JPH06304469A - Fluorocompound-containing capsule and method for molding fluorocompound-containing molded item - Google Patents

Abstract

PURPOSE:To obtain a fluorocompd.-contg. capsule which does not generate slippage on the surface of a mixer and can be mixed with a synthetic resin by coating a liq. substance wherein the fluorocompd. is a main component with a coating material for capsule. CONSTITUTION:This fluorocompd.-contg. capsule is prepd. by coating a liq. substance wherein a fluorocompd. is a main component with a coating material for capsule. The content of the capsule is a liq. substance wherein a fluorocompd. which has properties giving lubricating properties, nontackiness, low critical surface tension, etc., to a synthetic resin when it is mixed with the synthetic resin is a main component. The coating material for capsule consists of a material wherein e.g. gelatin, Japanese gelatin, carageenan, plasticized glycerol is a base material and physical properties wherein when the capsule is mixed with a matrix material such as a synthetic resin, good mixing can be performed and, at this instance or thereafter, the capsule is destroyed and the content uniformly mixed with the synthetic resin, is required.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a capsule for satisfactorily mixing a fluorine compound with a synthetic resin or the like, and to a capsule containing a liquid substance of the fluorine compound as a content.

[0002]

2. Description of the Related Art Conventionally, liquid fluorine compounds have been used in vacuum pump oils for semiconductors, mechanical lubricating oils for high heat, and semiconductors because of their inertness, chemical resistance, heat resistance and weather resistance. It is used as a leak detector.

Particularly in recent years, liquid fluorine compounds have attracted attention for their lubricity and non-adhesiveness, and since they are low-molecular and have a low critical surface tension, they tend to be deposited on the surface when mixed with a synthetic resin. Applications have been opened up for addition as surface modifiers for synthetic resins. However, when mixed with a synthetic resin or the like, it slips on the surface of the mixer due to its lubricity and is difficult to mix in the synthetic resin, which makes the work extremely difficult. Therefore, although it is expected that the synthetic resin can be modified, its application to many applications is delayed.

The present invention has been made in view of the above problems, and an object thereof is to be able to mix with a synthetic resin or the like without causing slippage on the mixer surface, as in the conventional synthetic resin additive. It is to provide a capsule containing a fluorine compound.

[0005]

That is, the present invention relates to a fluorine compound-containing capsule obtained by coating a liquid material containing a fluorine compound as a main component with a capsule coating material.

[0006]

Functions and Examples The contents of the capsule of the present invention contain a fluorine compound having a property of imparting, for example, lubricity, non-adhesiveness, low critical interfacial tension, etc. to a synthetic resin when mixed with the synthetic resin. It is a liquid substance that is the main component.

As such a liquid material, a matrix material in a liquid state, such as a fluorine compound or a dispersion or suspension thereof which is a liquid itself, or a dispersion, suspension or slurry of a fluoropolymer in the form of a solid powder, is used. Some are difficult to mix.

Preferred liquid fluorine compounds include, for example, perfluoropolyether oils, trifluorochloroethylene low polymers, carboxylates having perfluoroalkyl groups, ammonium salts, ethylene oxide adducts,
Examples thereof include compounds such as betaine. As a medium for making these liquid compounds into dispersions and suspensions, trichlorotrifluoroethane, 1,1-dichloro-1-fluoroethane, pentafluoropropanol,
Examples include pentafluorodichloropropane, perfluoropolyether, perfluorotrianneamine, perfluoroperhydrophenanthrene and the like.

As the solid powdery fluoropolymer,
For example, a polymer mainly containing acrylate or methacrylate having a perfluoroalkyl group or a monohydrofluoroalkyl group can be used. Examples of media for obtaining dispersions, suspensions and slurries from these solid powdery polymers include the above media and fluororesins such as PTFE dispersed in the above media or high boiling organic solvents.

It goes without saying that a plurality of the above-mentioned fluorine compounds and fluorine-containing polymers may be contained in the capsule as contents.

In addition to the above-mentioned fluorine compound, fluorine-containing polymer, and medium, the contents include additives usually used for modifying synthetic resins, for example, ultraviolet absorbers such as benzophenone, flame retardants such as bromine compounds, and the like. You may stay.

The coating material for the capsule of the fluorine compound-containing capsule of the present invention comprises a material based on one or more of gelatin, agar, carrageenan and plastic glycerin.

This coating material for capsules is well mixed when the capsule of the present invention is mixed with a matrix material such as a synthetic resin, and at that time or thereafter, the capsule is broken and the content is changed to a synthetic resin or the like. It is required to have physical properties such that they can be uniformly mixed. That is,
It is necessary to have appropriate elasticity and strength, and depending on the application, a material that melts by heating during mixing or molding is preferable. Further, it is preferable that this coating material is one that is incinerated or vaporized by heating during mixing or during molding. It is desired that the residual resin does not adversely affect the synthetic resin. Furthermore, it is desirable to select a material that does not block the capsules during storage.

In the present invention, the shape of the capsule is an oval shape, an oblong shape, a bottle shape, a spherical shape, an irregular shape, etc.,
The size (average of maximum diameter) is 0.5 mm to 50 m
m, especially about 0.5 mm to 5 mm is preferable. The thickness of the capsule depends on the purpose and the material, but is 10 μm to 50 μm.
0 μm, particularly 100 μm or less is preferable.

The capsules of the present invention can be manufactured by various methods. For example, the following conventional microencapsulation method, that is, a punching method such as a flat plate method and a rotary die method, and a dropping method can be used.

The punching method is a method in which two sheets of the coating material for capsules are combined and punched into each capsule shape by a die, and heat sealing of the sheet, capsule molding,
The capsule contents are filled at the same time (flat plate method). The rotary die method is a mechanized method of this.
The band-shaped coating material for capsules is fed from both sides into a rotating cylindrical mold, and the contents are press-fitted by a piston interlocked with this, and the capsules are formed by pressing off both molds. At this time, the capsule coating film is heated to an appropriate temperature by the die, and a capsule having a perfect adhesive surface is formed by pressure and heat sealing.

In the dropping method, the coating material liquid wraps the contents and spheres are formed by cutting the flow of a two-layer liquid consisting of the coating material liquid for capsules on the outside of the double nozzle and the capsule contents liquid on the inside. It is formed. The spheres are encapsulated by being placed in a coating material solution or a solution that does not dissolve the coating material.

With respect to the shape of the capsule, various shapes such as an oval shape, an oblong shape, a bottle shape, a spherical shape, and an irregular shape can be selected by the punching method. The size (average value of the maximum diameter) can be about 1 mm to 5 cm. The film thickness of the capsule is 10 μm to 50
It can be 0 μm. According to the dropping method, the shape of the capsule is limited to the spherical shape or the oval shape, the size (average value of the maximum diameter) is about 0.5 mm to 10 mm, and the film thickness of the capsule can be set to 10 μm to 300 μm. .

The capsule of the present invention and the matrix material are mixed by various means. When a matrix material such as synthetic resin or rubber is used, the compounding amount of the capsule with respect to the matrix material is measured, and then the capsule and the matrix material are dry-mixed with a mixer such as a tumbler mixer or a blender. At the start of mixing, the capsule contents, for example, the liquid fluorine compound do not touch the surface of the mixer, so that the capsule and the matrix material are mixed well. There is a case where the capsule is gradually broken during mixing due to mechanical force and heat during mixing and the fluorine compound is uniformly mixed with the matrix material. According to the prior art, it was difficult to uniformly mix the liquid fluorine compound with this tumbler mixer.

Dry mixing can be referred to as premixing before molding. That is, the mixture obtained by the premix is put into an extrusion molding machine equipped with a kneader or a twin-screw extruder, or a hopper of an injection molding machine to be molded. It is preferable that, when the liquid fluorine compound is charged into the molding machine, the capsule is broken by the mechanical force and heat in the molding machine so that the liquid fluorine compound is uniformly mixed in the mixture. When slippage of the mixture in the molding machine becomes a problem, it is desirable that the capsules thus uniformly mixed in the molding machine break for the first time in the molding machine.

Specific examples of the matrix material include olefin resins such as polyethylene and polypropylene, thermoplastic resins such as polyvinyl chloride, polyamide and polyester resins, thermosetting resins such as phenol resins, melamine resins and epoxy resins, Examples include natural rubber and synthetic rubber such as isoprene. The matrix material is
Liquids, powders, pellets, lumps, fibrous materials and woven and non-woven fabrics are mixed with the capsule of the present invention.

A fluorine compound-containing molded article is obtained by mixing the above-mentioned fluorine compound-containing capsule of the present invention with a matrix material and molding. Examples of the matrix material include synthetic resins, rubbers, paints, films, fibrous and woven fabrics, non-woven fabrics, and the like, and multilayer structures such as bonding and coating are included. For example, a synthetic resin containing a fluorine compound is molded into a specific shape using a mold, a coating material obtained by applying a coating material containing a fluorine compound and heating the molded body, a fluorine compound. A film obtained by rolling and stretching a film material containing a, a film processed material, and the like are included.

When the matrix material is a coating material, capsules are present in the coating material, and coating is carried out in that state, and then the capsules are destroyed by heating, and the fluorine-based content of the content in the coating film. The compounds are mixed and the coating film surface is modified, for example, surface lubricity is imparted.
In the case of film material, the capsule is broken in the molding machine during film molding, similar to molding with synthetic resin mold,
The fluorine compound is mixed in the film material, and a film is formed in that state, and for example, the surface antifouling property which is a property of the fluorine compound is imparted.

It is preferable that the capsule coating material is incinerated or vaporized after the capsule coating is melted by heating during the mixing or injection molding and the liquid content is uniformly mixed. A part of the capsule coating material may remain in the synthetic resin, but there is no problem as long as it is a small amount that does not affect the properties of the synthetic resin molded body.

As described above, for example, the fluorine compound-containing capsule of the present invention and the matrix material powder or pellets are dry-mixed and then molded to obtain the characteristics of the fluorine compound, that is, lubricity, non-adhesiveness, and low critical interfacial tension. It is possible to easily produce a fluorine compound-containing molded product having, for example, More specifically, it can be used as an antifouling wall material for building interior and exterior walls using the capsule of the present invention, an external structural material that imparts antifouling properties for home appliances, a mechanical component material such as gears that imparts surface lubricity, etc. A molded article containing a different fluorine compound is produced.

Next, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.

Example According to the dropping method, perfluoropolyether oil (Demnum Oil S-20 manufactured by Daikin Industries, Ltd.) was supplied from a nozzle inside a double-nozzle type liquid container pump.
A solution of gelatin in water (concentration 50
%), And the liquid is separated by introducing vibration, and the separated liquid is introduced into ethyl acetate to be encapsulated, and then ethyl acetate is dried to obtain a diameter of about 1 mm,
Spherical microcapsules having a film thickness of 20 μm were formed. Approximately 2 mg of perfluoropolyether oil was contained in the capsule, and the total weight of the capsule was 3 m.
It was g. 150 g of this microcapsule was weighed with respect to 10 kg of pellet-shaped (average particle size 3 mm) polyamide (nylon-66), and dry-mixed with a tumbler mixer. This mixing was carried out without problems, and a homogeneous mixture was obtained. This mixture was put into a hopper of an injection molding machine and molded under normal molding conditions (molding temperature 280 ° C.).
In this method, the capsules were broken during mixing and the demnum oil S-20 was mixed uniformly. The broken capsule was vaporized by the heat during injection molding and did not remain in the molded body.

Using this molded body and a molded body of nylon-66 alone molded under the same conditions as test pieces, the contact angle to water and the coefficient of static friction (Bauden-Leben type measuring instrument (steel ball load 1 kg)) were measured. The results are shown in Table 1.

Comparative Example 1 10 kg of the nylon-66 pellets used in the examples
In contrast, the demnum oil S-20 used in the examples was 150
Weighed g and tried to knead them with a kneader, roll, or twin-screw extruder, but slippage occurred on the resin surface and the wall surface of the kneader, and the kneading effect due to mechanical force did not occur, and kneading could not be done. .

Comparative Example 2 Nylon-66 was pulverized to obtain a powder having an average particle size of about 50 μm. To 10 kg of this powder, 150 g of demnum oil S-20 used in the example was weighed and mixed with a tumbler mixer while adding the oil little by little so that the powder of the matrix would absorb it.
After kneading little by little with a kneader, the mixture was further kneaded with a twin-screw extruder to obtain a compound. The kneading was carried out under the condition that it was difficult to knead by slipping a little. Since the powder of the matrix absorbed the oil and the mixture was in a powder state, it was easy to apply mechanical force, so that kneading could be managed somehow. This kneaded product was put into an injection molding machine in the same manner as in the example to obtain a molded body, and the contact angle and the coefficient of static friction were measured under the same conditions as in the example. The results are shown in Table 1.

[0031]

[Table 1]

As shown in Table 1, it can be seen that the molded product using the microcapsules of the present invention has excellent surface lubricity and non-adhesiveness due to good mixing of demnum oil S-20.

[0033]

According to the capsule of the present invention, the fluorine compound can be uniformly mixed with the synthetic resin or the like without causing slippage on the mixer surface. In addition, since the liquid fluorine compound, which is inconvenient to handle, can be handled as a solid such as powder or granules and dry mixing is possible, the liquid fluorine compound can be applied to many applications.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08J 3/20 Z 9268-4F // C08L 77:00

Claims (5)

[Claims] 1. A fluorine compound-containing capsule in which a liquid material containing a fluorine compound as a main component is coated with a capsule coating material. 2. The capsule according to claim 1, wherein the fluorine compound is liquid. 3. The capsule according to claim 2, wherein the liquid fluorine compound is perfluoropolyether oil, a low polymer of ethylene trifluoride chloride or a compound having them in a part of the molecule. 4. The capsule according to claim 1, 2 or 3, wherein the coating material for capsule is based on gelatin, agar, carrageenan, or glycerin. 5. A method of molding a fluorine compound-containing molded body, which comprises dry-mixing the fluorine compound-containing capsule according to claim 1, 2, 3 or 4 and matrix material powder or pellets and then melt-molding the mixture.