JPH04187229A - Reformed powder - Google Patents

Abstract

PURPOSE:To obtain a reformed powder excellent in water repellency and dispersibility and with the second aggregation reduced by mixing the powders and the organosilicons having 1-350cSt viscosity at 25 deg.C in a specified ratio, agitating the mixture and then heat-treating the mixture. CONSTITUTION:The powders and the organosilicons having 1-350cSt viscosity at 25 deg.C are mixed in the weight ratio of (100:3) to (100:20) and agitated, and then the mixture is heat-treated to obtain a reformed powder. A colored pigment such as yellow iron oxide and red iron oxide and a white pigment such as zinc oxide, rutile or anatase-type titanium oxide and cerium oxide are exemplified as the powders. A powder agitator such as Henshell type mixer is used to agitate and mix the powders and organosilicons. Heat treatment is performed by allowing the treated powder to stand on a metallic vat and then drying the powder by a blast drier, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a modified powder obtained by stirring and mixing powders and organosilicones having a specific viscosity and then subjecting the mixture to a heat treatment.

More specifically, the present invention relates to a modified powder produced by a novel dry method, which is characterized by almost no secondary aggregation of powder due to organosilicones and which provides powder with excellent water repellency. .

[Problems to be solved by conventional techniques and inventions] Conventionally,
Methods for coating powders with organosilicones include: 1) A method using mechanochemicals such as a ball mill 2) Adding organosilicones dissolved in a solvent to the powders and, if necessary, distilling off the solvent. 3) A vapor phase method in which powders are brought into contact with gaseous organosilicones and then coated with heat. 2) 4) A method in which powders are coated with organosilicones using a spray dryer, etc. is commonly used. However, the above method using mechanochemicals (l) has problems in that the coating is non-uniform and the amount that can be treated at a time is limited, resulting in low productivity. Although the wet method (2) has the feature of being able to uniformly coat the powder with the organosilicon, it has the problem of unavoidable agglomeration of the powder during the process of distilling off the solvent or drying.

The gas phase method (3) has the feature of being able to form a uniform film on powders, but has problems such as the need for a closed type production device. The problem with the spray dryer (4) is that it becomes a large manufacturing device when processing a large amount.

That is, the object of the present invention is to eliminate secondary agglomeration of powders,
The object of the present invention is to provide a modified powder having a uniform organosilicon film.

[Means to solve the problem]

As a result of intensive research in view of the above problems, the present inventors found that
In the process of coating powders with organosilicones, we unexpectedly discovered that the cause of secondary aggregation of powders was the use of solvents, and furthermore, we discovered that the use of solvents was the cause of secondary aggregation of powders, and that Regarding the mixing ratio of organosilicones and the viscosity of organosilicones, it was found that the dry method coating treatment resulted in less secondary aggregation of the powder that was the base material.
The invention has been completed.

That is, the present invention uses powders and a viscosity at 25°C of 1
~350cst of organosilicones at a weight ratio of powder and organosilicones of 100:0.3.
It is a modified powder obtained by stirring and mixing at a ratio of ~100.20, followed by heat treatment.

The present invention will be explained in detail below.

Powders used in the present invention include colored pigments such as yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, and carphone black; white pigments such as zinc oxide, rutile type titanium oxide, anatase type titanium oxide, and cerium oxide; Extender pigments such as talc, mica, sericite, and kaolin, bar pigments such as titanium mica, metal salts such as barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, and magnesium silicate, and organic coatings such as N-acylaspartic acid coated mica. Pigments and metallic soap-treated pigments, polymer powders such as nylon powder, silk powder, urethane powder, Teflon powder, cellulose powder, inorganic powders such as theolite smectite, silica, alumina, gypsum, glass beads, etc., blue No. 404, etc. Examples include pigments, fine particles of titanium oxide, fine particles of zinc oxide, fine particles of black iron oxide, silica-treated fine particles of titanium oxide, and alumina-treated fine particles of titanium oxide.

Preferred particle sizes of the powders used in the present invention are, for example,
Titanium oxide is 0.1 to 1.2 μm, zinc oxide is 0.
4 to 1.0 μm, 0.1 to 2.0 μm for iron oxide, 0.1 to 5.0 μm for ultramarine, 0.5 to 20.0 μm for sericite, kaolin, talc, mica1 Silica beads,
Glass beads are 0.1 to Imm.

Particulate titanium oxide, particulate zinc oxide, particulate black iron oxide,
For Aerosil, it is 0.01 to 0.1 μm; for nylon powder, it is 10 to 150 μm.

The organosilicones used in the present invention can be used regardless of whether they are polymerizable or non-polymerizable.

That is, for example, as polymerizable organosilicones, olefin-modified silicone 2, methylhydrodiene polysiloxane, alkylhydrodiene polysiloxane, 'Si-OH group-containing methylpolysiloxane, 5i
-H group-containing cyclic organopolysiloxanes, 5i-H group-containing fluorine-modified silicones, alkylarylpolysiloxanes, etc., and non-polymerizable organosilicones include dimethylpolysiloxanes and alkylpolysiloxanes.

Examples include methylphenylpolysiloxane, cyclic organopolysiloxane, and fluorine-modified soricone. These organosolicones can be used alone or in combination of two or more.

The viscosity of the organosilicones is 1 to 350 cst, preferably 1 to 100 cst.

If it is smaller than 1 cst, the evaporation rate during heating will be too fast, making it difficult to coat the powder. Moreover, when the temperature exceeds 350 cst, aggregates are formed in which the organosilicones are used as cores and the powders are gathered around the powders. This tendency is noticeable in fine particle powders with a particle size of 0.1 μm or less, such as fine titanium oxide.

The blending ratio of organosilicones and powders is 0.3 to 20 parts by weight, preferably 1 to 12 parts by weight, based on 100 parts by weight of powders.

If the amount of organosilicones is less than 0.3 parts by weight, the effects of organosilicones cannot be obtained.

If the amount of organosilicones exceeds 20 parts by weight, secondary aggregation of powders may occur.

A conventionally used powder stirring device such as a Henschel mixer can be used to stir and mix the powders and organosilicones used in the present invention. However, for powders that tend to agglomerate, such as titanium oxide, after mixing and stirring with a Henschel mixer, use a grinding device such as an atomizer-1 free grinder to thoroughly pulverize the powder before heat treatment. It is necessary to release the agglomeration of the particles and turn them into secondary particles.

If the agglomeration of the powders is not sufficiently released before the heat treatment, secondary agglomerates of the powders will occur after the heat treatment.

The heat treatment used in the present invention is performed by leaving the powder treated above in a metal vat, and then using a blow dryer or the like, or by stirring the powder using a ribbon blender or the like. Regarding the heat treatment conditions, in the case of polymerizable organosilicones, the heating temperature is 100 to 200°C, and the heating time is 3 to 1
8 hours, more preferably a heating temperature of 120 to 1
The temperature is 80°C and the heating time is 4 to 8 hours. When the heating temperature is low, the polymerization reaction is slow, so it may be necessary to lengthen the heating time. Furthermore, materials that are not heat resistant, such as organic dyes, need to be processed at low temperatures for long periods of time. Further, even if the polymerizable organosilicones are used, when the boiling point is low such as a 5t-H group-containing cyclic organopolysiloxane, the heating temperature is 70 to 140°C and the heating time is 3 to 18 hours. In this case, in order to avoid the organosilicones from evaporating and disappearing, it is desirable to use, for example, a blower dryer as the heating device, and set the airflow containing the organosilicones vapor to reflux. - side, heating temperature 200
In the case of the above-mentioned organosilicones which are non-polymerizable at temperatures below .degree. C., the heating temperature is 70 to 200.degree. C. and the heating time is 1 to 4 hours.

The organosilicones dispersed in the powder by the dry method uniformly cover the powder by this heating process. In particular, it is thought that methyl hydrodiene polysiloxane polysiloxane is fixed on the surface of the powder by the catalytic action of the powder during the heat treatment step, and a silicone network structure is formed.

Furthermore, the difference between the conventional production method and the present invention lies in the amount of solvent used during powder processing. In conventional manufacturing methods, even if the amount of solvent is relatively small, the amount of solvent for powders needs to be 6 to 15 parts by weight per 100 parts by weight of powder. However, after mixing and stirring the powders and organosilicones, the atomizer
Even though the secondary agglomerated particles were reduced by pulverization through processing, the secondary agglomeration of the powder was not completely eliminated. In this case, the agglomerates are only agglomerates that can be loosened by a weak force before the heat treatment, but they change into strong agglomerates by the next heat treatment step. Especially when using polymerizable organosilicones such as methylhydrodiene polysiloxane,
Forms stronger agglomerates. A similar phenomenon occurs when highly viscous organosilicones or oil agents are used. As a result of considering these causes, the present invention does not use a solvent,
Furthermore, by using organosilicones with low viscosity and sufficiently pulverizing the powder before heat treatment, we succeeded in obtaining modified powder with very little agglomeration even after heat treatment.

Furthermore, when the modified powder of the present invention is applied to decorative adhesives, resins, paints, adhesives, immobilization carriers, column packing materials for chromatography, etc., it has excellent ultraviolet scattering ability and Due to its excellent dispersibility, it is possible to obtain products with excellent storage stability.

〔Example〕

The present invention will be explained below with reference to Examples.

The test methods for cohesion and feel described in the Examples are as follows.

Moreover, all the viscosities described below are the viscosities at 25°C.

(1) - (Evaluation of cohesiveness) Particle size distribution measuring device (,,sK LASERMICRON
The average particle size of the modified powder was determined using ZERPRO-7000 Seishin Enterprise Q). The measurement conditions were as follows: ethyl alcohol was used as a dispersion solvent, and the modified powder was dispersed by operating the attached ultrasonic transmitter for 60 seconds.

- the particle size is Do, the particle size of the modified powder is D, and D/
Cohesiveness was evaluated from the D6 value as follows.

In addition, regarding the fine particle powder which cannot be measured by this device, the cohesiveness was evaluated by the method shown in (I)-■ below.

(1)-〇 (Evaluation of cohesiveness of fine particle powder) A photograph of the coated fine particle powder was taken using a transmission electron microscope, and the agglomeration state of the powder was evaluated as follows. The evaluation criteria were as follows: Untreated Powder (II) (Method for Evaluating the Feel of Powder) A total of 10 men and women between the ages of 20 and 50 were tested using the powders prepared in each Example and Comparative Example. The feel was evaluated. The numerical value indicates how many out of 10 people judged each evaluation item, and IO means all 10 people judged it, and 1 means that 1 out of 10 people judged it.

Example 1 30 g of methylhydrodiene polysiloxane (KF-99P viscosity 19 cst, manufactured by Shin-Etsu Chemical Co., Ltd. (Kiki)) was added to IKg of titanium oxide (particle size 0.6 μm) and mixed in a mixer.
Shredded. The obtained powder was transferred to a stainless steel vat and heat-treated at 180° C. for 8 hours using a blow dryer to obtain a modified powder, and the various experiments described above were carried out.

Comparative Example 1 A solution of 30 g of methylhydrodiene polysiloxane (KF-99P) dissolved in 120 g of isopropyl alcohol was added to IKg of titanium oxide (particle size 0.6 μm),
Mixing and pulverization were performed using a mixer. The conditions for pulverization were the same as in Example 1. The obtained powder was transferred to a stainless steel vat and heat-treated at 180° C. for 8 hours using a blow dryer to obtain a powder, and the various experiments described above were conducted.

Example 2 2 g of methylhydrodiene polysiloxane (KF-99P) was added to 100 g of yellow iron oxide (particle size: 0.7 μm), and the mixture was mixed and pulverized using a mixer. The obtained powder was transferred to a stainless steel vat and dried at 130°C using a blow dryer.
A heat treatment was performed at ℃ for 12 hours to obtain a modified powder, and the various experiments described above were conducted.

Comparative Example 2 A solution of 2 g of methylhytronene polysiloxane (KF-99P) dissolved in 10 g of isopropyl alcohol was added to 100 g of yellow iron oxide (particle size 0.7 μm), and the mixture was mixed and pulverized using a mixer. The conditions for pulverization were the same as in Example 2. The obtained powder was transferred to a stainless steel vat and heat-treated at 130° C. for 12 hours using a blow dryer to obtain a powder, and the various experiments described above were conducted.

Example 3 Methylhydrodiene polysiloxane (KF-99P) 0.5K to 1Kg of sericite (particle size 10.6μm)
g and methylhytronene polysiloxane (KF-99
0.5 kg of the mixture (01 viscosity 19C8t manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed and stirred using a Henschel mixer. The obtained powder was transferred to a stainless steel vat and heat-treated at 160° C. for 6 hours using a blow dryer to obtain a modified powder, and the various experiments described above were conducted.

Comparative Example 3 Methylhydrodiene polysiloxane (KF-99P) 5' Og to sericite (particle size 1016 μm) IKg
and methylhydrodiene polysiloxane (KF-990
1) A solution of 50 g dissolved in 100 g of trichloroethane was added and mixed and stirred using a Henschel mixer. The mixing and stirring conditions were the same as in Example 3.

The obtained powder was transferred to a stainless steel vat and heat-treated at 160° C. for 6 hours using a blow dryer to obtain a powder, and the various experiments described above were conducted.

Example 4 Zinc oxide (particle size 0.4 μm) loOg and methylpolysiloxane (KF-56 viscosity 5 cst manufactured by Shin-Etsu Chemical Co., Ltd.) 1
0 g was added, mixed and pulverized using a mixer. The obtained powder was transferred to a stainless steel vat and heat-treated at 120° C. for 4 hours using a blow dryer to obtain a modified powder, and the various experiments described above were conducted.

Comparative Example 4 A solution prepared by dissolving 20 g of methylpolysiloxane (KF-56) in 230 g of hexane was added to 200 g of zinc oxide (particle size: 0.4 μm), and the mixture was stirred and mixed using a mixer.

After distilling off the solvent using an evaporator, the obtained powder was pulverized using a mixer to obtain a powder, and the various experiments described above were conducted using the powder.

Example 5 Fluorine-modified silicone (X-22-822 viscosity 100 cst) was added to 100 g of nylon powder (particle size 14.0 μm).
Add 4g of Shin-Etsu Chemical (manufactured by Kiki) and mix with a mixer.
Shredded. The obtained powder was transferred to a stainless steel vat and heat-treated at 140° C. for 4 hours using a blow dryer to obtain a modified powder, and the various experiments described above were carried out.

Comparative Example 5 130 g of trichloroethane was added to 4 g of nylon powder (particle size 14.1zm) and 4 g of fluorine-modified silicone (X-22-s22), and the mixture was stirred and mixed using a mixer. After distilling off the solvent using an evaporator, the obtained powder is pulverized using a mixer to obtain a powder,
The above experiments were conducted.

Example 6 Spherical fine particle titanium oxide (average particle size 0.03 μm) 1Kg
Methylhydrodiene polysiloxane (KF-99P)
) 80 g were added and mixed by stirring using a Henschel mixer. Then, it was pulverized using an atomizer. The obtained powder was transferred to a stainless steel container and heat-treated at 150° C. for 8 hours using a blow dryer to obtain a modified powder, and the various tests described above were conducted.

Comparative Example 6 Spherical fine particle titanium oxide (average particle size 0.03 μm) IKg
Methylhydrodiene polysiloxane (KP-99P)
) A solution of 80 g dissolved in 120 g of isopropyl alcohol was added and mixed by stirring using a Henschel mixer. Then, it was pulverized using an atomizer. The stirring mixing and pulverizing conditions were the same as in Example 6. The obtained powder was transferred to a stainless steel container and dried using a blow dryer.
Heat treatment was performed at 50° C. for 8 hours to obtain powder, and the various tests described above were conducted.

Example 7 Methylhydrodiene polysiloxane (KF-99P) 5 was added to 100 g of fine particle zinc oxide (average particle size 0.03 μm).
g, and mixed and pulverized using a mixer.

The obtained powder was transferred to a stainless steel vat and heat-treated at 18'0° C. for 4 hours using a blow dryer to obtain a modified powder, and the various tests described above were conducted.

Comparative Example 7 5 methyl hydrodiene polysiloxane (KP-99P) was added to 100 g of fine particle zinc oxide (average particle size 0103 μm).
A solution prepared by dissolving 1.5 g in 7 g of isopropyl alcohol was added, and the mixture was mixed and pulverized using a mixer.

The conditions for pulverization were the same as in Example 7. The obtained powder was transferred to a stainless steel vat and dried at 180°C using a blow dryer.
Heat treatment was performed at ℃ for 4 hours to obtain a powder, and the various tests described above were conducted.

Example 8 Methylhydrodiene polysiloxane (KP-99
A mixture of 0.5 kg of P) and 0.15 kg of methylhydrodiene polysiloxane (KF-9901) was added, and the mixture was mixed and stirred using a Henschel mixer. Then, it was pulverized using an atomizer. The obtained powder was transferred to a stainless steel container and heated to 120°C using a blow dryer.
A heat treatment was performed for 8 hours to obtain a modified powder, and the various tests described above were conducted on the modified powder.

Comparative Example 8 Methylhydrodiene polysiloxane (KF-99P) 50 Ikg of fine black iron oxide (average particle size 0.01 μm)
g and methylhydrodiene polysoloxane (KF-99
01) A solution prepared by dissolving 50 g of cyclohexane I K g was added, and the mixture was mixed and stirred using a mixer.

The solvent was distilled off under reduced pressure, and the resulting powder was pulverized using an atomizer. The powder was transferred to a stainless steel container and heat-treated at 120° C. for 8 hours using a blow dryer to obtain a powder, and the various tests described above were performed.

Example 9 9 g of methylpolysiloxane (KF-56 viscosity 5 cst) in 100 g of fine titanium oxide (average particle size 0.06 μm)
was added, mixed and pulverized using a mixer. The obtained powder was transferred to a stainless steel vat and dried using a blow dryer.
A heat treatment was performed at 150° C. for 4 hours to obtain a modified powder, and the various tests described above were conducted.

Comparative Example 9 9 g of methylpolysiloxane (KF-56 viscosity 5 cst) in 100 g of fine titanium oxide (average particle size 0.06 μm)
A solution prepared by dissolving 180 g of hexane was added thereto, and the mixture was stirred and mixed using a mixer. After distilling off the solvent using an evaporator, the obtained powder was mixed and pulverized using a mixer to obtain a powder, and the various tests described above were conducted.

Example 10 200 g of octamethylcyclotetrasiloxane (SH244 viscosity 2.5 cst bundle, manufactured by Dow Corning Silicone Co., Ltd.) was added to IKg of ultramarine blue (particle size 1.0 μm),
Mixing and pulverization were performed using a mixer. The obtained powder was transferred to a stainless steel hat, and heat-treated at 70° C. for 1 hour using a blow dryer to obtain a modified powder.

Example 1I N-acylaspartic acid coated mica (particle size 11.0μ
m) Add 20g of methyl hydride 0 diene polysiloxane (viscosity 350cst) to IKg and mix with a mixer.
Shredded. The obtained powder was transferred to a stainless steel vat and heat-treated at 120° C. for 4 hours using a blow dryer to obtain a modified powder.

Example 12 60 g of olefin-modified soricone (KF-414 viscosity + 00 cst manufactured by Shin-Etsu Chemical Co., Ltd. (1 TL)) was added to Ikg of Teflon powder (particle size 16.0 μm), and mixed and pulverized using a mixer. The obtained powder was transferred to a stainless steel vat, and heat-treated at 170° C. for 9 hours using a blow dryer to obtain a modified powder.

Example 13 Ikg of silica beads (particle size 0.2mm) was mixed with methylhydrodiene polysiwaxane (SH1107C viscosity 25cs).
45 g (manufactured by Toshi, Dow Corning, Silicone) was added and mixed using a mixer. The obtained powder was transferred to a stainless steel vat and heat-treated at 160° C. for 10 hours using a blow dryer to obtain a modified powder.

Example 14 35 g of methylhydrodiene polysiloxane (SH1107C) to IKg of glass beads (particle size 0.2 mm)
was added and mixed using a vibration mixer. The obtained powder was transferred to a stainless steel vat and heated to +9 using a blow dryer.
A modified powder was obtained by heat treatment at 0'C for 4 hours.

Example 15 3 g of fluorine-modified silicone (X-22-822) was added to 1 kg of fine-particle titanium oxide (average particle size: 0.03 μm), and the mixture was stirred and mixed using a Henschel mixer. Then, it was pulverized using an atomizer. The obtained powder was transferred to a stainless steel container and heat-treated at 120° C. for 2 hours using a blow dryer to obtain a modified powder.

Example 16 Decamethylcyclopentanoloxane (SH-245 viscosity 4
．． 2cs (manufactured by Dow Corning Silicone) was added to the mixture, and the mixture was stirred and mixed using a Henschel mixer. Then, it was pulverized using an atomizer. The obtained powder was transferred to a stainless steel container and heated at 90°C for 2 hours using a blow dryer. It can be seen that, unlike powders obtained by manufacturing methods, powders with less secondary aggregation and excellent texture can be obtained.

〔Effect of the invention〕

As described above, the present invention is useful as a raw material for cosmetics, resins, paints, adhesives, immobilization carriers, column packing materials for chromatography, etc., with little secondary aggregation, excellent water clarity, and dispersibility. It is clear that a modified powder having the following properties can be obtained.

Procedural amendment February 26, 1991 1990 Patent Application No. 319'379 2 Name of the invention Modified powder 4 3. Relationship with the person making the amendment Patent applicant's address Sumida Go, Sumida-ku, Tokyo Chome 17-4 Name (095
) Kanebo Co., Ltd. 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka 534, Japan Patent Department Tel: (06) 921-1251 4. Date of amendment order 5. Number of claims increased by amendment None 6 ．． In the specification to be amended, "Detailed Description of the Invention, Column 7, Contents of Amendment 1) "Excellent Product" in Line 6, Page 1 O of the Specification is amended to read "Excellent Cosmetics, etc." I will.

2) On page 14, line 11 of the specification, "manufactured by Shin-Etsu Chemical Co., Ltd." will be corrected to "manufactured by Shin-Etsu Chemical Co., Ltd. flit."

3) The rKF-56 viscosity 5C3tJ on page 15, line 9, page 19, line 16, and page 20, line 4 of the specification will be corrected to rKF-96A viscosity 20C3tJ.

4) On page 15, line 17 of the specification, "(KF-56)" will be corrected to r(KF-96A viscosity 20cst)J.

5) [Table 1] on page 24 of the specification will be amended as follows. (Corrected parts are underlined) Table 1 and above

Claims (1)

[Claims] After mixing and stirring powders and organosilicones having a viscosity of 1 to 350 cst at 25°C at a weight ratio of powders and organosilicones of 100:0.3 to 100:20, Modified powder obtained by heat treatment.