
Shown in 3.2. Untreated ultramarine is hydrophilic and has the ability to decompose linalool, but Example 3.3 is coated with a silicone polymer, making it water repellent, and the linalool decomposition reaction that occurs on the ultramarine surface does not occur. Therefore, the stability against fragrances was also very good. (4) According to the results of the hydrogen sulfide detection method, untreated ultramarine rapidly generates hydrogen sulfide, with a concentration of 1.0% in 10 minutes.
However, the ultramarine blue obtained in Example 3.3 hardly generates hydrogen sulfide. As described above, the ultramarine blue obtained in Example 3.3 has excellent acid resistance. (5) In the silver plate blackening test, the ultramarine blue obtained in Example 3.3 remained unchanged, but the untreated ultramarine blue was completely blackened. According to this result, it can be seen that the ultramarine blue obtained in Example 3.3 has excellent heat resistance. Example 3.4 10 g of ultramarine blue and 5 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers and left in a desiccator at 80°C. After 48 hours, the ultramarine was taken out and its weight was measured, and 10.18 g of treated ultramarine was obtained.When it was left in a dryer at 120°C for 24 hours, 10.12 g of treated ultramarine was obtained. The crosslinking rate of this treated product was 52%. This product showed remarkable water repellency, and the linalool decomposition effect had also disappeared. It also had excellent acid resistance and heat resistance. Example 3.5 Put 100 g of potash navy blue and 50 g of tetrahydrotetramethylcyclotetrasiloxane into separate containers.
It was left in a desiccator at 80°C. After 72 hours, the navy blue was taken out and its weight was measured.
132.3g was obtained, and when the product was left in a dryer at 80°C for 24 hours, 130.1g of treated navy blue was obtained. Example 3.6 100 g of ammonium navy blue and 50 g of trihydropentamethylcyclotetrasiloxane were placed in separate containers and left in a closed container at 50°C. After 72 hours, the navy blue was taken out and its weight was measured.
125.3 g was obtained, and when the product was left in a dryer at 80° C. for 24 hours, 124.3 g of treated navy blue was obtained. (Measurement items) (1) crosslinking rate, (2) measurement of chloroform elution of silicone polymer, (3) determination of water repellency, and (4) measurement of stability of linalool by the method described in Example 3.3 above. It was measured. (Results and evaluation regarding Example 3.5) (1) As a result of infrared absorption spectrum, it was found that the crosslinking rate of Example 3.5 was 61%. Therefore, the structure of the film in Example 3.5 is [CH ₃ SiO _3/2 ] _x [(CH ₃ )HSiO] _y , with 61% of the structure being x. (2) Gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment revealed that silicone polymers do not elute in chloroform. This indicates that the silicone polymer on the treated navy blue surface has become polymerized to the extent that it is not soluble in chloroform. In a similar gel permeation experiment, silicone polymers with a molecular weight of less than 200,000 were eluted in chloroform, so it is thought that the silicone polymer polymerized on the treated dark blue surface has a molecular weight of 200,000 or more. This result is
This result agrees well with the above result of 100x/(x+y)=61, indicating that the network-structured silicone polymer tightly coats the treated dark blue surface. (3) When the water repellency of Example 3.5 was evaluated, it was found that untreated Prussian blue showed hydrophilicity, but Example 3.5 showed water repellency and was coated with a silicone polymer film. As a result of the decomposition measurement of linalool, untreated ultramarine decomposes linalool and decomposition products such as myrcene, limonene, ocimene, alloocimene, α-terpinene, and terpinolene are generated, but in Example 3.5, linalool is only slightly decomposed. The products were dehydrated products such as myrcene and ocimene, but none were cyclized or isomerized. From this, it can be seen that in Example 3.5, the silicone polymer film covers the active sites of the dark blue color and enhances the fragrance stability. (Results and evaluation regarding Example 3.6) The crosslinking rate of Example 3.6 was 57%. Therefore, the structure of the silicone polymer in Example 3.6 is [CH ₃ SiO _3/2 ] _x [(CH ₃ )HSiO] _y [(CH ₃ ) ₂ SiO] _z , with 42.75% x units and 32.25% y units. %,z
The unit is 25%. The treated powder of Example 3.6 was water repellent and had no linalool decomposition activity, indicating that the dark blue surface was uniformly coated with the silicone resin. Example 3.7 5 kg of potassium navy blue was placed in a rotating double cone type reaction tank (made of stainless steel, equipped with a heat insulating jacket) having a capacity of 100 ml. The structural formula is 500 g of silicone compound was added, and the pressure of the system was reduced to 20 mmHg using a vacuum pump. The temperature of the system is determined by supplying a heating medium heated to 90℃ from a heating medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump.
It was kept at 90℃. The reaction tank is rotated 10 times by a timer.
Let stand for 3 minutes and then rotate 3 times.
Time repeated. While the rotation was repeated, the Prussian blue was mixed and stirred in the reaction tank, and then nitrogen gas was introduced into the system to return it to normal pressure, yielding 6.4 kg of silicone-coated Prussian blue. (Measurement items) (1) Measurement of crosslinking rate, (2) Measurement of chloroform elution of silicone polymer, (3) Measurement of water repellency, and (4) Measurement of stability of linalool in Example 3.3 above.
It was measured by the method described in connection with . (Results and evaluation regarding Example 3.7) (1) As a result of infrared absorption spectrum, it was found that the crosslinking rate of Example 3.7 was 64%. Therefore, the structure of the silicone polymer in Example 3.7 is: [CH ₃ SiO _3/2 ] _x [(CH ₃ )HSiO] _y [(CH ₃ ) ₃ SiO _1/2 ]
_z , and 64% of x+y has the structure of x. (2) As a result of gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment, it was found that the silicone polymer did not elute in chloroform. This indicates that in Example 3.7, the silicone polymer was polymerized and no longer eluted in chloroform. In a similar gel permeation experiment, silicone polymers with a molecular weight of less than 200,000 were eluted in chloroform.
3.7 silicone polymer is thought to have a molecular weight of 200,000 or more. This result is in good agreement with the crosslinking rate of 100x/(x/y)=64 and the development of a network structure. (3) When the water repellency of Example 3.7 was evaluated, the untreated Prussian blue showed hydrophilicity, but the Prussian blue of Example 3.7 showed water repellency, indicating that it was coated with a silicone polymer film. . As a result of the decomposition measurement of linalool, untreated navy blue decomposes linalool and produces myrcene, limonene,
Decomposition products such as ocimene, alloocimene, α-tapinene, and terpinolene are produced, but in the example
In 3.7, linalool was only slightly decomposed, and the products were dehydrated products such as myrcene and ocimene, with no cyclization or isomerization. From this, it can be seen that in Example 3.7, the silicone polymer film covers the active sites of the dark blue color, increasing the fragrance stability. Example 3.8 10 kg of ammonium navy blue is placed in a rotating double cone type reaction tank (made of stainless steel, with a heat insulating jacket) having a capacity of 100, and a stock solution supply tank (made of stainless steel, with a heat insulating jacket) is directly connected to the reaction tank with a stainless steel pipe. expression 3 kg of silicone compound was added, and nitrogen was bubbled from the bottom of the stock solution supply tank to supply it to the reaction tank. The temperature of the system was maintained at 70°C by supplying a heating medium heated to 70°C from a heating medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump. The reaction tank is rotated by a timer after it has been left still for 10 minutes.
This rotation was repeated for 7 hours. Thereafter, the silicone compound was removed, and rotation was continued for 2 hours while only nitrogen was introduced into the reaction tank, and after the temperature was returned to room temperature, 12.3 kg of treated material was obtained. Example 4.1 10 g of yellow iron oxide powder and 5 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers and left in a desiccator at 80°C. After 72 hours, the yellow iron oxide was taken out and its weight was measured, and 10.50 g of treated yellow iron oxide was obtained.After leaving it in a dryer at 50°C for 24 hours, 10.20 g of treated yellow iron oxide was obtained.
was gotten. Example 4.2 100 g of finely divided titanium dioxide (0.025 μm) and 20 g of tetrahydrotetramethylcyclotetrasiloxane
and were placed in separate containers and left in a sealed container at room temperature. After 96 hours, the fine particles of titanium dioxide were removed and their weight was measured.
107.85 g was obtained, and when it was left in a dryer at 50° C. for 24 hours, 104.80 g of treated fine particle titanium oxide was obtained. Example 4.3 100 g of red iron oxide powder and 20 g of dihydrohexamethylcyclotetrasiloxane were placed in separate containers and left in a closed container at 80°C. After 72 hours, the red iron oxide was taken out and weighed, and 101.50 g of treated red iron oxide was obtained, which was then placed in a dryer at 50℃.
After standing for 24 hours, 100.60 g of treated red iron oxide was obtained. Example 4.4 Dihydrohexamethylcyclotetrasiloxane
A mixed solution of 2 g and 2 g of pentahydropentamethylcyclopentasiloxane and 10 g of zinc white powder were placed in separate containers and left in a closed container at 90°C. After 12 hours, the zinc white powder was taken out and its weight was measured, and 10.90 g of zinc white powder was obtained.
When it was left in a dryer at ℃ for 24 hours, 10.60 g of final treated zinc white was obtained. Example 4.5 A mixed solution of 2 g of tetrahydrotetramethylcyclotetrasiloxane and 2 g of pentahydropentamethylcyclopentasiloxane and 10 g of zirconium oxide were placed in separate containers and left in a closed container at 30°C. After 24 hours, the zirconium oxide was taken out and its weight was measured, and 11.60 g of zirconium oxide was obtained. When it was further left in a dryer at 90° C. for 24 hours, 10.80 g of final treated zirconium oxide was obtained. Example 4.6 Put 10 g of silica powder and 5 g of tetrahydrotetramethylcyclotetrasiloxane in separate containers,
It was left in a desiccator at 80°C. After 48 hours, the silica was removed and its weight was measured.
14.50 g of treated silica was obtained, and 13.20 g of treated silica was obtained by leaving it in a dryer at 120° C. for 24 hours. (Items to be measured, etc.) (1) Measurement of coating state In the present invention, the state in which the silicone polymer coated on the powder surface is uniformly coated can be measured using an X-ray photoelectron spectrometer. The device is Shimadzu ESCA750, the anode is a conical anode (Mg), the filament is a semicircular filament, and the filter is 2μ aluminum.
Measured at 12KW and 30mA. Glue the sample to double-sided tape and attach it to 0~
Measurements were made in the 760eV range. Unlike untreated metal oxides, those coated with a silicone polymer film can be judged because they show the binding energies of Si ₂ s and Si ₂ p orbitals.
(2) Measurement of crosslinking rate, (3) Measurement of chloroform elution of silicone polymer, (4) Determination of water repellency, and (5) Measurement of stability of linalool (using a microreactor) were performed in accordance with Example 3.3 above. It was carried out using the method described in . (6) Color measurement The sample was filled into a cell for powder measurement, and the color was measured in the range of 380-780 nm using a Hitachi Color Analyzer Model 607. The color measurement results were displayed as L, a, and b, and the color difference ΔE was calculated. (7) Measurement of specific volume Put 5g of powder into a test tube for tapping specific volume.
Tapping was performed 200 times to determine the specific volume. Judgment of leaf agent stability (8) In order to examine the interaction with drugs, vitamin E, resorcinol, or γ-oryzanol was brought into direct contact with the powder and judged whether browning occurred or not. The judgments in Table 4.2 below are as follows. ×: Browning Δ: Slight yellowing ○: No change (Results and evaluation regarding Example 4.1) (1) The coating state of the silicone polymer was measured using an X-ray photoelectron spectrometer, and the results are shown in FIG. In yellow iron oxide before treatment, Fe ₂ s, Fe ₂ p, Fe ₃ p
and Fe Auger binding energies were observed. On the other hand, after treatment (coating),
All the Fe-based peaks that appeared in the untreated sample disappeared, and new Si ₂ s and Si ₂ p appeared. From the above, it can be seen that there is no Fe and only Si on the surface. Coverage amount and surface area of treated yellow iron oxide (9.8m ² /
g), the uniform coating thickness of Example 4.1 is approximately 20 Å
it is conceivable that. If the silicone polymer is present in clumps or if there is an untreated surface, Fe would naturally appear, but the treated yellow iron oxide of Example 4.1 does not have such a problem and has a uniform silicone polymer film. You can see that it's covered. (2) Crosslinking rate in gas phase treatment with cyclic silicone compounds based on the results of infrared absorption spectra
100x/(x+y) was found to be 52%. Therefore, 52% of the structure of the silicone polymer [CH ₃ SiO _3/2 ] _x [(CH ₃ )HSiO] _y covering the surface is derived from x, and a network structure has developed. I understand that. (3) As a result of gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment, it was found that the silicone polymer did not elute in chloroform. This indicates that the silicone polymer on the surface of the treated yellow iron oxide has become polymerized to the extent that it cannot be dissolved in chloroform. In a similar gel permeation experiment, silicone polymers with a molecular weight of less than 200,000 were eluted in chloroform, suggesting that the silicone polymer polymerized on the treated yellow iron oxide surface had a molecular weight of more than 200,000. This result agrees well with the above result of 100x/(x+y)=52, indicating that the network-structured silicone polymer tightly coats the treated yellow iron oxide surface. The colorimetry, water repellency, specific volume, and linalool stability (by microreactor) are summarized in Table 4.1 for the powder and untreated yellow iron oxide of Example 4.1. Looking at the color difference, the powder of Example 4.1 shows almost no change from the untreated powder. In terms of water repellency, the powder of Example 4.1 has good properties, and in terms of specific volume, there is almost no difference from that of untreated powder. From the results of linalool stability (degradation activity),
It can be seen that the powder of Example 4.1 well blocks the activity of yellow iron oxide and hardly decomposes linalool. (Results and evaluation regarding Examples 4.2 to 4.6) As shown in Table 4.2, the metal oxides obtained in Examples 4.2 to 4.6 were stable, similar to the metal hydroxide obtained in Example 4.1. . In particular, titanium dioxide adsorbs vitamin E and γ-oryzanol and turns brown, but the powder of Example 4.2 does not turn brown and is stable against chemicals. Similarly, zinc white turns brown when coexisting with resorcinol, but the powder of Example 4.4 does not turn brown and is stable. These results are consistent with the stability of linalool and indicate that the active sites of titanium dioxide and zinc white were blocked.

【table】

[Table] Example 4.7 5 kg of particulate titanium dioxide (0.025 μm) was placed in a rotating double cone type reaction tank (made of stainless steel, equipped with a heat insulating jacket) having a volume of 100 mm. The raw solution supply tank (made of stainless steel, with heat insulation jacket) is directly connected to this reaction tank with a stainless steel pipe. 500 g of silicone compound was added, and the pressure of the system was reduced to 20 mmHg using a vacuum pump. The temperature of the system is set by supplying the heat medium heated to 90℃ from the heat medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump.
It was kept at 90℃. The reaction tank is rotated 10 times by a timer.
Let stand for 3 minutes and then rotate 3 times.
Time repeated. While the rotation was repeated, titanium dioxide was mixed and stirred in the reaction tank, and then nitrogen gas was introduced into the system to return it to normal pressure, yielding 5.3 kg of silicone polymer-coated titanium dioxide. (Measurement items) (1) Measurement of coating state In the present invention, the state that the silicone polymer coated on the powder surface is uniformly coated can be measured using an X-ray photoelectron spectrometer. The device is ESCA-5300 manufactured by Albac Fire Co., Ltd.
The X-ray source was 15KV dual anode Mg300W, the energy analyzer was a hemispherical electrostatic analyzer (SCA), and the detector was a PSD (position sensitive detector). The binding energy was determined by correcting the value of C ₁ s as a standard. Materials coated with a silicone polymer film can be judged because they exhibit bond energies of Si ₂ s and Si ₂ p orbitals, unlike untreated metal oxides. (2) Measurement of crosslinking rate, (3) Measurement of chloroform elution of silicone polymer, (4) Determination of water repellency, and (5) Measurement of stability of linalool (using a microreactor) were performed in accordance with Example 3.3 above. It was carried out using the method described in . (6) Drug stability was determined by the method described in connection with Example 4.1 above. (Results and Evaluation Regarding Example 4.7) (1) The coating state of the silicone polymer was measured using an X-ray photoelectron spectroscopy analyzer, and the results are shown in FIG. In the titanium dioxide before treatment [a in Figure 7],
Ti ₃ s, Ti ₃ p, O ₂ s, etc. are observed, indicating that the surface is composed of Ti and O elements. On the other hand, the sample of Example 4.7 [Fig. 7b]
In addition to Ti ₃ s, Ti ₃ p, and O ₂ s, bond energies of Si ₂ s and Si ₂ p are observed, indicating that the surface is coated with a Si compound in addition to titanium dioxide. However, the silicone polymer film has a
It is thought to be thinner than Å, and titanium dioxide has also been observed inside. (2) The results of the infrared absorption spectrum are shown in Figure 8. a is untreated titanium dioxide, b is an example
This is the infrared absorption spectrum of 4.7. 1270 in b
There is also an absorption caused by Si—CH ₃ near cm ^-1 .
Absorption caused by Si—H groups is seen near 2170 cm ⁻¹ . Furthermore, when the absorption of Si--CH ₃ near 1270 cm ^-1 was peak-divided by the decomposition method, it was found that 100x/(x+y) was 66. Therefore, the ratio of x to y in the silicone polymer [CH ₃ SiO _3/2 ] _x [CH ₃ )HSiO] _y [(CH ₃ ) ₃ SiO _1/2 ] _z that coats the surface is 66.
%, y is 34%, and 66% of the initial Si-H groups are
This indicates that it was used for Si-O-Si bonding. In addition, in the case of Example 4.7, the ratio of (a+b): is 3:2, and since the terminal group does not participate in the reaction, it is always present at a ratio of 40%, so the example
x:y:z of silicone polymer in 4.7
It is estimated that =39.6:20.4:40.0. The higher the proportion of x units, the more developed the network structure is and the better the film is formed. If the structure of the monomer initially added is known, the structure can be clearly determined by measuring the crosslinking rate in this way. (3) As a result of gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment, it was found that the silicone polymer did not elute in chloroform. This means that the silicone polymer in Example 4.7 is polymerized and
This indicates that it is no longer eluted in chloroform. In a similar gel permeation experiment, silicone polymers with molecular weights less than 200,000 were eluted in chloroform, so it is thought that the silicone polymers of Examples 4.9 and 4.10 had molecular weights of 200,000 or more. This result shows that the crosslinking rate is 100x/
(x+y)=66, which agrees well with the development of a network structure. The test results for water repellency, linalool stability, vitamin E and γ-oryzanol stability for Example 4.7 and untreated titanium dioxide are summarized in Table 4.3. Although untreated titanium dioxide is hydrophilic, Examples
4.7 is water repellent, probably because it is coated with a silicone polymer film. In addition, due to the surface activity of microparticle titanium dioxide, linalool, which is one of the fragrance components, is decomposed, and vitamin E and γ-oryzanol turn brown on the surface, but Example 4.7
In this case, there is no interaction because of the silicone polymer film on the titanium dioxide. This clearly shows that when the stable metal oxide of the present invention is mixed with various other compounds, there is no interaction with other compounds and the stability over time is also good.

[Table] 10 mg of methyl ammonium salt and 0.5 g of docosene were added and mixed and ground for 2 hours. Although it was difficult to measure the infrared absorption spectrum of black iron oxide, and it was not possible to determine the crosslinking rate and addition rate, the linalool decomposition activity had disappeared, suggesting that the surface was covered with a good film. It will be done. Example 4.8 A rotary double-cone reactor (made of stainless steel, with heat-insulating jacket) of 100 mL capacity was equipped with
10kg of spherical composite powder made of 5μ nylon powder (65 parts) coated with 0.2μ titanium dioxide (35 parts)
I put it in. The raw solution supply tank (made of stainless steel, with heat insulation jacket) is directly connected to this reaction tank with a stainless steel pipe. 1 kg of silicone was added, and nitrogen was bubbled from the bottom of the stock solution supply tank to supply it to the reaction tank.
The temperature of the system was maintained at 70°C by supplying a heating medium heated to 70°C from a heating medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump. The reaction tank is rotated by a timer after it has been left still for 10 minutes.
This rotation was repeated for 7 hours. Thereafter, the silicone compound was removed, and rotation was continued for 2 hours while only nitrogen was introduced into the reaction tank, and after the temperature was returned to room temperature, 10.4 kg of treated product was obtained. This treated product not only has the slipperiness characteristic of the original composite powder, but also exhibits remarkable water repellency, and there is no browning caused by vitamin E or γ-oryzanol, which was observed in the untreated composite powder. Nakatsuta. Example 4.9 10 kg of spherical silica (particle size 5 μ, specific surface area 350 m ² /g) was placed in the same reaction tank as in Example 4.7, and the structural formula was added to the stock solution supply tank. Example: Add 3 kg of silicone compound and heat at 100℃.
The same operation as in 4.7 was performed to obtain 12.4 kg of silicone polymer-coated spherical silica. Example 5.1 1000 g of red No. 202 (crystal type β type) and tetrahydrotetramethylcyclotetrasiloxane
100g were placed in separate containers and left in a desiccator at 80°C. After 16 hours, take out red No. 202,
When it was left in a dryer at 90°C for 24 hours, 1043g of treated red No. 202 was obtained. Example 5.2 Red No. 202 (crystal type β type) 300g and formula and 100g of silicone compound in separate containers,
It was left in a desiccator at 80°C. After 16 hours, Red No. 202 was taken out and left in a dryer at 90°C for 24 hours, yielding 311 g of treated Red No. 202. Examples 5.1 and 5.2 and untreated Red No. 202 were subjected to a chloroform elution test, an X-ray crystal type evaluation, and a bleedability evaluation. In the chloroform elution test for silicone polymer films, 100 g of the sample was dispersed in 500 ml of chloroform, filtered, the filtrate was concentrated in an evaporator and weighed, and then dissolved in chloroform and the molecular weight was measured by gel permeation chromatography. . The equipment was manufactured by Japan Analytical Industry Co.
Ltd LC-08 with B4H and B3H as columns.
Measurement was carried out using three ×2 pieces. The solvent was chloroform (1.07ml/min).
The detector used an infrared absorption spectrum. The molecular weight was measured using a standard polystyrene calibration curve. As a result, in Example 5.1 the silicone polymer
82 mg was eluted, and its average molecular weight was approximately 8000. The amount of this eluted silicone polymer was about 1.9% of the coated silicone polymer, and it is believed that the other silicone polymer was coated with Red No. 202. In addition, in Example 5.2, 230 mg of silicone polymer
was eluted, and its average molecular weight was approximately 4,500. The amount of this eluted silicone polymer was about 6.3% of the coated silicone polymer, and it is believed that the other silicone polymer was coated with Red No. 202. [Measurement of α, β transition] Red No. 202 has two crystal forms: α type and β type. In the presence of water, the β form changes to the α form and changes color. The experiment was conducted under 100% humidification. The amounts of α and β forms can be determined from the following X-ray peaks: hα: Height at 2θ = 20.75° hβ: Height at 2θ = 21.60° α type transition rate (%) = hα/hα + hβ × 100 Example 5.1 and Example 5.2 and untreated red No. 202 α transition rate Shown in Table 5.1.

[Table] Compared to the untreated samples, the samples of Examples 5.1 and 5.2 showed a slower transition from β-type to α-type. This is thought to be because Red No. 202 is completely covered with a silicone polymer film, making it difficult for water to pass through. [Bleeding] Since Red No. 202 is a calcium lake pigment, it dissolves slightly when dispersed in water. We investigated how much the bleeding property was improved by this treatment. 0.5 g of Red No. 202 was dispersed in 100 ml of ion-exchanged water, filtered after one day, and the amount of dissolved Red No. 202 was determined from the absorbance at a maximum absorption wavelength of 490 nm (measured with a 1 cm cell).

[Table] As shown in Table 5.2, untreated powder bleeds into water, but treated powder suppresses bleed. When such treated powder is blended into a composition product, discoloration of the composition product can be suppressed. Particularly in the field of cosmetics, there are many powder-molded products, and it is known that even such products can bleed under humid conditions, but the pigment of the present invention can suppress such discoloration. Example 5.3 Put 1000g of blue No. 404 into a beaker and add 100g of tetrahydrohexamethylcyclopentasiloxane.
and another beaker containing 50 g of pentahydropentamethylcyclopentasiloxane were placed in a vacuum low-temperature dryer DPF31 made by Yamato Scientific at 20 mmHg.
The pressure was reduced to 50°C and the mixture was left at 50°C. Blue 404 after 48 hours
When the No. 404 treated blue color was taken out and dried for 4 hours in a dryer at 90°C, 1048 g of treated blue No. 404 was obtained. When a chloroform elution test was performed, 57 mg of silicone polymer was eluted, and its average molecular weight was 23,000. This eluted silicone polymer accounts for about 1.2% of the coated silicone polymer, and it is believed that the other silicone polymer coats Blue No. 404. Furthermore, the dispersibility of the obtained pigment was investigated. [Dispersibility test] Pigment: 10 parts Alkyd (Hitachi Chemical 133-60NV60) 54 parts Melamine (Hitachi Chemical Melan-20NV50) 26 parts The particle dispersion was observed using a gauge. The results are shown in Table 5.3 below, and it can be seen that by using the pigment of Example 5.3, paint can be formed in approximately half the dispersion time of untreated powder.

[Table] Example 6.1 Mica titanium pearl agent (average particle size 25μ) 20g
and 2 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers and left in a desiccator at 80°C. After 12 hours, the mica titanium pearl agent was taken out and left in a dryer at 100° C. for 24 hours, yielding 20.8 g of coated mica titanium pearl agent. Example 6.2 20 kg of a mica iron oxide pearling agent was placed in a rotating double cone type reaction tank (made of stainless steel, equipped with a heat insulating jacket) with a capacity of 100 ml. A stock solution supply tank (made of stainless steel, with heat insulating jacket) is directly connected to this reaction tank with a stainless steel pipe.
400 g of tetrahydrotetramethylcyclotetrasiloxane was added to the system, and the pressure of the system was reduced to 100 mmHg using a vacuum pump. The temperature of the system was maintained at 90°C by supplying a heating medium heated to 90°C from a heating medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump. The reaction tank was rotated 3 times by a timer after being allowed to stand still for 10 minutes, and this rotation was repeated for 10 hours. While the rotation was repeated, mica iron oxide was mixed and stirred in the reaction tank, and then N ₂ gas was introduced into the system to return it to normal pressure, yielding 20.3 kg of a coated mica iron oxide pearl agent. Example 6.3 Gas sterilizer Capocalizer CL-30B (Fuji
100 g of bismuth oxychloride and 20 g of pentahydropentamethylcyclopentacycloxane were placed in separate containers in a container (Electric Co Ltd), and the internal pressure was reduced to 300 mmHg using an aspirator, and the temperature was maintained at 90°C. After leaving it for one night, air was added to restore the pressure to normal pressure, and the mixture was evacuated several times to obtain 103.6 g of coated bismuth oxychloride. Example 6.4 In a vacuum low-temperature dryer DPF31 (manufactured by Yamato Scientific Co., Ltd.), 200 g of a dark blue coated mica titanium pearl agent was added.
and 30 g of trihydropentamethylcyclotetrasiloxane were placed in separate containers and left to stand at 50° C. for 48 hours. Thereafter, the navy blue-coated mica titanium pearl agent was taken out, heated at 80° C. for 6 hours, and then weighed to obtain 218.3 g of a navy blue coated mica titanium pearl agent coated with a silicone compound. Example 6.5 50g of green pearl pigment (mica coated with titanium oxynitride) obtained by reducing powder obtained by reducing flamenco blue, a commercially available pearl pigment manufactured by Marl Inc. with NH ₃ gas, and 10% titanium dioxide, and tetrahydrotetramethylcyclo 10 g of tetrasiloxane were placed in a separate container and left in a desiccator at 30°C.
After 4 days, it was taken out and left in a dryer at 100° C. for 3 hours to obtain 52.3 g of titanium oxynitride-coated mica coated with a silicone compound. For the coated pearlescent materials and untreated pearlescent materials obtained in Examples 6.1 to 6.5, (1) the x,y ratio of [R ²¹ SiO _3/2 ] _x [R ²¹ R ²² SiO] _y , (2 ) Measurements of chloroform elution rate, (3) water repellency and (4) linalool decomposition were carried out by the methods described in connection with Example 3.3 above. Furthermore, (5) the gloss was measured. (5) Glossiness measurement The glossiness of the pearlescent material was measured using a Hitachi glossmeter at an incident angle of 15° and an acceptance angle of 30°. The measured value was expressed as the average of two measurements. (Example 6.1 and evaluation results of untreated pearlescent material) (1) Results of infrared absorption spectrum measurement, Example 6.1
The x,y ratio in the coated pearlescent material is
It was found that 100x/(x+y)=68.
Therefore, 68% of the structure of the silicone polymer [CH ₃ SiO _3/2 ] _x [(CH ₃ )HSiO] _y covering the surface is derived from x, and a network structure has developed. I understand that. (2) Gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment revealed that silicone polymers do not elute in chloroform. This indicates that the silicone polymer on the surface of the coated titanium mica has become polymerized to the extent that it cannot be dissolved in chloroform. (3) The water repellency measurement results show that untreated titanium mica disperses in water, whereas the titanium coated mica of Example 6.1 has extremely strong water repellency and floats to the surface of water. This phenomenon is in good agreement with the fact that the silicone polymer film is firmly adhered to the titanium mica. (4) As a result of the decomposition measurement of linalool using a microreactor, the decomposition of linalool was suppressed in the coated pearlescent material of Example 6.1 compared to the untreated pearlescent material, and the active sites on the surface were blocked. I understood. From this, it can be seen that in Example 6.1, there was no fragrance decomposition compared to the untreated sample, resulting in mica titanium with high odor stability. (5) The results of gloss measurement are shown in Table 6.1. It can be seen that the coated mica titanium of Example 6.1 has a larger value of L and is glossier than the untreated mica titanium.

[Table] (Results and evaluation regarding Examples 6.2 to 6.5) As shown in Table 6.2, the treated pearlescent materials obtained in Examples 6.2 to 6.5 were stable like those in Example 6.1.

【table】

[Table] Example 6.6 Mica titanium pearl agent (average particle size 25μ) 20g
and expression and 2g of silicone compound in separate containers.
It was left in a desiccator at 80°C. After 12 hours, the mica titanium pearl agent was taken out and left in a dryer at 100° C. for 24 hours, yielding 21.2 g of a coated mica titanium pearl agent. Example 6.7 20 kg of mica iron oxide pearling agent was placed in a rotary double cone type reaction tank (made of stainless steel, with heat insulating jacket) having a capacity of 100 mm, and directly connected to this reaction tank with a stainless steel pipe, and a stock solution supply tank (stainless steel (with thermal jacket) 400 g of silicone compound was added, and the pressure of the system was reduced to 20 mmHg using a vacuum pump. The temperature of the system was maintained at 90°C by supplying a heating medium heated to 90°C from the heating medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump. The reaction tank was rotated 3 times by a timer after being allowed to stand still for 10 minutes, and this rotation was repeated for 10 hours. While the rotation was repeated, mica iron oxide was mixed and stirred in the reaction tank, and then N ₂ gas was introduced into the system to return it to normal pressure, yielding 20.36 kg of a coated mica iron oxide pearl agent. For the coated pearlescent materials and untreated pearlescent materials obtained in Examples 6.6 and 6.7, (1) [R ²¹ SiO _3/2 ] _x [R ²¹ R ²² SiO] _y [(R ²¹ ) ₃ SiO _{1 /2} ] _z crosslinking rate, alkene addition rate, (2) chloroform elution rate, (3) water repellency, and (4) linalool decomposition were measured by the method described in connection with Example 3.3 above. Furthermore, (5) measurement of gloss was carried out in Examples 6.1 to 6.5.
It was carried out according to the method described in connection with . (Examples 6.6 and 6.7 and evaluation results of untreated pearlescent material) (1) Results of infrared absorption spectrum measurement, Example 6.6
The x,y ratio in the coated pearlescent material is
It was found that 100x/(x+y)=74.
Terminal unit [(CH ₃ ) ₃ SiO _2/1 ] _z is 2/5 of the whole
40% is in z units. Since the z unit does not participate in the reaction, it still accounts for 40% after treatment. y unit [[CH ₃ ) HSiO] _y accounts for the remaining 60%,
After the reaction, 74% becomes [(CH ₃ )SiO _3/2 ] _x units. In other words, the structure of the silicone covering the surface is: [CH ₃ SiO _2/3 ] _x [(CH ₃ )HSiO] _y [(CH ₃ ) ₃ SiO _2/1 ]
_z , and x:y:z=44.4:15.6:40.0. Further, the crosslinking rate of the silicone polymer of Example 6.7 was 62%. (2) As a result of gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment, it was found that the silicone polymers of Examples 6.6 and 6.7 were not eluted in chloroform. This indicates that the silicone polymer on the surface of the coated titanium mica has become polymerized to the extent that it cannot be dissolved in chloroform. (3) The water repellency measurement results show that untreated titanium mica disperses in water, whereas the coated titanium mica of Examples 6.6 and 6.7 has extremely strong water repellency and floats to the surface of water. This phenomenon is in good agreement with the fact that the silicone polymer film is firmly adhered to the titanium mica. (4) As a result of the decomposition measurement of linalool using a microreactor, the decomposition of linalool was suppressed in the coated pearlescent materials of Examples 6.6 and 6.7 compared to the untreated pearlescent materials, and the active sites on the surface were blocked. I found out that there was. From this, it can be seen that in Examples 6.6 and 6.7, there was no fragrance decomposition compared to the untreated samples, resulting in mica titanium with high odor stability. (5) The results of gloss measurement are shown in Table 5.3. It can be seen that the coated mica titanium of Example 6.6 has a larger L value and is more glossy than the untreated mica titanium.

[Table] Example 7.1 100g of kaolinite (average particle size 5μ) and 20g of tetrahydrotetramethylcyclotetrasiloxane
and were placed in separate containers and left in a desiccator at 80°C. After 12 hours, remove the kaolinite and
When the mixture was left in a dryer at 100°C for 24 hours, 102.6 g of treated kaolinite was obtained. Example 7.2 20 kg of talc is placed in a 100-volume rotary double cone reaction tank (made of stainless steel, with heat insulating jacket), and a stock solution supply tank (made of stainless steel, with heat insulating jacket) is directly connected to this reaction tank with a stainless steel pipe. 400 g of tetrahydrotetramethylcyclotetrasiloxane was added to the system, and the pressure of the system was reduced to 20 mmHg using a vacuum pump. The temperature of the system was maintained at 90°C by supplying a heating medium heated to 90°C from a heating medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump. The reaction tank was rotated three times after being left still for 10 minutes using a timer, and the operation of mixing and stirring the talc in the reaction tank was repeated for 10 hours.
After that, N ₂ gas was introduced into the system and the pressure was returned to normal, and 20.3 kg of treated powder was taken out. Example 7.3 100 g of Y-type zeolite and 20 g of pentahydropentamethylcyclopentasiloxane were placed in separate containers, and both were placed in a gas sterilizer Capocalizer CL-
30B (Fuji-Electric Co Ltd), the internal pressure was reduced to 300 mmHg using an aspirator, and the temperature was maintained at 90°C. After leaving it overnight, let air in to return it to normal pressure, then evacuate it several times to remove the treated powder.
Obtained 101.2g. Example 7.4 5 kg of montmorillonite was placed in a rotating double cone type reaction tank (made of stainless steel, with a heat insulating jacket) with a capacity of 100, and placed in a stock solution supply tank (made of stainless steel, with a heat insulating jacket) directly connected to the reaction tank with a stainless steel pipe. Add 500g of trihydropentamethylcyclotetrasiloxane,
Nitrogen was supplied to the reaction tank by bubbling from the bottom of the stock solution supply tank. The temperature of the system is set at 70°C by supplying a heat medium heated to 70°C from the heat medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump.
It was kept at ℃. The reaction tank was rotated by a timer for 10 minutes and then rotated 3 times, and this rotation was repeated for 7 hours. Thereafter, the silicone compound was removed, the temperature of the entire system was raised to 100° C. while continuing a nitrogen stream, and rotation was continued for an additional 2 hours in order to remove the silicone monomer in the reactor from the system. Thereafter, the temperature was returned to room temperature to obtain treated montmorillonite. Example 7.5 50 g of organically modified montmorillonite (Bentone 38, manufactured by National Red Co., Ltd.) and 50 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers, and both were charged into a vacuum low temperature dryer DPF31 (manufactured by Yamato Scientific Co., Ltd.). It was kept at 50°C for 48 hours. After that, it was dried at 80°C and weighed, and 85 g of the treated product was obtained. This treated product had expanded compared to before treatment. (1) Measurement of crosslinking rate of treated powders of Examples 7.1 to 7.5;
(2) Chloroform elution measurement of silicone polymers,
(3) Measurement of water repellency and (4) measurement of linalool stability were carried out by the method described in connection with Example 3.3 above. (Evaluation Results of Example 7.1) (1) From the results of the infrared absorption spectrum, it was found that the ratio 100x/(x+y) in the gas phase treatment with the cyclic silicone compound of Example 7.1 was 35. Therefore, 35% of the structure of the silicone polymer [CH ₃ SiO _3/2 ] _x [(CH ₃ )HSiO] _y covering the surface is derived from x, and a network structure has developed. I understand that. (2) As a result of gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment, it was found that the silicone polymer did not elute in chloroform. This indicates that the silicone polymer on the surface of the treated kaolinite has become polymerized to the extent that it cannot be eluted in chloroform. In a similar gel permeation experiment, silicone polymers with a molecular weight of less than 200,000 were eluted in chloroform, suggesting that the silicone polymer polymerized on the surface of the treated kaolinite had a molecular weight of 200,000 or more. This result agrees well with the above result of 100x/(x+y)=35, indicating that the network-structured silicone polymer tightly coats the treated kaolinite surface. (3) Evaluation of water repellency Untreated kaolinite was hydrophilic and dispersed well in water, but Example 7.1 showed strong water repellency. This shows that in Example 7.1, the kaolinite surface is coated with silicone polymer. (4) Evaluation of linalool stability Kaolinite is a strong solid acid, and tertiary alcohols such as linalool are easily dehydrated and isomerized to produce ocimene, allocimene, terpinolene, etc. In contrast, Example 7.1
The dehydration rate of linalool was significantly reduced, and the fragrance stability of kaolinite was improved by the present invention. (Evaluation results of Examples 7.2 to 7.5) As shown in Table 7.1, the silicate minerals obtained in Examples 7.2 to 7.5 were stable, similar to those obtained in Example 7.1. In addition, in Example 7.5, an interlayer of 26.8 Å was observed in the untreated X-ray diffraction pattern, but it disappeared in Example 7.5, indicating that peeling had occurred. It was found that a coating of

【table】

[Table] Example 7.6 100g of kaolinite (average particle size 5μ) and 1,1,
20 g of 1,2,3,4,4,4-octamethyltetrasiloxane were placed in a separate container and left in a desiccator at 80°C. After 12 hours, the kaolinite was taken out and left in a dryer at 100°C for 24 hours, yielding 103.4 g of treated kaolinite. Example 7.7 Put 20 kg of talc into a 100-volume rotary double-cone reaction tank (made of stainless steel, with a heat-insulating jacket), and place it in a stock solution supply tank (made of stainless steel, with a heat-insulating jacket) that is directly connected to the reaction tank with a stainless steel pipe. 1, 1, 1, 2, 3,
4,4,4-octamethyltetrasiloxane
400g was added, and the pressure of the system was reduced to 20mmHg using a vacuum pump. The temperature of the system was maintained at 90°C by supplying a heating medium heated to 90°C from a heating medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump. The reaction tank was rotated 3 times after being left still for 10 minutes using a timer, and the talc was mixed and stirred in the reaction tank for 10 minutes.
After repeating this for several hours, N ₂ gas was introduced into the system and the pressure was returned to normal, and 20.3 kg of treated powder was taken out. Example 7.8 100g of Y-type zeolite and 1,1,1,2,3,
4,5,5,5-nanomethylpentasiloxane
Put 20g into a separate container, charge it into a gas sterilizer capocalizer CL-30B (Fuji-Electric Co Ltd), and increase the internal pressure to 300mmHg using an aspirator.
The pressure was reduced to 90°C and the temperature was maintained at 90°C. After leaving it for one night, after putting air in it and returning it to normal pressure,
After evacuation several times, 102.1 g of treated powder was obtained. (1) Measurement of crosslinking rate of treated powders of Examples 7.6 to 7.8;
(2) Chloroform elution measurement of silicone polymers,
(3) Measurement of water repellency and (4) measurement of linalool stability were carried out by the method described in connection with Example 3.3 above. (Evaluation results of Examples 7.6 to 7.8) (1) From the results of the infrared absorption spectrum, it was found that the ratio 100x/(x+y) in the gas phase treatment with the cyclic silicone compound of Example 7.6 was 39. Therefore, the silicone polymer covering the surface [CH ₃ SiO _3/2 ] _x [(CH ₃ )HSiO] _y [(CH ₃ ) ₃ SiO _1/2
] It can be seen that 19.5% of the structure of _z is a structure derived from x, indicating that a network structure is developed. Further, the crosslinking rates of the silicone polymers of Examples 7.7 and 7.8 were 43% and 55%, respectively. (2) As a result of gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment, it was found that the silicone polymer of Example 7.6 was not eluted in chloroform. This indicates that the silicone polymer on the surface of the treated kaolinite has become polymerized to the extent that it cannot be eluted in chloroform.
In a similar gel permeation experiment, a molecular weight of 20
Since silicone polymers with a molecular weight of less than 10,000 yen are eluted in chloroform, the silicone polymer polymerized on the surface of the treated kaolinite is thought to have a molecular weight of 200,000 or more. This result is 100x/(x+
This result agrees well with the above result for y) = 39, indicating that the network-structured silicone polymer tightly coats the treated kaolinite surface. (3) Evaluation of water repellency Untreated kaolinite was hydrophilic and dispersed well in water, but Examples 7.6 to 7.8 showed strong water repellency. This shows that in Examples 7.6 to 7.8, the kaolinite surface was coated with a silicone polymer film. (4) Evaluation of linalool stability Kaolinite is a strong solid acid, and tertiary alcohols such as linalool are easily dehydrated and isomerized to produce ocimene, allocimene, terpinolene, etc. In contrast, Example 7.6
At ~7.8, the dehydration rate of linalool decreased significantly;
The fragrance stability of kaolinite has been improved by the present invention. Example 7.9 Dissolve 20 g of 2,2',4,4'-tetrahydroxybenzophenone in 500 ml of ethyl alcohol, add 200 g of Laponite XLG and 2.5 g of water,
After stirring at 60°C for 20 minutes with a homomixer to form a uniform gel, it was transferred to a vat and dried at 80°C. Put 5 g of dry powder and 5 g of tetramethylcyclotetrasiloxane into the same desiccator,
After standing at 80°C for a day and night, 5.8g of treated product was obtained. This treated powder showed remarkable water repellency. Example 8.1 Alumina (7 mmφ,
Specific surface area 2 m ² /g) 100 g and 10 g of tetramethyltetrahydrodienecyclotetrasiloxane in a 20 ml sample tube were placed in a desiccator and left at 50°C. After 24 hours, it was taken out of the desiccator and left at 50°C for 3 hours to obtain 100.075 g of treated product. Take about 15g of each of these treated powders and place them in citrus-based mixed fragrance, rose-based mixed fragrance, and diasmine-based mixed fragrance (all commercially available products) overnight at room temperature (20 g).
℃) to absorb the fragrance. Example 8.2 Alumina (7 mmφ,
Specific surface area 2 m ² /g) 100 g and 10 g of tetramethyltetrahydrodienecyclotetrasiloxane in a 20 ml sample tube were placed in a desiccator and left at 50°C. After 6 hours, it was taken out from the desiccator and left at 50°C for 3 hours to obtain 100.033 g of treated product. Approximately 15 g of this treated product was taken and placed in a citrus-based mixed fragrance, a rose-based mixed fragrance, and a diasmine-based mixed fragrance (all commercially available products) overnight at room temperature (20 g).
℃) to absorb the fragrance. Comparative Example 8.1 Take about 15 g of the alumina used in Example 8.1,
Example without treatment with silicone compound
Each sample was immersed overnight at room temperature (20°C) in the citrus-based blended fragrance, rose-based blended fragrance, and diasmine-based blended fragrance (all commercially available) used in 8.1 to adsorb the fragrance. Example 8.3 Alumina (7 mmφ,
Specific surface area 2 m ² /g) 100 g and 10 g of pentamethyltrihydrodienecyclotetrasiloxane in a 20 ml sample tube were placed in a desiccator.
It was left at 80°C. After 24 hours, it was taken out of the desiccator and left at 100°C for 3 hours to obtain 100.065 g of treated product. Approximately 15 g of this treated product was taken and placed in a citrus-based mixed fragrance, a rose-based mixed fragrance, and a diasmine-based mixed fragrance (all commercially available products) overnight at room temperature (20 g).
℃) to absorb the fragrance. Comparative Example 8.2 Take about 15 g of the alumina used in Example 8.3,
Example without treatment with silicone compound
Each sample was immersed overnight at room temperature (20°C) in the citrus-based mixed fragrance, rose-based mixed fragrance, and diasmine-based mixed fragrance (all commercially available) used in 8.3 to adsorb the fragrance. Example 8.4 Calcium sulfate fired board (105mm x 65mm x 20
mm) 175.3 g and 10 g of tetramethyltetrahydrodienecyclotetrasiloxane in a 20 ml sample tube were placed in a desiccator and left at 50°C. After 24 hours, remove from the desiccator and store at 50℃.
After leaving for 3 hours, 176.2 g of treated product was obtained. This treated product was immersed in a rose-based blended fragrance (commercially available) overnight at room temperature (20°C) to adsorb the fragrance. Comparative Example 8.3 The board used in Example 8.4 was left overnight at room temperature (20°C) in the rose-based blended fragrance (commercially available) used in Example 8.4 without being treated with a silicone compound.
Soaked in water to absorb fragrance. Example 8.5 Silica (specific surface area 300) in a 200 ml beaker
m ² /g) 50 g and 20 g of pentamethyltrihydrodienecyclotetrasiloxane in 50 ml sample tubes were placed in a desiccator and left at 80°C. After 24 hours, remove from the desiccator and
After being left at ℃ for 3 hours, 58.65 g of treated product was obtained. Approximately 5 g of this treated product was taken and placed in a citrus-based mixed fragrance, a rose-based mixed fragrance, and a diasmine-based mixed fragrance (all commercially available products) overnight at room temperature (20 ml).
℃) to absorb the fragrance. Comparative Example 8.4 Approximately 5 g of the silica used in Example 8.5 was taken and the same amount as in Example 8.5 was taken without treatment with a silicone compound.
Each sample was left overnight at room temperature (20°C) in the citrus-based mixed fragrance, rose-based mixed fragrance, and diasmine-based mixed fragrance (all commercially available products) used in 8.5 to adsorb the fragrance. Examples 8.1 to 8.5 and Comparative Examples 8.1 to Comparative Examples
Each of the flavoring carriers in 8.4 was placed in a sealed glass container and stored at 40°C for 30 days, and then the flavor stability was evaluated. The evaluation was performed sensually by a panel of five experts on fragrances. The judgment is as follows. ◎: No change in aroma tone is observed. ○: Almost no change in aroma tone is observed. Δ: Change in fragrance is observed. ×: The fragrance tone has completely changed. The results are shown in Table 8.1.

[Table] In the carriers of Examples 8.1 to 8.5, which were treated according to the present invention as described above, no or almost no change was observed in any fragrance tone. On the other hand, in the carriers of Comparative Examples 8.1 to 8.4, which were not treated with a silicone compound, considerable changes were observed in all fragrance tones. In other words, the carrier treated with the silicone compound according to the present invention has significantly improved fragrance stability. Example 9.1 10 g of activated carbon and 10 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers and heated to 80 g.
It was left in a desiccator at ℃. After 72 hours, the activated carbon was taken out and its weight was measured.
15.50 g was obtained, and when it was left in a dryer at 50° C. for 24 hours, 13.60 g of treated activated carbon was obtained. Example 9.2 100 g of carbon black and 50 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers and left in a sealed container at room temperature. After 96 hours, the carbon black was taken out and its weight was measured, and 126.50g of treated fine particle carbon black was obtained.The carbon black was left in a dryer at 50℃ for 24 hours.
120.30 g of treated carbon black was obtained. Regarding the treated powders of Examples 9.1 and 9.2, (1) measurement of crosslinking rate, (2) measurement of chloroform elution of silicone polymer, (3) determination of water repellency, and (4) measurement of stability of linalool were performed as described above. Performed according to the method described in connection with Example 3.3. (Results and evaluation) (1) Crosslinking rate in gas phase treatment with cyclic silicone compound based on infrared absorption spectrum results
It turns out that 100x/(x+y) is 59.
Therefore, 59% of the structure of the silicone polymer [CH ₃ SiO _3/2 ] _x [(CH ₃ )HSiO] _y covering the surface is derived from x, and a network structure has developed. I understand that. The crosslinking rate of the silicone polymer of Example 9.2 is
It was 70%. (2) As a result of gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment, it was found that the silicone polymer of Example 9.1 was not dissolved in chloroform. This indicates that the silicone polymer on the treated carbon surface has become a polymer and is no longer eluted in chloroform. In a similar gel permeation experiment, silicone polymers with a molecular weight of less than 200,000 were eluted in chloroform, so it is thought that the silicone polymer polymerized on the treated carbon surface has a molecular weight of 200,000 or more. This result agrees well with the above result of 100x/(x+y)=59, indicating that the network-structured silicone polymer tightly coats the treated carbon surface. The water repellency, linalool stability (by microreactor) is summarized in Table 9.1 for the products of Examples 9.1 and 9.2 and for untreated carbon. In terms of water repellency, the products of Example 9.1 and Example 9.2 were good. The results of stability (decomposition activity) of linalool show that the products of Examples 9.1 and 9.2 sequester the activity of each carbon well and hardly decompose linalool.

[Table] Example 10.1 The following components were blended in the following proportions and sufficiently kneaded in a ball mill to prepare a paint. Parts by weight Modified ultramarine of Example 3.1 100 Vinyl chloride-vinyl acetate copolymer 10 Polyurethane resin 20 Toluene 100 Methyl ethyl ketone 100 Comparative example 10.1 A paint was similarly prepared by replacing the modified ultramarine of Example 3.1 with untreated ultramarine. . When each of the paints of Example 10.1 and Comparative Example 10.1 was applied to a polyester film in a conventional manner,
Compared to Comparative Example 10.1, Example 10.1 showed better dispersion, deeper color, and better gloss. Example 11 A cosmetic containing the modified powder according to the present invention will be specifically described. The blending amount is in weight%. First, I will explain the evaluation method. (Evaluation method) A sensory test was conducted by a panel of 20 experts regarding the spread and makeup durability. The rating was expressed on a 5-point scale from 1 to 5 points. 1...poor 2...slightly bad 3...fair 4...slightly good 5...good Results are expressed as average values as follows. ◎...4.5~5.0 〇...3.5~4.4 △...2.5~3.4 ×...1.0~2.4 ××...1.0~1.4 For water repellency, 0.5 cc of water was placed on top of the press-molded powder cosmetic. The time it took for the water to soak in was measured. The results were expressed as follows. ◎...Does not penetrate〇...2 hours to 6 hours △...30 minutes to 2 hours ×...10 minutes to 30 minutes A sensory comparison was made between the stored cosmetic sample and the control (immediately after manufacture). The results were expressed as follows. ◎...It's almost the same as the control. 〇……It has a strange odor compared to the control. ×...The odor is quite strange compared to the control. Example 11.1: Pressed Powder A pressed powder was produced from the following ingredients using the modified powder of the present invention. Parts by weight (1) Modified muscovite of Example 13.8 30 (2) Modified talc of Example 7.2 65.8 (3) Iron oxide pigment 0.1 (4) Squalane 2.0 (5) 2-ethylhexyl palmitate 2.0 (6) Perfume 0.1 Mix ingredients (1), (2), and (3) in a Henschel mixer, spray a heated mixture of ingredients (4), (5), and (6) on this, and after mixing, crush and mix A pressed powder was obtained by molding into a dish. Comparative Example 11.1 A pressed powder of Comparative Example 11.1 was obtained in the same manner as in Example 11.1 except that untreated mica and talc were substituted for modified mica and modified talc in the formulation of Example 11.1. The evaluation results are shown in Table 11.1. Example 11.1 of the invention
It turns out that it is excellent.

[Table] Example 11.2: Dual-use foundation 10 parts titanium oxide, 10 parts muscovite, 35 sericite
A mixed powder of 20 parts of talc, 20 parts of talc, and 3 parts of iron oxide pigment was treated in the same manner as in Example 2.3 to obtain a modified mixed powder. A dual-use foundation was prepared using this. Parts by weight (1) Modified powder mixture 78 (2) 2-ethylhexyl palmitate 5.5 (3) Liquid paraffin 5.0 (4) Sorbitan sesquiolate 1.0 (5) Preservative 0.3 (6) Fragrance 0.2 Ingredients (2), ( 3), (4), (5), and (6) are heated and mixed, then added to component (1), mixed, crushed, and filled into a medium tray for dual use, which can be used with or without water. I got the foundation. Comparative Example 11.2 A dual-use foundation of Comparative Example 11.2 was obtained in the same manner as in Example 11.2, except that the mixed modified powder of Example 11.2 was replaced with a metal soap-coated powder of the same powder composition. The evaluation results of Example 11.2 and Comparative Example 11.2 are shown.
Shown in 11.2. It can be seen that Example 11.2 of the present invention is superior.

[Table] Example 11.3: Powder eye shadow Eye shadow was prepared using the following modified powder according to the present invention. Parts by weight (1) Modified talc of Example 7.2 20 (2) Modified pearl pigment of Example 6.7 18.5 (3) Modified ultramarine of Example 3.1 50 (4) Modified iron oxide of Example 4.3 4.0 (5 ) Squalane 4.0 (6) Cetyl 2-ethylhexanoate 2.0 (7) Sorbitan sesquiolate 1.0 (8) Preservative 0.3 (9) Fragrance 0.2 Ingredients (1), (2), (3), and (4) Mix with a shell mixer, spray a heated and melted mixture of components (5), (6), (7), (8), and (9) on this, crush it, and mold it into a medium plate to obtain eye shadow. Ta. Comparative Example 11.3 and Comparative Example 11.4 The procedure of Comparative Example 11.3 was repeated in the same manner as in Example 11.3, except that in each of the coated powders of Example 11.3, ultramarine was replaced with silica-coated ultramarine, and the other powders were replaced with untreated powders. I got the powder eye shadow. Comparative Example 11.4 was carried out in the same manner as in Example 11.3, except that all the coated powders in Example 11.3 were replaced with untreated powders.
I got an eye shadow. Table 11.3 shows the evaluation results of Example 11.3, Comparative Example 11.3, and Comparative Example 11.4. It can be seen that Example 11.3 of the present invention is superior. Note that when a formulation containing ultramarine blue is mixed with a Henschel mixer, there is usually a hydrogen sulfide odor, but in Example 11.3 of the present invention, there was no hydrogen sulfide odor. It was also excellent in gloss.

[Table] Example 11.4: Nail enamel The following nail enamel was prepared using the modified powder according to the present invention. (1) Nitrocellulose 12% (2) Modified alkyd resin 12 (3) Acetyl tolbutyl citrate 5 (4) Butyl acetate 38.4 (5) Ethyl acetate 6 (6) n-Butyl alcohol 2 (7) Toluene 21 (8) ) Modified yellow iron oxide of Example 2.1 0.5 (9) Modified titanium dioxide of Example 4.2 0.1 (10) Pearl pigment 2 (11) Organically modified montmorillonite 1 Components (1) to (3) and component (4) Components (5) to (7) are dissolved, a gel-like mixture of component (11) and the remainder of component (4) is added and mixed, and further components (8) to (10) are dissolved. ) were added and mixed and filled into a container to obtain nail enamel. Comparative Example 11.5 Nail enamel of Comparative Example 11.5 was prepared in the same manner as in Example 11.4 except that the modified yellow iron oxide and modified titanium dioxide in the formulation of Example 11.4 were replaced with untreated yellow iron oxide and titanium dioxide, respectively. I got it. The one of Example 11.4 is compared with that of Comparative Example 11.5,
The dispersion stability of the pigment was good, and the powder did not adhere to the bottle, indicating good stability. Example 11.5: UV protection stick A UV protection stick was made using the coated titanium dioxide of Example 1.5 above. (1) Modified titanium dioxide of Example 1.5 20% (2) Talc 10 (3) Mica 11 (4) Iron oxide 0.5 (5) Carnauba wax 1 (6) Solid paraffin 3 (7) Liquid paraffin 45 (8) Isopropyl Myristate 8 (9) Sorbitan Sesquiolate 1.5 (10) Flavor Appropriate amount Place ingredients (7) and (8) in a pot, heat to 80-90℃, add ingredients (5) and (6), and dissolve. Ingredients (1) to (4)
Add to disperse uniformly, and after degassing, add component (10) and stir gently. A UV protection stick was obtained by pouring this into a container at 80°C and cooling it to room temperature. Comparative Example 11.6 Example 11.5 except that the coated titanium dioxide was replaced with untreated titanium dioxide.
An ultraviolet protection stick of Comparative Example 11.6 was obtained in the same manner as in 11.5. The one of Example 11.5 is compared with that of Comparative Example 11.6,
Titanium dioxide has good dispersibility and a beautiful finish.
It was a highly effective sunscreen. Example 11.6: Lipstick A lipstick was prepared from the following composition. (Parts by weight) (1) Hydrocarbon wax 3 (2) Carnauba wax 1 (3) Glyceryl isostearate 40 (4) Liquid paraffin 45.8 (5) Modified titanium dioxide of Example 4.2 4 (6) h-BN (3 μm ) 3 (7) Organic pigment 3 (8) Fragrance 0.2 Components (1) to (4) were dissolved at 85°C, and components (5) to (7) were added under stirring. Finally, component (8) was added under stirring.
The resulting mixture was filled into containers. A desired lipstick with excellent dispersibility was obtained. Example 12.1 20 g of muscovite (average particle size 2 μ) and 2 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers and left in a desiccator at 80°C. After 16 hours, the muscovite was taken out and its weight was measured, and 21.8 g of treated muscovite was obtained.When the muscovite was left in a dryer at 100℃ for 24 hours, the treated muscovite was
21.4g was obtained. Comparative Example 12.1 2 g of octamethylcyclotetrasiloxane was added to 20 g of muscovite (average particle size 2 μ) and stirred with a small stirrer. Thereafter, it was fired in an electric furnace at 250°C for 2 hours. Comparative Example 12.2 20 g of muscovite (average particle size 2 μ) and 1.4 g of hydrogen methyl polysiloxane (average molecular weight 3000) were placed in a ball mill and mixed and ground for 30 minutes. Example 12.2 1 g of muscovite (average particle size 2 μ) and 20 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers and left in a desiccator at 50°C.
The weight was measured 1 day, 2 days later, and 7 days later, the weight had increased to 8.2 g. Comparative Example 12.3 1 g of muscovite (average particle size 2 μ) and 9 g of octamethylcyclotetrasiloxane were placed in a sample tube and left at room temperature for 24 hours. Comparative Example 12.4 1 g of muscovite (average particle diameter: 2 μ) and 9 g of hydrogen methyl polysiloxane (average molecular weight: 3000) were placed in a sample tube and left at room temperature for 24 hours. Example 12.4 100 g of biotite (average particle size 5 μm) and 1 g of dihydrohexamethylcyclotetrasiloxane were placed in separate containers, which were then placed in a sealed container and left at 80°C. When taken out after 72 hours and dried at 100℃,
100.6 g of treated biotite was obtained. Example 12.5 100 g of synthetic mica (average particle size 8 μ) and 5 g of a 1:1 mixed solution of tetrahydrotetramethylcyclotetrasiloxane and pentahydropentamethylcyclopentasiloxane were mixed into capocalizer CL-
Place them separately in 30B (manufactured by Fuji Electric),
The internal pressure was reduced to 100 mmHg using an aspirator, and the temperature was maintained at 30°C. After 6 hours, air was introduced to return the pressure to normal pressure, and the mixture was evacuated several times to obtain 103.2 g of treated synthetic mica. Example 12.6 When raw biotite ore and 10 g of tetrahydrotetramethylcyclotetrasiloxane were placed in a desiccator and left at 50°C for 24 hours, the biotite surface cleaved, expanded, and turned white. It cleaves thinner if it is brought into contact with gas. A photograph of the cleavage is shown in Figure 9. Example 12.7 When raw phlogopite ore and 10 g of pentahydropentamethylcyclopentasiloxane were placed in a desiccator and left at 80°C for 24 hours, the surface of the phlogopite cleaved, expanded, and turned white. A photograph of phlogopite cleavage is shown in Figure 10. Regarding Examples, Comparative Examples and untreated ones,
Measurements such as (1) crosslinking rate, (2) chloroform elution, (3) water repellency, and (4) decomposition of linalool were carried out in the above example.
It was performed according to the method described in connection with 3.3. (Results and evaluation regarding Example 12.1) From the results of the infrared absorption spectrum, it was found that 100x/(x+y)=45 in the gas phase treatment.
Therefore, 45% of the structure of the silicone polymer [CH ₃ SiO _3/2 ] _z [(CH ₃ )HSiO] _y covering the surface is [CH ₃ SiO _3/2 ], and a network structure has developed. I know what you're doing. As a result of gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment, it was found that the silicone polymer did not elute in chloroform. This indicates that the silicone polymer on the mica surface has become polymerized to the extent that it cannot be dissolved in chloroform. In a similar gel permeation experiment, silicone compounds with a molecular weight of less than 200,000 were eluted in chloroform, so it is thought that the silicone polymer polymerized on the mica surface has a molecular weight of 200,000 or more. This result agrees well with the above result of 100x/(x+y)=45, indicating that the network-structured silicone polymer tightly coats the mica surface. Table 12.1 shows the results of measuring water repellency, linalool decomposition, etc. for Example 12.1, Comparative Examples 12.1 and 12.2, and untreated mica.

[Table] The mica surface of Example 12.1 is uniformly coated with silicone polymer, has good water repellency, and does not cause decomposition of linalool. The mica of Example 12.1 does not cause odor even when coexisting with perfume. When the mica of Comparative Example 12.1 is dispersed in water, a portion of it floats on the water and most of it migrates into the water. The decomposition of linalool was greater than in the untreated case, but this is thought to be because octamethyltetracyclosiloxane was only partially adsorbed and most of the mica surface was more activated by the heat treatment. When such mica and fragrance coexist, the fragrance is thought to change in quality and change odor. In Comparative Example 12.2, the water repellency is better than that of the untreated product, but the linalool decomposition rate is about the same, and even if the surface is coated with silicone polymer to some extent, a new surface appears due to ball milling, so active sites are generated. it is conceivable that. As described above, it can be seen that the mica of the present invention has excellent water repellency and fragrance stability. The mica of Example 12.2 is 8-10 compared to the untreated mica.
Comparative Example 12.3, Comparative Example 12.4
There was no expansion. It can be seen that the compound that expands mica must have Si-H groups, and the molecular weight must be small, such as a tetramer. From this, when polymerization occurs on the surface of mica,
It is thought that polymerization occurs not only on the surface but also between the layers of mica, resulting in cleavage. However, regardless of whether or not cleavage occurred, the surface was covered with a silicone polymer film, making it water repellent and without linalool decomposition activity. Examples 12.4 and 12.5 had similar water repellency and no linalool decomposition activity. In Examples 12.6 and 12.7, raw ore mica was treated. Compared to untreated mica, cleavage has occurred in treated mica, resulting in open layers and whitening. Fine mica particles are also treated in this way and are expanded as a result. Example 12.8 5 kg of muscovite (average particle diameter 2 μm) was placed in a rotating double cone type reaction tank (made of stainless steel, equipped with a heat insulating jacket) having a volume of 100 mm. A stock solution supply tank (made of stainless steel, with heat insulating jacket) directly connected to this reaction tank with a stainless steel pipe.
In the expression 500 g of silicone compound was added, and the pressure of the system was reduced to 20 mmHg using a vacuum pump. The temperature of the system was maintained at 90°C by supplying a heating medium heated to 90°C from a heating medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump. The reaction tank was allowed to stand still for 10 minutes using a timer and then rotated three times, and this rotation was repeated for 5 hours. Thereafter, nitrogen gas was introduced into the system to return it to normal pressure, and 5.3 kg of silicone polymer-coated muscovite was obtained. Regarding Example 12.8 and the untreated one, (1) measurement of crosslinking rate, (2) chloroform elution, (3) water repellency, (4)
Measurements of linalool decomposition etc. were carried out by the method described in connection with Example 3.3 above. (Results and evaluation regarding Example 12.8) (1) From the results of the infrared absorption spectrum, it was found that 100x/(x+y)=70 in the gas phase treatment of Example 12.8. Two-fifths of the silicone compounds adsorbed in the gas phase are unterminated groups (x+y): z=
The ratio is 3:2. The terminal groups among these do not participate in the reaction, and crosslinking means that y units become x units, and at a crosslinking rate of 70%, x:y:z=42:18:40
becomes. The more x units there are, the more developed the network structure is, and the better the film is formed. In the case of Example 12.8, 42% was crosslinked, and more than two-thirds of the initially supplied silicone monomer Si-H was crosslinked, so the network structure was maintained. From the above results, the structure of the silicone polymer in Example 12.8 is [CH ₃ SiO _3/2 ] _x [CH ₃ (H)SiO] _y
[(CH ₃ ) ₃ SiO _1/2 ] _z , and x:y:z=42:
It is 18:40. As described above, if the initial monomer is known, the structure can be determined by measuring the crosslinking rate and addition rate. (2) As a result of gel permeation chromatography of the chloroform eluate obtained in the chloroform elution experiment, it was found that the silicone polymer did not elute in chloroform. This indicates that the silicone polymer of Example 12.8 had become a polymer and could no longer be eluted in chloroform. In a similar gel permeation experiment, silicone compounds with a molecular weight of less than 200,000 were eluted in chloroform, so the silicone polymer of Example 12.8 is considered to have a molecular weight of 200,000 or more.
This result agrees well with the crosslinking rate {100x/(x+y)}=70 and the development of a network structure. (3) Showing the results of water repellency and linalool decomposition measurements.
Shown in 12.2. Untreated muscovite is hydrophilic and has the ability to decompose linalool,
Since Example 12.8 is coated with a silicone polymer, it becomes water repellent and the linalool decomposition reaction that occurs on the mica surface does not occur. Therefore, the stability against fragrances was also very good. Table 12.2—Water repellency and linalool stability

[Table] Example 12.9 10 kg of synthetic mica (muscovite in which the -OH group is replaced with -F) was placed in a rotating double cone type reaction tank (made of stainless steel, with a heat insulating jacket) having a capacity of 100 cm. The stock solution supply tank (made of stainless steel, with a thermal jacket) is directly connected to the 10 kg of a silicone compound was put therein, and nitrogen was bubbled from the bottom of the stock solution supply tank to supply it to the reaction tank. The temperature of the system was maintained at 70°C by supplying a heating medium heated to 70°C from a heating medium heating tank to the heat insulation jackets of the reaction tank and stock solution supply tank using a circulation pump. The reaction tank is rotated by a timer after 10 minutes of rotation.
This rotation was repeated for 7 hours. Thereafter, the silicone was removed, and rotation was continued for 12 hours while introducing only nitrogen into the reaction tank. After returning to room temperature, 19.6 kg of treated product was obtained. The processed product obtained in this way is fluffy,
It showed remarkable water repellency. Furthermore, the linalool decomposition activity disappeared and the fragrance stability became good. Example 12.10 5 g of 2,2',4,4'-tetrahydroxybenzophenone, 100 g of muscovite and 300 ml of ethanol were mixed, dried at 80°C, and then placed in a desiccator at 80°C with 20 g of tetrahydrotetramethylcyclotetrasiloxane. Put it inside and process for 16 hours, 112g
A treated powder was obtained. This treated powder showed remarkable water repellency. Example 12.11 Two ultraviolet absorbers were added in the same manner as in Example 12.10.
Methyl 5-diisopropyl silicate was produced. This treated powder showed significant hydrophobicity. Example 13.1 100 g of spherical porous silica (specific surface area 350 m ² /g, pore size 102 Å, particle size 10 μ) and 100 g of tetramethylcyclotetrasiloxane are placed in separate containers,
It was left at 80°C in a desiccator. After 24 hours, it was taken out of the desiccator and left at 100°C for 2 hours to obtain 123.3 g of treated product. Comparative Example 13.1 10 g of tetramethylcyclotetrasiloxane and 50 ml of chloroform were added to 10 g of the porous silica used in Example 13.1, and a reaction was carried out for 24 hours on an oil solution, followed by dry up. Comparative Example 13.2 10 g of the porous silica used in Example 13.1 and 20 g of alumina balls were placed in a planetary ball mill, and
After stirring for a minute, 10 g of tetramethylcyclotetrasiloxane was added and stirring was continued for an additional hour. (Evaluation of Example 13.1, Comparative Example 13.1, and Comparative Example 13.2) Changes in shape of Example 13.1, Comparative Example 13.1, and Comparative Example 13.2 were evaluated with the naked eye and with a microscope. (1) Change in shape In Example 13.1, it maintained a spherical shape, had a smooth feel, and no aggregation was observed. On the other hand, in Comparative Example 13.1, although the shape remained spherical, it agglomerated and agglomerated. Comparative Example 13.2 did not maintain a spherical shape at all, and moreover, it had slurry properties, and the resin and silica were mixed together and solidified. (2) Change in pore diameter The pore diameter was measured using Autosorb 1 manufactured by Quantachrome. In Example 13.1 the diameter of 102 Å changes to 90 Å,
The 6 Å pore became smaller in radius. This indicates that a thin film of approximately 6 Å is uniformly coated on the inner surface of the pore. On the other hand, in Comparative Examples 13.1 and 13.2, most of the pores are lost, and it is clear that it is difficult to thinly cover only the pore surfaces in a liquid state that has entered the pores. (3) Evaluation of surface activity To evaluate the surface activity, a microreactor was used to measure the decomposition of linalool, which is one of the fragrance ingredients. The measurement method was to fix a porous material in a Pyrex glass tube with an inner diameter of 4 mm with 20 mg of quartz wool, and heat it at 180°C.
Injected 0.3μ of linalool. The carrier gas was nitrogen at 50 ml/min. Analysis was performed with a Shimadzu GC-7A, and the column was 5% FFAP/Chromosorb w.
80/100 mesh, 3mm x 3m, column temperature 80℃
(maintained for 4 min.) to 220°C (heating rate 5°C/min.). Untreated silica decomposes linalool, producing myrcene, limonene, cis-ocimene, trans-ocimene, etc. This indicates that a solid acid exists on the untreated silica surface and has the effect of dehydrating the tertiary alcohol of linalool. In contrast, in Example 13.1, linalool was not decomposed at all, and it can be seen that the acid sites on the silica surface were completely covered with silicone resin. Comparative Examples 13.1 and 13.2 were not evaluated in the reactor because silicon oligomers were present. However, since more than enough silicone oligomer adheres to the silica surface, it seems that the acid sites of the silica are blocked. From the above, it can be seen from the decomposition measurements of linalool that Example 13.1 can be coated with a thin film of approximately 6 Å to the inside of the pores without changing its shape at all, and that this amount is sufficient for coating. It also became clear. Comparative Examples 13.1 and 13.2 can similarly coat the surface of silica with a polymer, but it is not possible to control the coating by coating only one layer of the surface inside the pores. In particular, in Comparative Example 13.2, the untreated spherical shape collapsed due to the treatment using crushing force. Example 13.2 Alumina (3 mmφ, specific surface area 2 m ² /g, after granulation
100g of the product (calcined at 1100°C) and 100g of tetramethylcyclotetrasiloxane were placed in separate containers and left at 25°C in a desiccator. After 72 hours, it was taken out of the desiccator and left at 50°C for 3 hours to obtain 100.6 g of treated product. This treated product showed significant hydrophobicity, Example 13.1
Similarly, the degrading activity of linalool had disappeared. Example 13.3 Silica alumina (Silica alumina ratio = 50:
50, 2 mmφ, specific surface area 3 m ² /g) and 10 g of dimethyldimethoxysilane were placed in separate containers and left at 100° C. in a desiccator. After 24 hours, it was taken out of the desiccator and left at 100°C for 3 hours to obtain 102.3 g of treated product. This treated product showed significant hydrophobicity, Example 13.1
Similarly, the degrading activity of linalool had disappeared. Example 13.4 Hollow silica (particle size 3μ, specific gravity 0.23, specific surface area 412
m ² /g) and 20 g of pentamethylcyclotetrasiloxane were placed in separate containers and left at 80° C. in a desiccator. After 24 hours, it was taken out of the desiccator and left at 100°C for 3 hours to obtain 61.4 g of treated product. This treated product showed significant hydrophobicity, Example 13.1
Similarly, the degrading activity of linalool had disappeared. Example 13.5 Molding and firing clay (mainly kaolin) (1000℃)
53.5 g of the prepared doll and 10 g of tetramethylcyclotetrasiloxane were placed in separate containers and left at 50° C. in a desiccator. After 24 hours, it was taken out of the desiccator and left at 50°C for 3 hours to obtain 56.2 g of treated product. This treated doll showed significant hydrophobicity. In addition, this treated doll is placed in a rose-based mixed fragrance (commercially available).
Leave it at room temperature (20℃) for 12 hours to absorb the fragrance, then place it in a suitable airtight glass container and heat it to 40℃.
Stored for 30 days. This product had significantly higher fragrance stability than the untreated product. Example 14.1 Wool powder pulverized by a pulverizer (average particle size
10μm) and 5g of tetrahydrotetramethylcyclotetrasiloxane in separate containers and heated at 50°C.
It was left in a desiccator. After 16 hours, the wool powder was taken out and dried at 60° C. for 2 hours, and the weight of the treated wool powder was measured and found to be 20.6 g.

[Brief explanation of drawings]

FIG. 1 is a spectral curve obtained by measuring untreated yellow iron oxide powder samples of Example 1.1, Comparative Example 1.1, and Comparative Example 1.2 using a Hitachi Color Analyzer Model 607 in the range of 380 nm to 780 nm. Figures 2 to 5 are
Untreated, Example 1.1, Comparative Example 1.1 and Comparative Example, respectively.
1.2 is a gas chromatogram pattern of linalool decomposition of each yellow iron oxide powder sample, where is the peak of linalool, and ~ are the peaks of decomposed products, respectively. FIG. 6 is an X-ray photoelectron spectroscopy diagram. In FIG. 6, a is a curve for yellow iron oxide before treatment in Example 4.1, and b is a spectrum for yellow iron oxide after the same treatment (coating). FIG. 7 is a drawing showing the results of measuring the surface state of titanium dioxide coated with the silicone polymer obtained in the present invention and titanium dioxide before coating using X-ray photoelectron spectroscopy. FIG. 8 is a drawing showing the results of measuring the surface condition of titanium dioxide coated with a silicone polymer obtained according to the present invention and titanium dioxide before coating using an infrared absorption spectrum. FIGS. 9 and 10 are photographs showing changes in the crystal structure of mica raw ore and the stable mica of the present invention obtained by coating the raw ore with a silicone polymer.

Claims (1)

[Claims] 1 General formula (R ¹ HSiO) _a (R ² R ³ SiO) _b (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _c (
) (wherein R ¹ , R ² and R ³ 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, However, R ¹ , R ² and R ³ are not hydrogen atoms at the same time, 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 an integer of 0 or 1 or more, b is an integer of 0 or 1 or more, and c is 0 or 2,
However, if c is 0, the sum of a and b shall be an integer of 3 or more). A modified powder having a silicone polymer film supported on substantially the entire surface thereof, which is obtained by contacting the powder with a body and polymerizing a silicone compound on substantially the entire surface of the powder. 2 General formula (R ¹ HSi0) _a (R ² R ³ Si0) _b (R ⁴ R ⁵ R ⁶ Si0 _1/2 ) _c (
) (wherein R ¹ , R ² and R ³ 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, However, R ¹ , R ² and R ³ are not hydrogen atoms at the same time, 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 an integer of 0 or 1 or more, b is an integer of 0 or 1 or more, and c is 0 or 2,
However, if c is 0, the sum of a and b shall be an integer of 3 or more). The modified powder is made by polymerizing a silicone compound on substantially the entire surface of the powder in contact with the body, and is characterized by containing a modified powder carrying a silicone polymer film on substantially the entire surface of the powder. , cosmetic composition. 3 General formula (R ¹ HSi0) _a (R ² R ³ Si0) _b (R ⁴ R ⁵ R ⁶ Si0 _1/2 ) _c (
) (wherein R ¹ , R ² and R ³ 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, However, R ¹ , R ² and R ³ are not hydrogen atoms at the same time, 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 an integer of 0 or 1 or more, b is an integer of 0 or 1 or more, and c is 0 or 2,
However, if c is 0, the sum of a and b shall be an integer of 3 or more). The modified powder is made by polymerizing a silicone compound on substantially the entire surface of the powder in contact with the body, and is characterized by containing a modified powder carrying a silicone polymer film on substantially the entire surface of the powder. , paint composition.