JP2000000449A - Continuous production of organopolysiloxane water based liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for continuously producing a grease like organopolysiloxane water based liquid having small emulsion particle diameter with hardly generating shear exothermic heat with improved productivity without pressurizing by the use of an organopolysiloxane which is liquid at the normal temp., an emulsifier and water as raw materials. SOLUTION: An organopolysiloxane liquid at the normal temp. by 100 pts.wt., an emulsifier by 0.1-100 pts.wt. and water by 0.5-20 pts.wt. are supplied from an upper part supply port of a continuous mixing device and the grease like organopolysiloxane water based liquid having >=100 Pa.s (25 deg.C) viscosity is taken out from a lower part discharge port of the continuous mixing device. The mixing device is constructed by providing a rotary disk 5 inside of a easing 1 provided with the supply port 2 of raw materials at the upper part and the discharge port 3 at the lower part, dividing the inside of the casing 1 into an upper mixing section 6 and a lower mixing section 10 with the rotary disk 5, arranging scrapers 7 and 9 respectively on the front surface and the back surface of the rotary disk, attaching a ring plate 11 on the inside wall of the lower mixing section, and inserting the inner peripheral end of the ring plate into a notch provided on the scraper 8 of the back surface side of the rotary disk in non-contact state to enable the scraper under the inserted state to be relatively movable to the ring plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for continuously producing an aqueous grease-like organopolysiloxane liquid having a small emulsion particle size.

[0002]

2. Description of the Related Art Conventionally, as a method of producing an O / W emulsion by dispersing a hydrophobic liquid such as fats, oils, paraffins, and synthetic oils in water, these hydrophobic liquids are mixed with an emulsifier, a protective colloid and the like together with a propeller. A method of emulsifying in water using an apparatus such as a stirrer, a colloid mill, a homogenizer, and an ultrasonic emulsifier has been widely adopted. However, silicone oils are extremely difficult to produce stable aqueous emulsions due to their extremely high hydrophobicity. For this reason, a method has been proposed in which an emulsifier and a relatively small amount of water are added to silicone oil to give a relatively high-viscosity paste-like substance by applying a strong shearing force by milling the roll, and then this is diluted with water to form an aqueous emulsion. Yes
0162 publication). However, this method has a problem that oil spots and oil separation occur in the emulsion diluted with water. This phenomenon was caused by the fact that water is evaporated during shear kneading because the roll is kneaded in the atmosphere. In order to solve this problem, a raw material consisting of silicone oil, emulsifier and water is continuously supplied into a cylindrical container equipped with a shear stirring mechanism,
There has been proposed a method of producing a grease-like aqueous silicone liquid by carrying out shearing and stirring at a shear rate of at least 501 / sec while maintaining the inside of the container at a pressure of 0.049 MPa or more (Japanese Patent Publication No. No. 59-51565). However, when a grease-like aqueous silicone liquid is produced by shearing under pressure, the temperature becomes high due to shear heat, so that the emulsifier is altered and a grease-like aqueous silicone liquid having a small emulsion particle diameter is obtained. There was no problem. On the other hand, as an inexpensive device for producing an aqueous emulsion of oil with a small heating value and no pressurization, a rotating disk is provided in the casing, which is divided into an upper kneading chamber and a lower kneading chamber. There has been proposed a continuous kneading apparatus having a structure equipped with a scraper (Japanese Patent Publication No. 57-984).
However, when emulsifying silicone oil with this kneading apparatus, emulsion particles tend to be large, and if the rotation of the rotating disk is increased, it is difficult to obtain a grease-like aqueous silicone liquid. I found it.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to prepare a grease-like organopolysiloxane aqueous liquid having a small emulsion particle size from a liquid organopolysiloxane, an emulsifier and water at room temperature with little heat generation by shearing. It is an object of the present invention to provide a method of continuously producing a product with good productivity without pressurizing.

[0004]

The object of the present invention is to provide a liquid organopolysiloxane at room temperature in an amount of 100 parts by weight, an emulsifier of 0.1 to 100 parts by weight.
Parts by weight and 0.5 to 20 parts by weight of water, a raw material supply port is provided at the top, a rotating disk is provided inside a casing provided with a discharge port at the bottom, and the inside of the casing is mixed with the upper mixing chamber and the lower mixing chamber by the rotating disk. Chambers, and a scraper is disposed on each of the upper and lower surfaces of the rotating disk. A ring plate is attached to the inner wall of the lower mixing chamber, and an inner peripheral end of the ring plate is provided on a scraper on the lower surface of the rotating disk. The scraper is inserted into the notch in a non-contact state, and the scraper is supplied from the upper supply port of the continuous mixing apparatus in which the scraper is relatively movable with respect to the ring plate under the inserted state.
This is achieved by continuously taking out an aqueous grease-like luganopolysiloxane liquid having a viscosity of not less than a · s (25 ° C.).

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The continuous mixing apparatus used in the present invention is described in JP-A-8-975. Although the publication states that the mixing apparatus is useful for continuous mixing of liquid and powder, the present inventors have found that the mixing apparatus is also effective for emulsifying a liquid organopolysiloxane at room temperature in water, and that the emulsion particle size is small. A grease-like organopolysiloxane aqueous liquid with a small particle size can be produced with little heat generation due to shearing, without pressurization, and even when the number of discharges is increased by increasing the rotation speed of the rotating disk, the grease having a small emulsion particle diameter. Found that aqueous organopolysiloxane liquids can be prepared,
The present invention has been completed.

In the present invention, a raw material supply port is provided at the upper part,
A rotating disk is provided inside a casing provided with a discharge port at a lower portion, the inside of the casing is divided into an upper mixing chamber and a lower mixing chamber by the rotating disk, and scrapers are arranged on the upper surface and the lower surface of the rotating disk, respectively. A ring plate is attached to the inner wall of the casing, and the inner peripheral end of the ring plate is inserted into a notch provided in a scraper on the lower surface of the rotating disk in a non-contact state, and the scraper is inserted into the ring plate under the inserted state. The organopolysiloxane liquid at room temperature is continuously emulsified in water using a continuous mixing device which is relatively movable.

FIG. 1 is a longitudinal sectional view of one embodiment of a continuous mixing apparatus main body 15, and FIG. 2 is a sectional view taken along the line AA. In these figures, a casing 1 forming an outer shell of a mixing device main body 15 is provided with a supply port 2 for receiving a raw material in the center of an upper plate 1a, and a lower portion is formed on an inverted conical inclined surface 1b. Outlet 3 is provided. Further, a conical portion 12 is provided in the center of the lower portion, and forms an annular V-groove bottom portion with the inclined surface 1b. The lower end of the liquid supply pipe 4 faces above the supply port 2 of the continuous mixing device main body 15, and the raw material is supplied from the liquid supply pipe 4 to the inside of the casing 1 via the supply port 2. A rotary disk 5 is provided horizontally inside the casing 1 of the continuous mixing apparatus main body 15 so as to face the supply port 2. The rotary disk 5 allows the inside of the casing 1 to perform the first-stage mixing. It is divided into a mixing chamber 6 and a lower mixing chamber 10 for performing the second-stage mixing. The rotating disk 5 has a rotation center fixed to an upper end of a rotating shaft 13, and a pulley 14 fixed to a lower end of the rotating shaft 13, and rotational power is input to the pulley 14 from a motor (not shown). The rotation speed of the rotating disk 5 is
A range from 500 to 10,000 rpm is preferred. On the rotating disk 5, three upper scrapers 7, three side scrapers 8, and three lower scrapers 9 are mounted on the upper, outer, and lower surfaces, respectively, at equal angles, and the raw materials are mixed by the stirring action and scraping action of these scrapers. Is done. The upper scraper 7 scrapes the mixture near the upper plate 1a, the side scraper 8 scrapes the mixture near the inner wall of the casing at the boundary between the upper mixing chamber 6 and the lower mixing chamber 10, and the lower scraper 9 tilts the lower part of the casing 1. The mixture in the vicinity of the surface 1b is agitated and mixed by scraping the mixture.

The number of the upper scraper 7, the side scraper 8, and the lower scraper 9 does not necessarily need to be three as shown in the figure, but may be any number of one or more. It may be a different number. The side scraper is preferably present, but is not essential. Further, a number of pins may be provided on the upper surface of the rotating disk 5 as needed, and the stirring action of these pins may further promote the stirring and mixing. The lower scraper 9 has a plate shape or a lattice plate shape extending in the radial direction and the vertical direction, and is provided with a notch 9a extending horizontally inward from an outer end in the radial direction. Further, a ring plate 11 is fixed to the inner wall of the casing 1 corresponding to the position of the notch 9a, and is inserted in a non-contact state so that an inner peripheral end of the ring plate 11 intersects the notch 9a. Have been. In this inserted state, the scraper 9 can move relative to the ring plate 11. Basically, the lower scraper 9 is fixed to the rotating disk 5, but the driving system of the rotating disk 5 and the scraper 9 may be different.

In the production method of the present invention, the organopolysiloxane liquid at room temperature to be emulsified is continuously charged together with the emulsifier and water from the liquid supply pipe 4 of the above-described continuous mixing apparatus main body 15, but is supplied at 100 Pa · s. To obtain an aqueous grease-like organopolysiloxane liquid having a viscosity of s (25 ° C.) or higher, an organopolysiloxane liquid at room temperature is used.
The emulsifier is used in an amount of 0.1 to 100 parts by weight, preferably 0.3 to 30 parts by weight, and water is used in an amount of 0.2 to 20 parts by weight, preferably 0.5 to 16 parts by weight, based on 100 parts by weight. When the amount of water is less than 0.2 parts by weight, it is difficult to obtain an O / W type grease-like substance. On the other hand, when the amount is more than 20 parts by weight, the viscosity of the mixed system of the charged components decreases, and And it becomes difficult to obtain a stable aqueous grease-like organopolysiloxane aqueous solution.

The organopolysiloxane which is liquid at room temperature as a raw material depends on the type of the emulsifier to be used, but is usually a few mPa · s or more, preferably 0.1 to 70 Pa · s, as long as it is a hydrophobic oily substance. Any type may be used. This includes
Dimethylpolysiloxane, methyloctylpolysiloxane, methylvinylpolysiloxane, dimethylsiloxane / methylvinylsiloxane copolymer, dimethylsiloxane / methylphenylsiloxane copolymer, dimethylsiloxane / diphenylsiloxane copolymer, Dimethylsiloxane / methylphenylsiloxane / methylvinylsiloxane copolymer or methyl (3,3,3-trifluoropropyl) polysiloxane, dimethylpolysiloxane with dimethylvinylsiloxy groups at both ends blocked, dimethylsiloxane / methylvinylsiloxane copolymer Copolymer, dimethylsiloxane / methylphenylsiloxane copolymer or dimethylsiloxane / diphenylsiloxane / methylvinylsiloxane copolymer, both ends of molecular chain Xyl-blocked dimethylpolysiloxane, methylvinylpolysiloxane, dimethylsiloxane / methylvinylsiloxane copolymer, dimethylsiloxy / methylphenylsiloxane copolymer or methyl (3,3,3-trifluoropropyl) polysiloxane However, in the case of a vinyl group-containing polysiloxane, it may contain an organohydrogen polysiloxane or a platinum compound.

As the emulsifier, those conventionally used for emulsifying silicone oil can be appropriately selected and used. These include long-chain alkyl sulfates, long-chain alkyl sulfonates, anionic surfactants such as sodium polyoxyethylene alkyl phenyl ether sulfate, cationic surfactants such as benzyl ammonium salt, polyoxyethylene alkyl phenyl ether, polyoxyethylene Non-ionic surfactants such as alkyl ethers and sorbitan monoesters are exemplified, but polyether-modified silicone oils and aminopolyether-modified silicone oils may also be used. In addition to emulsifiers, polyvinyl alcohol as protective colloid or thickener,
Water-soluble polymers such as methylcellulose, carboxymethylcellulose and hydroxymethylcellulose, dyes and fillers may be added.

The components may or may not be premixed in advance, and the components may be supplied to the supply port 2 of the main body 15 at a predetermined ratio. Each of the supplied components descends from the supply port 2 to the upper mixing chamber 6 and moves radially outward on the rotating disk 5 while rotating on the rotating disk 5.
And the scraping action of the upper scraper 7 causes the mixing action of the first step surface. The mixture subjected to the first-stage mixing action falls onto the ring plate 11 from the outer peripheral edge of the rotating disk 5, where the narrow notch 9 of the lower scraper 9 is formed.
a. This shear force is applied to the ring plate 1
It is even stronger because it is received between 1 and the narrow notch 9a. In addition, since the rotation speed of the rotating disk 5 can be changed from a low-speed rotation range to a high-speed rotation range, emulsification can be performed more efficiently by rotating at high speed. The emulsion that has been sheared by the ring plate 11 further falls on the inclined surface 1b, is also sheared while being scraped off by the end of the lower scraper 9, and is discharged from the discharge port 3 as a grease. If the pressure loss at the discharge port is large, the liquid overflows at the supply port 2, so that the outlet adjustment pressure at the discharge port 3 is preferably 0.49 MPa or less.

The aqueous grease-like organopolysiloxane solution thus obtained is an O / W emulsion, having a small emulsion particle size and excellent stability. It can be used as it is without dilution with water, or diluted with water, as a release agent, polishing agent, defoaming agent, fiber treatment agent, medical ointment, base for cosmetics and the like.

[0014]

Examples Examples of the present invention and comparative examples will be given. The viscosity is a value at 25 ° C. The viscosity of the grease was measured using a single cylindrical rotational viscometer (Vismetron VS-HW rotor N0.7, Shibaura System Co., Ltd.) at a rotational speed of 2.
Measured at 5 rpm. The particle size of the emulsion was measured with a laser particle size analyzer (manufactured by Horiba) after diluting with water so that the obtained grease-like substance became 50% by weight.

[0015]

EXAMPLE 1 100 parts by weight of a dimethylpolysiloxane capped at both ends with a trimethylsiloxy group having a viscosity of 3 Pa · s, 0.6 parts by weight of cetyltrimethylammonium chloride, and 1.4 parts by weight of water were continuously mixed using the individual metering pumps as shown in FIG. The liquid was supplied to the supply port 2 quantitatively from the liquid supply pipe of the main body 15. The diameter of the rotating disk 5 in the continuous mixing device main body 15 was 100 mm, and the width of the ring plate was 10 mm. Set the rotation speed of the rotating disk 5 to 1,500 rpm or 4,500 rpm, and
Is rotated and emulsified, the continuous mixing device body 15
Grease-like organopolysiloxane aqueous liquids having a temperature of 70 ° C. or less were obtained from the discharge port 3 of the above. After cooling these aqueous liquids to room temperature in a thermostat, the viscosity was measured, and the results are shown in Table 1. In addition, as a comparative example, emulsification was attempted under the same conditions using the same raw material, using the same continuous mixing device main body as the continuous mixing device main body 15 except that the ring plate 11 was not provided. The results are shown in Table 1.

[Table 1]

[0016]

Example 2 100 parts by weight of a dimethylpolysiloxane having a viscosity of 1 Pa · s and capped at both ends with a trimethylsiloxy group, an ethylene oxide adduct of a secondary higher alcohol (molecular weight: 40
6) 3 parts by weight and 6 parts by weight of water were quantitatively supplied to the supply port 2 from the liquid supply pipe 4 of the main body 15 of the continuous mixing apparatus used in Example 1 using individual metering pumps. The number of revolutions of the rotating disk 5 is set to 1,500 rpm or 3,000 rpm, and the rotating disk 5 is rotated to perform emulsification.
A grease-like organopolysiloxane aqueous solution having a temperature of 50 ° C. or less was obtained from the discharge port 3 of the above. These aqueous liquids were cooled to room temperature in a thermostat, and their viscosities were measured. The obtained grease-like organopolysiloxane aqueous liquid was diluted with water so as to have a concentration of 50% by weight, and the particle size of the obtained emulsion was measured. The results are shown in Table 2. As a comparative example, emulsification was attempted under the same conditions using the same raw material and the same raw material as the continuous mixing device main body 15 except that the ring plate 11 was not provided. The results are shown in Table 2.

[Table 2]

[0017]

According to the continuous production method of the present invention, a stable grease-like aqueous solution of luganopolysiloxane having a small emulsion particle diameter can be easily and continuously produced without applying pressure and hardly generating heat due to shearing. be able to. Even if the amount of discharge is increased by increasing the rotation speed of the rotating disk, the temperature of the discharge remains at 80 ° C., and a stable grease-like aqueous luganopolysiloxane liquid having a small emulsion particle diameter can be produced with high productivity.

[0018]

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a continuous mixing apparatus main body 15 used in an embodiment of the present invention.

FIG. 2 is a view taken along the line AA of FIG. 1;

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Casing 2 Supply port 3 Discharge port 4 Liquid supply pipe 5 Rotating disk 6 Upper mixing chamber 7 Upper scraper 8 Side scraper 9 Lower scraper 10 Lower mixing chamber 11 Ring plate 12 Conical part 13 Rotating shaft 14 Pulley 15 Main body of continuous mixing device

Continued on the front page (72) Inventor Hideyuki Mori 2-2 Chikusa Beach, Ichihara City, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd. Engineering Department (72) Inventor Toyohiko Yamadera 2-2 Chigusa Coast, Ichihara City, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd. Engineering Department (72) Inventor Mitsuo Hamada 2-2 Chigusa Coast, Ichihara-shi, Chiba Dow Corning Silicone Co., Ltd. Engineering Department F-term (reference) 4F070 AA60 AB24 AC12 AE14 AE28 CA03 CA17 CB03 CB13 4G035 AB38 AB40 AB41 AB54 AE13 4G078 AA08 AA10 AA26 AA30 AB05 AB20 BA05 CA08 CA09 DA23

Claims (3)

[Claims] 1. An organopolysiloxane 10 which is liquid at room temperature.
0 parts by weight, 0.1 to 100 parts by weight of emulsifier and 0.5 to 20 parts by weight of water, a raw material supply port is provided at the top, a rotating disk is provided inside a casing provided with a discharge port at the bottom, and the casing is provided by the rotating disk. The interior is divided into an upper mixing chamber and a lower mixing chamber, and scrapers are respectively arranged on the upper surface and the lower surface of the rotating disk, a ring plate is attached to the inner wall of the lower mixing chamber, and the inner peripheral end of the ring plate is The scraper is inserted into a notch provided in the scraper on the lower surface side of the rotating disk in a non-contact state. Under the inserted state, the scraper is supplied from an upper supply port of a continuous mixing device which is relatively movable with respect to the ring plate. A method for continuously producing an aqueous organopolysiloxane liquid, comprising continuously extracting a grease-like organopolysiloxane aqueous liquid having a viscosity of 100 Pa · s (25 ° C.) or more from a lower outlet of a mixing device. 2. The continuous production method according to claim 1, wherein the organopolysiloxane liquid at room temperature is a diorganopolysiloxane. 3. The continuous production method according to claim 2, wherein the diorganopolysiloxane is dimethylpolysiloxane.