JPH07164432A - Production of polymeric blend material - Google Patents

Abstract

PURPOSE:To produce a polymeric blend material containing a large amt. of a monomeric material uniformly and reduced in the bleeding of the monomeric material by kneading a thermoplastic polymeric material and a large amt. of the monomeric material using a high shearing special mixer. CONSTITUTION:A high shearing special mixer is constituted by providing a stator 2 having radial buffles 2A provided thereto in a protruding state and a rotor 3 having a turbine 3B attached to the lower part of the central bearing 3A thereof in a tank 1. When a thermoplastic polymeric material and a monomeric material are kneaded within the high shearing special mixer, both materials are sucked from the upper part of the stator 2 by the suction force generated by the high speed rotation of the turbine 3B and receives strong shearing action in the clearances (t) between the turbine 3B and the buffles 2A of the stator 2 to be emitted from emitting orifices 2B and deflected by a distribution plate 4 to be allowed to flow in the stator 2 from the bottom part of the tank 1 to be kneaded. Therefore, both materials are mixed in a uniformly dispersed state and a polymeric blend material reduced in the bleeding of the monomeric material and enhanced in characteristics is easily obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer blend material, and more particularly to a thermoplastic polymer blend material containing a large amount of liquid low molecular weight material uniformly and having little bleeding of the low molecular weight material. The present invention relates to a method for producing a polymer blend material which is suitably used in all industrial fields, particularly household appliances, sports equipment, industrial equipment, precision equipment, transportation equipment, construction, civil engineering, medical care, leisure and the like.

[0002]

2. Description of the Related Art At present, the progress of blending technology of polymer materials is remarkable, and improvement such as improvement of existing function and addition of new function by blending polymer material and polymer material or polymer material and low molecular weight material. Development of blended materials and polymer alloys that have been made.

Further, academically, researches on the mechanism of phase separation and development of physical properties in polymer blend materials have been widely conducted from the viewpoint of thermodynamic treatment and rheological consideration.

Particularly, thermodynamic studies have been actively conducted with the compatibility between materials and the temperature as basic parameters, and it has been reported that the phase structure of the blend material in the equilibrium state can be theoretically predicted.

As described above, the research on the phase separation mechanism in the compatible region, the metastable region, and the incompatible region of the polymer blend material has been actively conducted. On the other hand, at present, little attention is paid to the relationship between a method for producing a polymer blend material in a specific mixed state, a production apparatus therefor, and the obtained mixed state.

By the way, generally, the equipment for mixing and kneading the materials is a mixer intended for uniform dispersion with almost no shearing force, and the size of the constituent components by applying shearing force. Is roughly classified into a kneader for the purpose of uniformly dispersing the components.

The former mixers include ribbon blenders, tumble mixers, and Henschel mixers, which mainly utilize the rotation of stirring blades, and the latter mixers, which utilize the shearing action between two rolls or rotors. Rolls, Banbury mixers, single screw or twin screw extruders, etc. are commonly used.

[0008]

As described above, in the research of polymer blend materials, there has been little research on the relationship between the manufacturing method and the manufacturing apparatus and the obtained mixed state. It is not easy to mix the low molecular weight materials described above in order to form a uniform composition. For example, a general mixer can hardly achieve uniform dispersion,
In addition, even if you try to forcefully knead both materials using the above-mentioned commonly used general kneader, in many cases,
The polymer material cannot slide effectively between the rotors for effective kneading. Further, even when it seems that uniform mixing is performed at first glance, the low molecular weight material is likely to bleed to the surface in such incomplete kneading.

As described above, it is not possible to obtain a polymer blend material having a uniform dispersion and a low bleeding property by mixing the polymer material with a large amount of the low molecular weight material in the conventional general equipment.

It is to be noted that a low molecular weight material and a high molecular weight material having good compatibility are selected, and these are mixed for a long time (in an extreme case, a long time of up to several days) and swollen to form a polymer blend material. Although there is a method for obtaining it, such a method is unsuitable for industrial production because the material is limited and the production efficiency is extremely low.

The present invention solves the above-mentioned conventional problems, and kneads a thermoplastic polymer material and a low-molecular material to uniformly contain a large amount of the low-molecular material and to reduce the bleeding of the low-molecular material. It is an object to provide a method for easily and efficiently obtaining a molecular blend material.

[0012]

The method for producing a polymer blend material according to the present invention has the ability of a thermoplastic polymer material and a low molecular material to have a rotor shear rate of 5.0 × 10 ² sec ^-1 or more. It is characterized in that a thermoplastic polymer blend material containing a large amount of low molecular weight material uniformly and less bleeding of the low molecular weight material is obtained by kneading with a high shear type special mixer.

That is, the inventors of the present invention have studied in detail the relationship between the method for producing a polymer blend material, the phase structure of the polymer blend material obtained by the production method, and the physical properties thereof.
In kneading a thermoplastic polymer material and a large amount of low molecular weight material, by using a predetermined high shear type special mixer,
Both materials are uniformly dispersed on the order of micron to form a desirable phase structure, and as a result, special physical properties are expressed, and in the polymer blend material thus obtained, bleeding of a low molecular weight material occurs. The present invention has been completed by finding that it is extremely small, and further, by controlling this kneading condition, it is possible to obtain a polymer blend material in which the thermoplastic polymer material forms a three-dimensional continuous network skeleton structure. The following describes the present invention in detail, the high-shear type special mixer used in the present invention is one that can give a high shear force and a high shear rate between a fixed wall and a rotating rotor, and is basically Satisfies the following condition.

That is, the distance (clearance) between the fixed wall and the rotating portion (rotor) is t (m), the rotating peripheral speed of the rotor is v (m / sec), and the shearing speed V of the rotor is V =
When defined as v / t (sec ⁻¹ ), V ≧ 5.0 × 10 ² (sec ⁻¹ ) preferably V ≧ 1.0 × 10 ³ (sec ⁻¹ ) more preferably V ≧ 2.5 × 10 ³ (sec ⁻¹ ) Most preferably, V = ≧ 5.0 × 10 ³ (sec ⁻¹ ) is satisfied.

Incidentally, in the case of a general kneader, V is 10 ²
It is about (sec ⁻¹ ).

The clearance t between the fixed wall and the rotor of the high shear type special mixer having such a shear rate is t
≦ 3 × 10 ⁻³ m is preferable, more preferably t ≦ 2 × 1
0 ⁻³ m, most preferably t ≦ 1 × 10 ⁻³ m. The rotation speed v ′ of the rotor is preferably v ′ ≧ 100 rpm, more preferably v ′ ≧ 300 rpm, further preferably v ′ ≧ 500 rpm, and most preferably v ′ ≧ 1.
000 rpm.

The mixer temperature at the time of kneading is basically the melting point of the thermoplastic polymer material used (when the polymer material has a crystal structure) or the glass transition point (where the polymer material has an aggregate structure). In some cases) it is preferable to keep the temperature higher. However, when the compatibility between the thermoplastic polymer material and the low molecular weight material to be used is extremely good, it is possible to carry out the kneading at a temperature below the melting point or glass transition point.

The kneading time varies depending on other kneading conditions and the compatibility between the low molecular weight material used and the thermoplastic polymer material, but is usually 5 to 300 minutes, preferably 10 to 10.
It will be about 150 minutes.

Next, the thermoplastic polymer material and the low molecular weight material used in the present invention will be described.

In the present invention, the low molecular weight material is 100 ° C.
At a viscosity of 5 × 10 ⁵ centipoise or less, the solubility parameter values δ (= ΔE / V) ^{1/2 of} the low molecular weight material and the thermoplastic polymer material, ΔE = molar evaporation energy, V = The difference in molar volume) is preferably 3.0 or less.

First, for low molecular weight materials, the viscosity at 100 ° C. is 5 × 10 ⁵ centipoise or less, especially 1 × 1.
Is preferably 0 ⁵ centipoise or less, from the viewpoint of molecular weight, number average molecular weight of the low molecular material 20,
000 or less, especially 10,000 or less, especially 5,000
It is preferably 0 or less. As such a low molecular weight material, a material that is liquid or liquid at room temperature is usually preferably used. Further, both hydrophilic and hydrophobic low molecular weight materials can be used. The low molecular weight material is not particularly limited,
The following are suitable:

Softeners: Mineral oil-based, vegetable oil-based, synthetic-based softeners for various rubbers or resins. Examples of the mineral oil-based oil include process oils such as aromatic oils, naphthene oils, and paraffin oils. As vegetable oils, castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil,
Examples include coconut oil, peanut oil, wood wax, pine oil, olive oil and the like.

Plasticizers: various ester plasticizers such as phthalic acid esters, phthalic acid mixed group esters, aliphatic dibasic acid esters, glycol esters, fatty acid esters, phosphoric acid esters, stearic acid esters, epoxy plasticizers, etc. Plasticizer for plastics or phthalate type,
Adipate-based, sebacate-based, phosphate-based, polyether-based, polyester-based, etc. plasticizers for NBR.

Tackifier: Various tackifiers such as coumarone resin, coumarone-indene resin, phenol terpene resin, petroleum hydrocarbon and rosin derivative (tackifier).

Oligomer: Crown ether, fluorine-containing oligomer, polyisobutylene, xylene resin, chlorinated rubber, polyethylene wax, petroleum resin, rosin ester rubber, polyalkylene glycol diacrylate,
Liquid rubber (polybutadiene, styrene-butadiene rubber, butadiene-acrylonitrile rubber, polychloroprene, etc.), silicone-based oligomers, various oligomers such as poly-α-olefins.

Lubricants: Hydrocarbon lubricants such as paraffin and wax, fatty acid lubricants such as higher fatty acids and oxyfatty acids, fatty acid amide lubricants such as fatty acid amides and alkylenebisfatty acid amides, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters. , Ester-based lubricants such as fatty acid polyglycol esters, alcohol-based lubricants such as fatty alcohols, polyhydric alcohols, polyglycols and polyglycerols, various lubricants such as metal soaps and mixed lubricants.

In addition, latex, emulsion, liquid crystal, bituminous composition, clay, natural starch, sugar, inorganic silicone oil, phosphazene and the like are also suitable as the low molecular weight material. Further, animal oil such as beef oil, pig oil, horse oil, bird oil or fish oil: honey, fruit juice, or dairy products such as chocolate and yogurt, hydrocarbon-based, halogenated hydrocarbon-based, alcohol-based, phenol-based, ether System, acetal system, ketone system, fatty acid system, ester system,
Nitrogen compound-based, sulfur compound-based organic solvents: or various medicinal components, soil modifiers, fertilizers, petroleum, water, aqueous solutions and the like can also be used.

On the other hand, as the thermoplastic polymer material, any material can be used as long as it can hold a large amount of the low molecular weight material as described above and can form a composite. A molecular material or various materials having the polymeric material as a constituent element is used.

Specifically, styrene type (butadiene styrene type, isoprene styrene type, etc.), vinyl chloride type, olefin type (butadiene type, isoprene type, ethylene propylene type, etc.), ester type, amide type, urethane type, etc. Various thermoplastic elastomers and their hydrogenated and other modified products, styrene type, ABS type, olefin type (ethylene type, propylene type, ethylene propylene type, ethylene styrene type, propylene styrene type, etc.), vinyl chloride type, Acrylic ester type (methyl acrylate type), methacrylic acid type (methyl methacrylate type), carbonate type, acetal type, nylon type, halogenated polyether type (chlorinated polyether type, etc.), halogenated olefin type (Ethylene tetrafluoride, Fluorine-Ethylene chloride -Based, fluorinated ethylene-propylene-based), cellulose-based (acetyl cellulose-based, ethyl cellulose-based, etc.), vinylidene-based, vinyl butyral-based, alkylene oxide-based (propylene oxide-based, etc.) thermoplastic resins, and rubbers of these resins Examples include modified products.

As the thermoplastic polymer material, it is particularly preferable to use a material in which a portion easily forming a hard block such as a crystal structure or an agglomerate structure and a soft block such as an amorphous structure are mixed together.

Further, in obtaining a polymer blend material containing a large amount of a low molecular weight material with a large amount of a low molecular weight material and a thermoplastic polymer material, as described above, each of the low molecular weight material and the thermoplastic polymer material to be used is used. It is preferable to select both materials so that the difference between the solubility parameter values of is 3.0 or less, preferably 2.5 or less. If this difference exceeds 3.0, it is difficult to retain a large amount of low molecular weight materials from the viewpoint of compatibility of both materials, which is an obstacle to lowering the elastic modulus of the polymer blend material to be obtained, and also the bleeding of low molecular weight materials. Is likely to occur, which is not preferable.

Further, the weight ratio of the low molecular weight material and the thermoplastic polymer material to be mixed is preferably 1.0 or more, particularly 2.0 or more, and especially 3.0 or more. When this weight ratio is less than 1.0, it is difficult to obtain a polymer blend material having a very low elastic modulus, which is not preferable.

The polymer blend material produced by the present invention includes:
If necessary, the following fillers may be further added. That is, clay, diatomaceous earth, carbon black, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxides, mica, graphite, scale-like inorganic fillers such as aluminum hydroxide, various metal powders, wood chips, glass powders , Ceramic powder, granular or powdered solid filler such as granular or powdered polymer, and other various natural or artificial short fibers and long fibers (for example, straw, hair, glass fiber, metal fiber, other various polymer fibers, etc.) Etc. can be blended.

The polymer blend material obtained by the present invention is not particularly limited such as ordinary bulk, gel, foam, etc., but it is in a gel state, especially a three-dimensional continuous uniform polymer thermoplastic material. Those in a gel state having a reticulated skeleton structure are effective for various applications.

Next, the use of the polymer blend material obtained in the present invention will be described.

Since the polymer blend material obtained in the present invention can hold a large amount of liquid low-molecular material, the elastic modulus can be controlled in an extremely low range, and the product can be provided in a wide range of industrial fields. Is.

For example, as the vibration-proof / vibration-damping / cushioning material, there may be mentioned a sealing material, a fixing member such as packing, a gasket, a grommet, a support member such as a mount, a holder and an insulator, and a cushioning member such as a stopper, a cushion and a bumper. . In addition, grabs, mitts, and shock absorbers
Golf equipment, sports equipment such as tennis rackets, insoles for shoes, various toys, audio equipment, electronic / electrical equipment, beds, chairs, medical beds, barber / beauty beds, theater, etc. It is suitably used as a material for chairs and vehicle seats that are subject to vibration.

Further, it is also used for medical equipment such as artificial legs, artificial hands, robots, electrode materials for electrocardiogram measurement, electrode materials for low frequency treatment devices and the like. Further, it is also used as an ultra-low hardness rubber for OA equipment, seismic isolation rubber, anti-vibration rubber, or racing tires. Further, it is suitable as a low hardness plastic as various molding materials. Further, since it is possible to control the release of the low molecular weight material to the outside, it is also used for various sustained release materials utilizing the release characteristics of aromatic agents, medical agents, functional materials and the like. Furthermore, it is also effective as various biomimetic materials by utilizing the feel of skin and meat.

Further, since various liquid low molecular weight materials can be handled in a solid state, they are also suitable for use as functional materials such as an electrolyte solution film, a liquid crystal film, an adhesive film and a paint film.

As described above, the polymer blend material obtained by the present invention is suitably used in all industrial fields, particularly household appliances, sports equipment, industrial equipment, precision equipment, transportation equipment, construction, civil engineering, medical care, leisure and the like. To be

[0041]

[Operation] A large amount of low molecular weight material is obtained by kneading the thermoplastic polymer material and the low molecular weight material using a high shear type special mixer having a rotor shear rate of 5.0 × 10 ² sec ⁻¹ or more. It is possible to easily and efficiently obtain a high-performance polymer blend material having various physical properties useful for various applications, by mixing a small amount of thermoplastic polymer material in a uniformly dispersed state, with little bleeding of low-molecular materials. it can.

[0042]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples below.

As the high-shear type special mixer, a high-shear type special mixer (“TK Auto Homo Mixer” manufactured by Tokushu Kika Kogyo Co., Ltd.) having the structure shown in FIG. 1 was used.

The high-shear type special mixer shown in FIG. 1 has a stator (fixed wall) 2 in which a radial baffle (blocking portion) 2A is projected in a tank 1, and a bearing 3 provided at the center of the stator 2. The kneading of the material is performed by applying a shearing action to the rotor (rotating part) 3 having the turbine 3B attached to the lower part of the. That is, as shown by the broken line in FIG. 1, the material is sucked from the lower portion of the stator 2 by the suction action generated by the high speed rotation of the turbine 3B, and a minute gap between the turbine 3B rotating at high speed and the baffle 2A of the stator 2, That is, in the clearance t, strong shearing, impact, turbulent flow, etc. are applied, and thereafter, the liquid is discharged upward from the discharge holes 2B of the stator 2. Then, this ascending flow is transformed by the upper commutation plate 4, descends along the side surface of the tank 1, and again flows into the stator 2 from the bottom of the tank 1 and is kneaded while receiving shearing force. In the figure, 5 is a turbine shaft.

The turbine 3B is inclined so that the lower end of the turbine 3B is separated from the turning center. The turning radius of the turbine 3B is 1.4 cm on the upper end side and 1.8 cm on the lower end side in the figure.
Is.

Examples 1 to 3 Using the high shear type special mixer shown in FIG. 1 and under the kneading conditions shown in Table 1, the thermoplastic polymer material and the low molecular weight material shown in Table 1 are in a weight ratio shown in Table 1. Kneaded in.

As a result, in each of the examples, the thermoplastic polymer material and the low molecular weight material were uniformly mixed in the order of micron, and in particular, the polymer material having a low elasticity forming a three-dimensional continuous uniform network structure. It was confirmed that a gel-like polymer blend material was obtained and that bleeding of low molecular weight material was extremely small.

Comparative Example 1 In Example 1, the rotation speed of the rotor of the high-shear type special mixer was changed, and the shear rate was 5.0 × 10 ² as shown in Table 1.
Kneading was carried out in the same manner except that it was smaller than sec ^-1 .

As a result, the thermoplastic polymer material and the low molecular weight material were in a separated state even after 1 hour, and a homogeneously blended polymer blend material could not be obtained.

[0050]

[Table 1]

Comparative Example 2 Using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.), which is a kneading machine generally used conventionally, the same thermoplastic polymer material and low molecular weight as those used in Example 1 were used under the following conditions. The materials were kneaded at the same mixing ratio. However, the kneading temperature and kneading time were the same as in Example 1.

Kneading conditions Rotational speed: 70 rpm Kneading temperature: 160 ° C. Kneading time: 1 hour As a result, the thermoplastic polymer material and the low molecular weight material are in a separated state even after 1 hour, and are uniformly mixed. No molecular blend material was obtained.

[0053]

As described in detail above, according to the method for producing a polymer blend material of the present invention, a large amount of low molecular weight material is uniformly contained, and bleeding of the low molecular weight material is small, which is useful for various purposes. A characteristic thermoplastic polymer blend material can be obtained easily and efficiently.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a high shear type special mixer used in Examples.

[Explanation of symbols]

 1 tank 2 stator 2A baffle 3 rotor 3A bearing 3B turbine 4 commutation plate

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takahiro Matsuse 3-3-5-209 Ogawa Higashicho, Kodaira-shi, Tokyo (72) Inventor Yuichiro Wakana 3-5-5-763 Ogawa Higashi-cho, Kodaira-shi, Tokyo

Claims (1)

[Claims] 1. A large amount of low-molecular material is obtained by kneading a thermoplastic polymer material and a low-molecular material using a high-shear type special mixer having a rotor shear rate of 5.0 × 10 ² sec ⁻¹ or more. A method for producing a polymer blend material, which comprises uniformly blending a molecular material and obtaining a thermoplastic polymer blend material having less bleeding of the low molecular material.