JPS61268763A - Production of treated powder - Google Patents

Abstract

PURPOSE:To provide powder surface such as of organic or inorganic pigment with uniform hydrophobicity with no need of calcination and no development of discoloration, by bringing powder with active points present on the surface into contact with gasified product from cyclic organosiloxane of specific structure to perform polymerization of said siloxane on the surface. CONSTITUTION:Within a closed chamber hold at constant temperature <=100 deg.C (e.g., sterilizer using gas, desiccator), (A) powder heaving on its surface, active points such as acid- or base ones (e.g., yellow iron oxide) and (B) a cyclic organosiloxane of formula I or II (n is 3-6) (e.g., tetramethyl tetrahydrogencyclotetrasiloxane) are each put in a vessel to be left to stand to bring said surface into contact with gasified product, in a molecular state, from said organosiloxane normally for 4-24hr, thus polymerizing said organosiloxane on the surface.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is directed to a treated powder in which the activity of a powder having surface activity such as acid sites and base sites is eliminated, and the surface is made hydrophobic. Concerning a method of manufacturing a body.

The treated powder obtained by the method of the present invention does not decompose resins, oils, fragrances, etc. even if they coexist.1 Therefore, it does not cause problems such as deterioration of quality and odor, so it can be used in cosmetics, pharmaceuticals, and other products. It can be used in fields such as paints.

[Conventional technology]

Conventionally, silicone oil has often been used to make powders hydrophobic.For example, Japanese Patent Publication No. 41-9890 describes the method of hydrophobizing powders by coating the surface of animal, plant, or mineral powders with silicone resin paint and drying the powders. Provides lubricity. Tokuko Showa 4
5-2915, water repellency is imparted to the powder by simply adhering mineral powder such as talc and silicone having hydrogen that directly bonds with silicon in the molecular chain by mixing with a blender, etc., and then heating and baking it. are doing. Also, special public service in 1972
-18999, dimethylpolysiloxane or methylhydrodienepolysiloxane is dissolved in an organic solvent and then contacted and adhered to talc, and then, if necessary, a substance such as zinc octoate is added as a crosslinking polymerization catalyst for methylhydrodienepolysiloxane and baked. , imparts free-flowing properties to the powder.

Furthermore, in Japanese Patent Publication No. 49-1769, titanium dioxide is directly coated with various alkyl polysiloxanes, emulsion coated or coated with a solvent solution, and if necessary, an ester compound having a total carbon number of 6 or more is used, and by dry baking and attaching. We are modifying the dust properties, dispersibility, etc. of the powder. Also, JP-A-5
6-1.6404, JP-A-55-136213, and JP-A-56-29512, silicone oil and oil agent are added and mixed by a mechanochemical reaction such as stirring or pulverization, and then baking treatment is performed. . Furthermore, Japanese Patent Publication No. 5
7-200306, by treating powder with (A) a silane compound having a specific structure, (B) a cyclic polyorganosiloxane, and (C) a linear polyorganosiloxane, water repellency, water repellency, and A method of providing liquidity is disclosed.

This method involves diluting 1 to 10% by weight of the above-mentioned organosilicon compound in a solvent and spraying, direct spraying, or gaseous spraying, or direct mixing and stirring to adsorb onto the powder;
This is followed by water and steam treatment, which are excluded.

[Problem that the invention seeks to solve]

However, these methods cannot treat most organic and inorganic pigments that are sensitive to heat, such as yellow iron oxide and dark blue.

For example, as an organic pigment, Red No. 202 (Reseal Lupine B
When CA) was dehydrated at 80°C, the crystal form changed from α type to β type and the color tone changed, so it could not be processed. In addition, Prussian blue decomposes when heated and gradually releases cyan gas at temperatures above 150°C. The baking treatment is expensive: 35
The process is carried out at 0° C. for 2 hours, or at 150° C. for 15 to 40 hours. Under these conditions, the deep blue color not only changes color but also emits toxic cyan gas, which is extremely dangerous.

This type of conventional baking treatment can only be applied to some stable inorganic pigments, and has the fatal drawback of damaging the color tone, which is the lifeblood of bright organic pigments.

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, resulting in significant changes over time, making it impractical. Met. In addition, the action of the catalyst promotes the decomposition of not only the silicone resin on the surface, but also other coexisting components 1, such as oil and fragrance, causing problems such as deterioration and odor, making it unsuitable for use in cosmetics, etc. There wasn't.

JP-A-56-16404 describes a silicon processing method using mechanochemical reactions. Since this method uses wall and crushing force, the shape of powders that are plate-shaped or spherical will change. Furthermore, it has been difficult to treat powders such as titanium dioxide that aggregate when stirred alone.

In JP-A-57-200306, in all cases, the molecular treatment agent does not come into contact with the powder, but rather in the form of a liquid or fine particle liquid. For this reason, the trimer, which is a solid among the cyclic polyorganosiloxanes, is excluded. The amount of processing agent is 1 to 10% of the powder.
However, depending on the type of powder, this amount may not be sufficient, and there are drawbacks such as surface activity remaining in the powder and, if perfume etc. coexist, the stability of the perfume deteriorates.

[Means for solving problems]

When processing powder with silicone oil in this way, most technologies require heat, catalysts, or crushing power.
This is because it is assumed that the silicone oil used is relatively inert and the powder used has no activity.

However, many powders have surface activity,
This surface activity causes coexisting fragrances, oils, etc. to deteriorate, but the present inventors utilized this surface activity to polymerize silicon on the powder surface, making the surface hydrophobic and We have discovered an innovative method to improve the stability of fragrances by eliminating their surface activity.

That is, the present invention relates to a method for producing treated powder that utilizes the activity of the powder surface and polymerizes a cyclic organosiloxane at a low temperature of 100° C. or lower to make the surface hydrophobic and at the same time block the surface activity.

Inorganic powders used in the present invention include clay minerals such as kaolin, talc, montmorillonite, hectorite, sericite, nacrite, detskiite, massikovite, hallosite, chlorite, and zeolite, titanium dioxide,
iron oxide, chromium oxide, chromium hydroxide, cobalt blue,
Metal oxides such as alumina, silica, zirconium oxide, zinc oxide, calcium oxide, and magnesium oxide, or metal composite oxides made of a combination of two or more of these, and colored pigments such as deep blue, ultramarine, and manganese violet, and titanium coatings. Examples include var pigments such as mica and bismuth oxychloride.

In addition, organic powder can also be used in the present invention, and typical organic pigments can be applied, such as Red No. 3, Red No. 104, Red No. 202, Red No. 204, Red No. 205, Red No. 207, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red 2
No. 30, Orange No. 203, Yellow No. 4, Yellow No. 5, Yellow No. 40
Examples include No. 1, Blue No. 1, and Blue No. 404. When these organic pigments are zirconium lake or aluminum lake, they may be surface-treated in advance by a known method to improve the effect.

The cyclic organosiloxane used in the present invention is represented by the following formula, and one type or a combination of two or more thereof can be selected.

ζB) n represents an integer of 3 to 6. The smaller the number of n, the lower the boiling point, and the greater the amount that is volatilized and adsorbed to the powder. In particular, trimers are most suitable because they are easier to polymerize due to their three-dimensional properties. Furthermore, those containing hydrogen atoms have high reactivity and are suitable for surface treatment. Regarding the amount of treatment, the amount of treatment is not fixed because the present invention is a gas phase treatment, and the volatilized cyclic organosiloxane is adsorbed onto the powder and then polymerized by the active sites of the powder. The end point is when all the points are covered.

In other words, the present invention is a processing method characterized in that the amount of processing agent to be added is not predetermined, but a necessary and sufficient amount of processing agent is supplied.

Therefore, the amount of # to be treated varies depending on the powder, but the most common ones are 32% of chromium oxyhydroxide, 33% of dark blue, and 20 to 30% of organic pigment. □In this way, the present invention can treat any powder without excess or deficiency, and this is because the method of adding the processing agent is different from conventional methods.

In the present invention, the processing agent is not added in liquid form, but is brought into contact with the powder in molecular form, so the original processing agent may be either solid or liquid.

In addition, considering polymerization on the powder surface, trimers are most easily polymerized and are therefore most suitable as processing agents. In other words, the feature of the present invention is that it is an energy-saving method that utilizes the fact that cyclic organosiloxane is adsorbed to the powder in its molecular state and polymerized from the active sites on the surface. This is completely different from the method of polymerization.

Since the method for producing hydrophobic powder of the present invention does not involve heat treatment, it can be applied to pigments with low temperature stability, and its range of applications is extremely wide.

(Leave below) To specifically describe the manufacturing method of the present invention, the basic embodiment is that the powder and the cyclic organosiloxane are placed in separate containers in a sealed room at 100°C or lower and the top is open. Just leave it there. If the powder is inactive when the treated powder is taken out of a sealed room, the cyclic organosiloxane will be desorbed and the powder will return to its original surface. In the case of a powder that has active sites, the cyclic organosiloxane polymerizes on the powder because it has polymerization activity, and the partial pressure of the cyclic organosiloxane on the powder surface decreases, causing the cyclic organosiloxane in the container to polymerize. Volatized and supplied. Since the surface polymerization occurs in this order, the cyclic organosiloxane is supplied in the required amount to the system, and there is no waste.

Because it is based on such a simple principle, no special equipment is required, just a closed room that can be kept at a constant temperature. Moreover, a desiccator can also be used to process a small amount. However, ideally, a device that can degas after treatment is desirable, and it is most efficient to use a gas sterilizer.
Only the powder is placed in advance in a sealed room at 100°C or lower, and in another sealed room at 100°C or lower, the cyclic organosiloxane is volatilized at the required partial pressure. It is also possible to introduce it into the room where the body is placed through a pipe or the like.

In either embodiment, the treatment time is from 4 hours to 24 hours, after which the unpolymerized cyclic organosiloxane is removed by degassing to obtain the desired product.

The treated powder obtained as described above has the following characteristics.

■ Baking does not require any processing, and polymerization occurs on the surface of the powder, which is effective in terms of energy savings and does not change color.

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

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

Note that the water repellency and surface activity of the treated powder are almost completely blocked.

Hereinafter, the present invention will be explained by examples.

Example 1 10g of yellow iron oxide in a 200mm beaker and 5g of tetramethyltetrahydrodienecyclotetrasiloxane in a 20ml sample tube were placed in a desiccator and left at 50°C.

After one day, it was taken out of the desiccator and left to stand at 50°C for 3 hours to obtain 10.185 g of treated product.

Comparative Example 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.

Thereafter, when it was baked at 250°C, it turned red.

Comparative Example 2 Yellow iron oxide 10g and calcium hydroxide 0.019g
was placed in a ball mill and mixed and ground for 30 minutes.

Then hydrogen methyl polysiloxane (molecular weight =
0.185g of 2600) was added, and mixing and grinding was further performed for 30 minutes. Next, 0.076 g of myristic acid was added, and the mixture was mixed and ground for 30 minutes to obtain a treated product.

Color measurement, water repellency, specific volume, and decomposition behavior of linalool in a microreactor were measured for each of Example 1, Comparative Example 1, Comparative Example 2, and untreated yellow iron oxide.

(Measurement f>- The sample was filled in 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 FIG. 1.

As is clear from the spectral curves, it can be seen that the untreated pattern and Example 1 are quite similar, and the patterns of Comparative Examples 1 and 2 are different. In addition, the colorimetric results were expressed in Lsasb, and the color difference ΔE was calculated and shown in Table 1. It can be seen that the color difference ΔE of Example 1 is significantly smaller than that of the comparative example.

(Water repellency) Five ion-exchanged water was placed in a 10-sized sample tube, and 0.1 g of powder was added and shaken.

The judgment is as follows.

×・・・・・・・・・・・・Dispersed in the water.

Δ・・・・・・・・・・・・ Water repellent, but some of it was dispersed in water.

O・・・・・・・・・・・・ Water repellent and floated on the surface of water.

The results are shown in Table-1. Untreated yellow iron oxide was well dispersed in water, but in Example 1 and Comparative Example 2, it was water repellent and floated on the water, but in Comparative Example 1, the treatment was not complete and a portion was dispersed in water.

(Specific Volume) 5 g of the powder was placed in a test tube for tapping specific volume, and tapping was performed 200 times to determine the specific volume. °Table of results-
Shown in 1.

It can be seen that in Comparative Example 2, because a ball mill was used, the material agglomerated and the specific volume became smaller. Although some aggregation occurred in Comparative Example 1 as well, this was probably due to the evaporation of the solvent.

On the other hand, in Example 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-1 (Decomposition of linalool by microreactor) Inner diameter 4
The powder was fixed in a Tsuru Pyrex glass tube with 20 mg of quartz wool, and the decomposition of linalool, one of the aroma components, was measured at a reaction temperature of 180 t'.

The linalool injection amount was 0.3 PR, and the carrier gas was nitrogen at a flow rate of 50 mm.

Analysis was performed using Shimabara GC-7A, and the column was 5% FPAP.
/ chromosorb w 80 / 1003
mn+X 3 m and column temperature 80℃ (4mm) → 22
The heating rate was 5° C./mm to 0”C.

FIG. 2 is a gas chromatography pattern of untreated yellow iron oxide glue decomposition. a is the peak of linalool, 2
．． The peak 3.4 is the peak of decomposed products. Figure 3 shows
It is a gask pattern of linalool decomposition in Example 1.

Decomposition products of 2.31.4 decreased compared to untreated ones,
It can be seen that the linalool degrading activity has disappeared. FIG. 4 shows the linalool decomposition pattern of Comparative Example 1. There is no linalool peak, only decomposition product 5 is present.

In other words, the powder of Comparative Example 1 has increased decomposition activity compared to untreated powder,
This indicates that the fragrance stability has deteriorated.

FIG. 5 shows the linalool decomposition pattern of Comparative Example 2. The activity is weaker than that of Comparative Example 1, and unreacted adhesive residue remains, but the activity is stronger than that of the untreated sample. .

As mentioned above, in Comparative Examples 1 and 2, the decomposition activity of linalool is stronger compared to untreated, and the flavor stability is worse, but in Example 1, the linalool decomposition activity is weaker, and the flavor stability is improved. There is.

Regarding the linalool decomposition activity in Table 1, untreated is marked as △, those whose activity is stronger than that of untreated are marked as ×, and those whose activity is weaker than that of untreated are marked as ○.

Comprehensively judging from Table 1, it can be seen that Example 1 has water repellency with almost the same color and parasitic properties 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 2 Gas sterilizer Capocalizer CL-30B (Fuji
100 g of yellow No. 5 aluminum lake and 50 g of trimethyltrihydrodienecyclotrisiloxane were placed in separate containers, and the internal pressure was increased to 100 mmHg using an abilator.
The pressure was reduced to 30°C and the temperature was maintained at 30°C.

After 6 hours, air was introduced into the reactor to return it to normal pressure, and the reactor was evacuated several times to obtain 128 g of treated powder. This treated powder showed significant hydrophobicity, and the ability to decompose linalool had disappeared.

Example 3 In a desiccator, 10 g of Prussian blue and 10 g of tetramethyltetrahydrodienecyclotetrasiloxane were placed in a separate container 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. Moreover, at this time, the navy blue did not decompose and there was no cyan odor.

Example 4 Gas sterilizer Cabokalyzer CL-30B (Fuji
10g of zinc white in Hlectric Co Ltd)
Put 5g of hexamethylcyclotrisiloxane into a separate container, and use an aspirator to increase the internal pressure to 300 m
The pressure was reduced to mHg and the temperature was maintained at 50°C.

After leaving it for one night, air was introduced to return the pressure to normal pressure, and the mixture was evacuated several times to obtain 10.2 g of treated powder. This treated powder showed significant hydrophobicity.

Example 5 20 kg of titanium dioxide was put into a rotary double cone type reaction tank (made of stainless steel, with a heat insulation jacket) having a volume of too l, and 20 kg of titanium dioxide was placed in a stock solution supply tank (made of stainless steel, with a heat insulation jacket) directly connected to the reaction tank with a stainless steel pipe. 400 g of methyltetrahydrodienecyclotetrasiloxane was added, and the pressure of the system was reduced to 100 mm II g 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 operation of mixing and stirring titanium dioxide in the reaction tank was repeated for 10 hours, after which it was introduced into a N2 gas system and the treated powder was returned to normal pressure.
3 kg was taken out. 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.

[Brief explanation of the drawing]

Figure 1 shows the yellow iron oxide powder samples of untreated, Example 1, Comparative Example 1, and Comparative Example 2, which were measured using a Hitachi Color Analyzer 60.
This is a spectral curve measured in the range of 380 nm to 780 nm using a Type 7 model. Figures 2 to 5 are untreated, Example 1, and Comparative Example 1, respectively.
and gas chromatography pattern of linalool decomposition of each yellow iron oxide powder sample of Comparative Example 2, a is a peak of linalool, and 1 to 6 are peaks of decomposed products, respectively. Patent Applicant: Shiseido Co., Ltd. 1 Ascendant A ← Figure 7 Figure 3 Figure 2 Figure R Proceeding Amendment Band (1) February 26, 1985 1, Case Indication 1985 Patent Application No. 265715 2. Title of the invention: Process for producing treated powder 3. Relationship with the case of the person making the amendment Patent applicant: February 13, 1985 (shipped on February 18, 1988) 5. Specification subject to amendment 6 , Contents of the amendment As per the engraving and attached sheet of the specification originally attached to the application (
(no change in content). Procedural amendment written 2) (Voluntary) February 26, 1986 l. Display of the case 1985 Patent Application No. 265715 2゜Name of the invention Process for producing treated powder 3, Person making the amendment Relationship to the case Column 5 of the detailed description of the invention in the patent applicant's specification, Contents of the amendment (1) Specification submitted as an attachment to procedural amendment (1) submitted at the same time (hereinafter referred to as the specification) Page 1θ, No. 1
Correct the lines from line 7 to 7th θ line as follows. ” Color No. 228, Red No. 405, Orange No. 203, Orange No. 204
Organic pigments selected from No. 1, Yellow No. 205, Yellow No. 401, and Blue No. 404, as well as Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, and Red No. 4.
Examples include organic pigments selected from zirconium, barium or aluminum lake such as No. 01, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1. . (2) Insert the following below the first line on page 22 of the statement. 5 cans example 6

Claims (9)

[Claims] (1) In a closed chamber maintained at a temperature of 100° C. or less, a vaporized cyclic organosiloxane represented by the following formula is brought into contact with the particle surface of a powder having active sites on the particle surface in a molecular state. A method for producing a hydrophobic powder, comprising polymerizing the cyclic organosiloxane on the surface of a powder particle. (a)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (b)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) Powder having active points on the particle surface is Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 2
No. 20, Red No. 226, Red No. 228, Red No. 405,
Orange No. 203, Orange No. 204, Yellow No. 205, Yellow 40
The method for producing a hydrophobic powder according to claim 1, which is an organic pigment selected from No. 1 and Blue No. 404. (3) Powders with active points on the particle surface are Red No. 3, Red No. 104, Red No. 106, Red No. 227, and Red 230.
No., Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green 3
The method for producing a hydrophobic powder according to claim 1, which is an organic pigment selected from zirconium, barium, or aluminum lake of No. 1 and Blue No. 1. (4) The powder having active sites on the particle surface is kaolin, talc, montmorillonite, hectorite, sericite,
The method for producing a hydrophobic powder according to claim 1, which is an inorganic powder selected from nacrite, deckite, mashicovite, halloysite, chlorite, and zeolite. (5) Powder having active points on the particle surface is deep blue, ultramarine,
The method for producing a hydrophobic powder according to claim 1, which is an inorganic pigment selected from manganese violet, titanium-coated mica, and bismuth oxychloride. (6) The method for producing a hydrophobic powder according to claim 1, wherein the powder having active sites on the particle surface is a metal oxide powder. (7) The metal oxide powder is titanium dioxide, red iron oxide,
Yellow iron oxide, black iron oxide, lower titanium oxide, chromium oxide, chromium hydroxide, cobalt blue, alumina, silica,
The method for producing a hydrophobic powder according to claim 1, which is selected from zirconium oxide, zinc oxide, calcium oxide, and magnesium oxide. (8) The method for producing a hydrophobic powder according to claim 1, wherein the powder having active sites on the particle surface is a metal composite oxide powder. (9) The method for producing a hydrophobic powder according to any one of claims 1 to 8, wherein the cyclic organosiloxane is a trimer.