JP2002347020A - Method and apparatus for kneading ultra-fine powder and resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable primary particles to be uniformly dispersed in a raw material resin by easily crushing secondary particles of ultra-fine powder of a nanometer order to the primary particles. SOLUTION: An apparatus 10 for kneading the ultra-fine powder and the resin comprises a screw feeder 22 concentrically mounted in a cylinder 21, a plurality of rotary discs 23 concentrically, integrally rotatably mounted at the feeder 22, and a plurality of fixed discs 24 concentrically mounted at the cylinder 21 so as to be opposed to side faces of the discs 23. A method for kneading the ultra-fine powder and the resin comprises the steps of forming a plurality of kneading zones K1 to K5 with a melting temperature of the raw material resin G in the cylinder 21 as a reference temperature on the premise of use of the apparatus 10 so that the zones K1 to K5 sequentially become high or low near the reference temperature, sequentially passing the powder U and the resin G through the plurality of the zones K1 to K5 by a drive rotation of the feeder 22, and thereby repeating the resin G in a semi-solid state and a soft state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for kneading ultrafine powder having a particle size of nanometer order and a resin, which are kneaded so as to be uniformly dispersed in the resin. It is.

[0002]

2. Description of the Related Art Conventionally, pigments, ferrites, carbons, and the like have been used for the purpose of imparting functions such as coloring, resin, magnetism, conductivity, antibacterial properties, slidability, flame retardancy, ultraviolet rays prevention, and mechanical rigidity improvement. , Various metal powders, talc, car, titanium oxide,
There is known a functional resin in which a functional filler such as barium oxide, glass fiber, or carbon fiber is added to a resin and kneaded and dispersed. The functional filler as described above has a particle size of 0.1.
1 to 10.0 μm and a specific surface area of 5 to 50 m ² / g (in the case of carbon for resin coloring, the specific surface area is 240 m ² / g and the primary particle diameter is 14 nm, but in practice, the secondary particle diameter is 0 However, such a functional filler is dispersed in a resin to form a functional resin. Such a functional resin is called a microcomposite.

[0003] As a method of uniformly dispersing the functional fine powder in a resin, a resin is charged into a predetermined continuous kneading extruder and heated and melted. Is mixed and kneaded and kneaded.
By doing so, the functional fine powders that have been aggregated with each other are disintegrated by receiving a force, and are uniformly dispersed in the resin.

In a kneading extruder used for such a purpose, a resin as a raw material and a functional fine powder are supplied between two parallel screw shafts rotating in the same direction. It is common to employ a twin screw type for kneading and kneading and a stone mill type for kneading and kneading the raw materials supplied on the front and back surfaces of the disk by disposing the disks concentrically in multiple stages.

[0005]

Recently, montmorillonite, which is a clay mineral having a primary particle size of nano unit, has attracted attention as a reinforcing material for increasing the mechanical rigidity of a resin. This is because, by adding a small amount of montmorillonite to the resin, the strength of the resin can be greatly improved, and gas permeation of the resin can be prevented. Incidentally, a material in which nano-unit ultrafine powder is dispersed in a resin is called a nanocomposite. In the future, functional resins are expected to shift from microcomposites to nanocomposites.

The montmorillonite has a thickness of about 1 nm, a length and a width of 100 to 200 nm, each of which is very small.
It has a specific surface area of the order of m ² / g.

[0007] In such montmorillonite, approximately 10 ⁹ primary particles are aggregated to form secondary particles, and the distance between the centers of gravity of adjacent primary particles is extremely small, approximately 2 nm. Because of its short length, the cohesive force (Van der Waals force) of the ultrafine powder, which is inversely proportional to the cube of the distance and directly proportional to the particle diameter, is 10,10 compared to that of the functional fine powder having a particle diameter of the order of 1 μm. 000 times.

Therefore, in order to crush the secondary particles of montmorillonite aggregated by such a large force into individual fine particles (primary particles), an aggregate of particles having a particle diameter of 1 μm is crushed. 10,000 times more force than required.

If the secondary particles requiring such a large force are to be crushed using a conventional twin-screw kneading extruder, the conventional rotation speed of the screw (usually,
Approximately 600 rpm) is increased 10,000 times to 6,000,000.
It must be 0 rpm, which is not feasible. Actually, trials have been made at a rotational speed of at most 2,000 to 2,500 rpm, but at such a rotational speed, secondary particles of montmorillonite cannot be broken into primary particles. The situation is the same in a stone mill type kneading extruder.

Therefore, in recent years, it has been put to practical use to employ a polymerization method in which montmorillonite and a resin are dispersed in the resin by a predetermined chemical reaction. In addition to the enormous cost, there is a problem that the polymerization reaction requires a long time, the treatment efficiency is inferior, and the operating cost increases.

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and easily crushes secondary particles of nanometer order ultrafine powder into primary particles at a low capital investment and operating cost. It is another object of the present invention to provide a kneading method and a kneading apparatus of an ultrafine powder and a resin capable of uniformly dispersing the primary particles in a raw resin.

[0012]

According to the first aspect of the present invention,
A kneading method for kneading an ultrafine powder and a resin while moving a raw material containing the ultrafine powder and a resin to a downstream side, wherein the resin is set to a temperature near a resin heat deformation temperature at which the resin maintains a solid state. A crushing process in which a superfine powder in the raw material is crushed by applying a shearing force to the raw material in the solidification zone, and a resin dispersion set at a temperature around a resin melting temperature at which the resin becomes a rubber viscoelastic state or a molten state. Dispersing the ultrafine powder in the raw material by applying a shearing force to the raw material in the zone, and performing at least one dispersion processing step after the crushing processing step. .

In the present invention, the term "resin" refers to a thermoplastic synthetic resin such as polyethylene, polypropylene, polyvinyl chloride, polyamide, and styrene-acryl copolymer.

In the present invention, the set temperature of the resin solid zone is determined not only by the temperature at which the resin becomes a solid state in the so-called ordinary concept, but also by the fact that the resin is set at a temperature near the heat deformation temperature of the resin. Is a temperature at which plastic deformation can occur slightly while having the temperature.

In the present invention, the set temperature of the resin dispersion zone is a temperature at which the resin is set to a temperature lower than the melting temperature so that the resin becomes a rubber-like rubber viscoelastic state. Note that the rubber viscoelastic state of the resin is referred to as a softened state in the section of the embodiment below.

In the present invention, the molten state of the resin is a state in which the temperature of the resin is set to a temperature equal to or higher than the melting temperature, whereby the resin is in a fluid state.

According to the present invention, in the resin solidification zone, the raw material in which the secondary particles of the ultrafine powder formed by agglomeration by Van der Waals force become solid at a temperature near the resin thermal deformation temperature The secondary particles in a state of being confined in the resin and in which the movement is restricted are restricted when the raw material resin in a solid state is cut by receiving a shearing force. Next, in the subsequent resin dispersion zone, the crushed secondary particles are dispersed in the raw material resin in a molten state or a rubber viscoelastic state.

Accordingly, the ultrafine powder and the raw material resin pass through the resin solidification zone and the resin dispersion zone, so that the secondary particles are reliably crushed and then dispersed, and each of the ultrafine powders is dispersed. A functional resin (nanocomposite) in which unit particles (primary particles) are uniformly dispersed in the raw material resin is formed.

Then, as conventionally performed, the raw material resin is heated to a temperature higher than the melting temperature to make it completely liquid, and the ultrafine powder is mixed into this liquid raw material resin and simply stirred. In such a kneading method, it is difficult to disintegrate the secondary particles of the ultrafine powder that has been strongly agglomerated by Van der Waals force. (In the state of primary particles) cannot be dispersed in the raw material resin, so that a high-quality functional resin could not be produced by the conventional method.
The conventional inconvenience is solved and the particle size is 0.3 μm
Even smaller ultrafine powders can be easily and uniformly dispersed in the raw resin in particle units,
High quality nanocomposites will be produced.

Further, since the ultrafine powder is pulverized by controlling the temperature of the raw resin and uniformly dispersed in the raw resin, the equipment scale is kept small and the internal This makes it possible to achieve uniform distribution to the equipment, contributing to a reduction in equipment costs.

According to a second aspect of the present invention, in the first aspect, the crushing step and the dispersion step are repeated a plurality of times.

According to the present invention, the ultrafine powder and the raw resin are repeatedly subjected to the crushing process and the dispersing process,
Disintegration and dispersion of the secondary particles are performed more reliably.

According to a third aspect of the present invention, in the second aspect of the present invention, the temperature of the resin dispersing zone in the dispersing step performed between the plurality of crushing steps is set to a resin melting temperature or lower. It is a feature.

According to the present invention, the temperature of the raw resin is set to a temperature equal to or lower than the melting temperature of the resin in a dispersion treatment step performed between a plurality of crushing treatment steps, so that the raw resin is in a rubber viscoelastic state. Therefore, a uniform and efficient kneading process is realized while suppressing heat loss without increasing the temperature difference between the dispersion process and the crushing process.

According to a fourth aspect of the present invention, in the first aspect of the present invention, a dispersion treatment step is performed before the first crushing treatment step.

According to the present invention, since the secondary particles of the ultrafine powder are dispersed in the dispersing step before the first disintegrating step, the secondary particles are disintegrated in the next disintegrating step. Is performed uniformly.

According to a fifth aspect of the present invention, in the invention according to any one of the first to fourth aspects, the temperature of the resin dispersion zone in the dispersion treatment step performed before the first crushing treatment step is higher than the resin melting temperature. It is characterized by setting.

According to the present invention, the secondary particles of the ultrafine powder are uniformly dispersed in the completely melted raw material resin before the first crushing process, so that the secondary Disintegration of the particles is performed uniformly, resulting in a more homogeneous nanocomposite.

The invention according to claim 6 is the invention according to any one of claims 1 to 5, wherein the temperature of the resin dispersion zone in the last dispersion treatment step is set to be equal to or higher than the resin melting temperature. It is.

According to the present invention, the final finishing of the dispersion treatment of the ultrafine powder into the resin is performed in the last dispersion treatment step, and the functional resin as a product is discharged out of the system in a fluidized state. Can be.

According to a seventh aspect of the present invention, there is provided a kneading apparatus for kneading an ultrafine powder and a resin while moving a raw material containing the ultrafine powder and a resin downstream. A cylinder loaded with resin, a screw feeder concentrically mounted in the cylinder, and a plurality of rotating disks concentrically and integrally rotatably mounted on the screw feeder,
A plurality of fixed disks that are concentrically mounted on the cylinder so as to face the side surfaces of the rotating disk are provided, and a resin solidification zone that is set at a temperature around a resin heat deformation temperature at which the resin maintains a solid state in the cylinder, A resin dispersion zone is set at a temperature near the resin melting temperature at which the resin is in a rubber viscoelastic state or a molten state, and a temperature adjusting means for adjusting the temperature of the raw material resin in each zone is provided. It is assumed that.

According to the present invention, the mixture of the ultrafine powder and the raw resin flows downstream between the surface of the rotating disk rotating by the drive of the screw feeder, the inner peripheral surface of the cylinder and the surface of the fixed disk. While moving toward the side, they are kneaded and kneaded by the shear force acting on the mixture between them,
The same operation and effect as those of the first aspect can be obtained.

In particular, since the raw material resin is kneaded by a stone mill effect due to shearing action while being sandwiched between the rotating disk and the fixed disk, the raw material resin is dispersed in the raw material resin as compared with the twin-screw kneading apparatus. Secondary particles are more efficiently disintegrated.

According to an eighth aspect of the present invention, in the seventh aspect of the invention, the temperature adjusting means includes a heating means and a cooling means.

According to the present invention, since the temperature of the resin in each zone is adjusted by the temperature adjusting means having the heating means and the cooling means, for example, when the temperature of the resin is higher than the target temperature, the cooling means cools the resin. While
When the temperature is low, the resin can be quickly returned to the target temperature by heating by the heating means, and the degree of freedom of temperature adjustment is increased as compared with the temperature adjustment by one of the heating means and the cooling means. In addition, quick and accurate temperature control is realized.

[0036]

FIG. 1 is a cross-sectional side view for explaining an embodiment of a kneading apparatus (that is, an apparatus of the present invention) for mixing an ultrafine powder and a resin used in the method of the present invention. The kneading device 10 includes an ultrafine powder U having a particle size smaller than 0.1 μm.
And the raw material resin G prepared in the form of granules are kneaded to form an ultrafine powder U.
Are uniformly dispersed in the raw material resin G, and are a product from the device main body 20, a raw material supply section 30 for supplying the ultrafine powder U and the raw material resin G to the main body 20, and a product from the main body 20. A product discharge portion 40 for leading the kneaded material (functional resin G1) out of the system, and a temperature control structure for controlling the temperature inside the apparatus main body 20 (a first heat medium flow passage 27 of the cylinder 21 described later, a fixed disk) 24, a second heat medium flow passage 28, a refrigerant supply device 60, an electric heating jacket 90, a power supply device 99, and the like.

The apparatus main body 20 includes a plurality of cylinders 2.
1, a screw feeder 22 provided concentrically inside the cylinder 21, a plurality of rotating disks 23 mounted concentrically and corotatably on the screw feeder 22, and concentrically opposed to the side surfaces of the rotating disk 23. It comprises a plurality of fixed disks 24 mounted on the cylinder 21 and a cylindrical casing 25 concentrically connected to the cylinder 21 on the most upstream side (right side in FIG. 1).

The plurality of cylinders 21, the plurality of rotating disks 23 and the plurality of fixed disks 24, which are fitted around the screw feeder 22 so as to be rotatable around the screw feeder 22, are concentrically and alternately overlapped on the base end side thereof. A casing 25 is concentrically joined, and a product discharge cylinder 41, which will be described later, forming a product discharge section 40 is concentrically connected to the cylinder 21 on the most downstream side, and a tie rod 29 is penetrated and fastened to these. 20 is formed between the casing 25 and the product discharge cylinder 41.

A driving device 26 is provided at the right end of the casing 25 of the device main body 20 in FIG.
The screw feeder 2 is driven by the driving device 26.
2 rotates around its own axis.

A screw 22 a is provided on the outer peripheral surface of the screw feeder 22.
The super fine powder U and the raw material resin G introduced into the screw 5 are rotated by the screw 22 a by the rotation of the screw feeder 22 around the axis.
, And moves toward the downstream side in the cylinder 21, the gap between the inner peripheral surface of each cylinder 21 and the outer peripheral surface of each rotating disk 23, and the side surface of each fixed disk 24 and each rotating disk 23. Kneading and kneading while passing through the gap with the side,
It becomes the functional resin G1 and is discharged from the product discharge cylinder 41 to the outside of the system.

The raw material supply section 30 includes an ultrafine powder hopper 31 for storing the ultrafine powder U,
Ultra-fine powder cutting conveyor 3 for cutting out ultra-fine powder U in 1
2, a raw resin hopper 33 for storing the raw resin G,
A raw resin cutting conveyor 34 for cutting the raw resin G in the raw resin hopper 33;
It comprises a vertically extending relay cylinder 35 for receiving the ultrafine powder U and the raw resin G from 34, and a raw material charging hopper 36 connected to the lower end of the relay cylinder 35.

The ultrafine powder cutting conveyor 32 has an ultrafine powder side driving motor 32a attached to its driving pulley, and the raw resin cutting conveyor 34 has a raw resin cutting motor attached to its driving pulley. A side drive motor 34a is provided, and the ultrafine powder U in the ultrafine powder hopper 31 is cut out by the rotation between the pulleys of the conveyors 32 and 34 driven by the drive motors 32a and 34a. The raw resin G in the raw resin hopper 33 is cut out.

The lower end of the raw material charging hopper 36 is fixed to the upper part of the peripheral surface of the casing 25, while the casing 25 is provided with a raw material charging hole 25 a at a position facing the lower opening of the raw material charging hopper 36. Have been. Accordingly, each hopper 3 is driven by the driving of each of the cutting conveyors 32 and 34.
Ultrafine powder U and raw material resin G cut out from 1,33
Is temporarily stored in the raw material charging hopper 36 via the relay cylinder 35, and is propelled by the driving rotation of the screw feeder 22, and the casing 25 is moved through the raw material charging hole 25a.
It is being introduced into.

Further, the ultra fine powder cutting conveyor 32 includes:
An ultrafine powder weighing device 37 for detecting the flow rate of the ultrafine powder U being cut out is attached, and the raw resin cutting conveyor 34 is for detecting the flow rate of the raw resin G being cut out. The raw material resin weigher 38 is provided.

In the present embodiment, these weighing devices 37 and 38 are of a so-called balance type, and the fulcrum 3 is used.
The balance rods 37b and 38b supported so as to be capable of rotating forward and backward by the reference numerals 7a and 38a, and the weighing sensors 37c and 38c provided at one end of the balance rods 37b and 38b (the ultrafine powder side weighing sensor 37c and the raw resin side). Weighing sensor 38c).

The other ends of the respective balance rods 37b and 38b are connected to the ultrafine powder cutting conveyor 32 and the raw resin cutting conveyor 34, respectively.
The weight fluctuations of the ultrafine powder U and the raw resin G being conveyed by the respective conveyors 32 and 34 are caused by swinging of the balance rods 37b and 38b around the fulcrums 37a and 38a. Weighing sensor 37
c, 38c, thereby detecting the ultrafine powder U
And the cutout flow rate of the raw material resin G is grasped one by one. Then, by detecting each cutting flow rate one by one, it is checked whether or not the ultrafine powder U and the raw material resin G have a preset mixing ratio.

The product discharge section 40 includes a product discharge cylinder 41 concentrically connected to the downstream end of the apparatus main body 20, a die member 42 concentrically connected to the downstream end of the product discharge cylinder 41,
It comprises a product pushing shaft 43 coaxially rotating with the screw feeder 22 which is provided concentrically inside the product discharge cylinder 41.

The product discharge cylinder 41 has a flange 41a at an upstream end and a downstream end, and the flange 41a on the upstream side is in contact with the cylinder 21 on the most downstream side.
a, each cylinder 21, fixed disk 24 and casing 2
5, the tie rod 29 is inserted and fastened, so that the apparatus body 20, the casing 25, and the product discharge section 4
0 are integrated. As shown in FIG. 3, a plurality of tie rods 29 (five in the example shown in FIG. 3) are used at equal pitches in the circumferential direction of the apparatus main body 20, whereby the apparatus main body 20, the casing 25 and the product discharge cylinder 41 are used. To ensure the connection state.

The die member 42 is a base for discharging the functional resin G1 pressed by the product pushing shaft 43 in the product discharge cylinder 41, and has an annular discharge hole 42a at the center position.
And the functional resin G extruded from the product discharge cylinder 41
1 is discharged to the outside of the system while passing through the annular discharge hole 42a of the die member 42 and becoming cylindrical.

FIG. 2 is a partial view showing a part of the apparatus main body 20, and FIG. 3 is a sectional view taken along line AA. As shown in these figures, the screw feeder 22 is fitted externally so as to be integrally rotatable concentrically with a spline shaft 26a projecting from a driving device 26 (FIG. 1). Incidentally, in FIG. 2, the spline shaft 26a between the adjacent rotating discs 23 is shown.
3 shows a state in which some of the screw feeders 22 are externally fitted, so that the spline shaft 26a is exposed outside the rotary disks 23 outside.

The spline shaft 26a has a longitudinally extending spline strip 26b projecting from the outer peripheral surface thereof at a constant pitch in the circumferential direction, while the spline shaft 26a is provided on the inner peripheral surfaces of the screw feeder 22 and the rotating disk 23. Grooves corresponding to the ridges 26b are respectively provided, and these screw grooves are fitted into the spline ridges 26b, so that the screw feeder 22 and the rotating disk 23 can rotate integrally with the spline shaft 26a. .

A plurality of threads 22a are provided on the outer peripheral surface of the screw feeder 22 at a constant pitch in the circumferential direction, and a plurality of sawtooth-like patterns are provided on the outer peripheral surface of the rotating disk 23 at the same pitch in the circumferential direction. A projection 23a is provided. Both the thread 22a and the serrated protrusion 23a are shown in FIG.
, The angle is set so as to incline leftward with respect to the horizontal direction, and the screw feeder 22 and the rotating disk 2
Ultrafine powder U (FIG. 1) and raw resin G
Is rotated counterclockwise about the spline shaft 26a of the screw feeder 22 and the rotating disk 23 in FIG.
While being guided by 3a, it is sequentially moved toward the downstream side (left side in FIG. 2).

On the front and back surfaces of the rotating disk 23, there are provided ridges 23b bulging radially at equal pitches in the circumferential direction, and valleys between adjacent ridges 23b. The concave portion 23c is provided, and by appropriately setting the angle in the radial direction, the surface of the rotating disk 23 (FIG.
The mixture of the ultrafine powder U and the raw material resin G located on the right side of the rotating disk 23 moves outward in the radial direction of the rotating disk 23, while the mixture located on the back side thereof moves toward the center of the rotating disk 23. It is made to move toward.

The fixed disk 24 is, as shown in FIG.
It is fastened by a plurality (FIG. 3) of tie rods 29 penetrating both while being sandwiched between adjacent cylinders 21. The fixed disk 24 includes a thick portion 24a provided concentrically at the center position and the above-mentioned wall extending concentrically from the peripheral surface of the thick portion 24a radially outward over the entire circumference. The thin portion 24b is thinner than the thick portion 24a. The thick portion 24a and the thin portion 24b are symmetrical in the cross-sectional view shown in FIG.

The thickness of the thick portion 24a is set slightly smaller than the gap between the adjacent rotating disks 23 (that is, the length of the screw feeder 22 between the rotating disks 23 is smaller than that of the thick portion 24a). The dimension is set slightly longer than the thickness dimension). The thick portion 24a has a through hole 24c having an inner diameter slightly larger than the outer diameter of the screw feeder 22 at the center thereof, and an outer diameter slightly larger than that of the rotating disk 23. Is set. By doing so, the mixture of the ultrafine powder U and the raw material resin G is formed between the thick portion 24a and the front and back surfaces of the rotating disk 23, the inner peripheral surface of the thick portion 24a and the outer peripheral surface of the screw feeder 22. It is possible to pass through the gap formed between them.

The cylinder 21 is, as shown in FIG.
A thin portion 21a concentrically provided at a center position, and a thick portion thicker than the thin portion 21a, which is concentrically extended from the peripheral surface of the thin portion 21a radially outward over the entire circumference. 2
1b. Thin part 21a and thick part 21
b is formed bilaterally symmetrically in the sectional view shown in FIG.
The thickness difference between the thin portion 21a and the thick portion 21b is set in the same manner as the thickness of the thick portion 24a and the thin portion 24b of the fixed disk 24.

The thin portion 21a of the casing 25 is
The thickness is set slightly thicker than the thickness of the rotating disk 23, and the rotating disk 23 is positioned at the center thereof.
A mounting hole 21c for mounting the rotating disk 23 having an inner diameter slightly larger than the outer diameter is provided.

Therefore, the rotating disk 2 is attached to the spline shaft 26a.
3 with the casing 25
And then the screw feeder 22 is externally fitted to the spline shaft 26a.
By repeating the assembling operation of fitting the fixed disk 24 to the outside of the device body 2 in order, as shown in FIG.
Is completed.

In the thin portion 21a of the casing 25,
A saw-tooth projection 21d is formed on the inner peripheral surface of the rotating disk 23 so as to face the saw-tooth projection 23a over the entire circumference. The saw-tooth projection 21d is formed so that the direction of sharpening is opposite to that of the saw-tooth projection 23a of the rotating disk 23. Therefore, the mixture of the ultrafine powder U and the raw material resin G introduced between the serrated protrusions 23a and 25d is:
A large shearing force is applied by the rotation of the rotary disk 23, and the fine particles are separated to promote further pulverization of the ultrafine powder U, and the mixing of the ultrafine powder U and the raw material resin G is performed well. It has become.

FIG. 4 is an enlarged sectional view of a portion surrounded by a dashed line in FIG. 2, and FIG. 5 is a sectional perspective view of a saw-tooth projection 21d of the casing 25. As shown in these figures,
The serrated protrusion 21d includes an arc-shaped concave portion 21e in which the inner peripheral surface of the thin portion 21a of the casing 25 is formed to be radially outwardly curved in a plane perpendicular to the hole center, and an arc-shaped concave portion 21e. A chord portion 21f protruding from the bottom of the to the chord position and an inclined portion 21g extending from one arcuate concave portion 21e to the adjacent chord portion 21f.

In the inclined portion 21g, the radius of curvature of the arc gradually increases from the arcuate concave portion 21e toward the adjacent chord portion 21f, and reaches the chord portion 21f so that the radius of curvature is infinite (that is, linear). ).

By forming the serrated projection 21d in this manner, the corner 21h in the casing 25 formed by the contact between the thin portion 21a of the casing 25 and the thick portion 24a of the fixed disk 24 is gentle. (Specifically, the angle formed between the inclined portion 21g and the thick portion 24a of the fixed disk 24 becomes an obtuse angle), and as a result, the corner 21h (conventionally, the corner is generally a right angle) The disadvantage of the prior art, in which the mixture stays, is eliminated.

Incidentally, if the mixture stays in the corner 21h for a long period of time, the staying material may be solidified, and the solidified material may fall off due to the vibration caused by the driving of the kneading device 10, thereby causing the ultrafine powder. The homogeneity of the mixture of U and the raw material resin G is impaired, which causes defective products. However, in the present embodiment, the obtuse angle of the corner 21h suppresses the formation of solidified products and the generation of defective products. Decrease.

As shown in FIGS. 2 to 4, the solid portion of the casing 25 is provided with an annular first cooling / heating medium flow passage 27 formed concentrically with the hole center. As shown in FIGS. 2 and 4, an annular second cooling medium flow passage 28 formed concentrically with the hole center is provided in 24. The cooling medium flow passages 27 and 28 are cooperated with an electric heating jacket 90 which will be described later in detail, and
This is for controlling the temperature of the raw material resin G in the inside, and by precisely performing this temperature control, the secondary particles, which are aggregates of the ultrafine powder U, are crushed and evenly distributed in the raw material resin G. Can be dispersed.

Hereinafter, the temperature control of the apparatus main body 20 will be described. In order to appropriately execute this temperature control, in the present embodiment, as shown in FIG.
Employs 10 units from the first cylinder 211 on the most upstream side (right side in FIG. 1) to the tenth cylinder 2110 on the most downstream side. Further, as the rotating disks 23, ten units from a first rotating disk 231 on the most upstream side to a tenth rotating disk 2310 on the most downstream side are employed. The fixed disk 24
From the first fixed disk 241 on the most upstream side to the tenth fixed disk 2
Nine up to 49 units have been employed.

The downstream half of the casing 25, the first cylinder 211 and the second cylinder 212,
A first kneading zone K1 is formed in a space surrounded by the first rotating disk 231 and the second rotating disk 232, the first fixed disk 241, and the screw feeder 22. In the first kneading zone K1, the first temperature T
Controlled to 1.

The third cylinder 213 and the fourth cylinder 214, the third rotating disk 233 and the fourth rotating disk 234, the second fixed disk 242 and the third fixed disk 24
A second kneading zone K2 is formed in a space surrounded by the third kneader 3 and the screw feeder 22. Second kneading zone K2
In, the inside of the apparatus main body 20 is controlled to the second temperature T2.

The fifth cylinder 215 and the sixth cylinder 216, the fifth rotating disk 235 and the sixth rotating disk 236, the fourth fixed disk 244 and the fifth fixed disk 24
The third kneading zone K3 is formed in a space surrounded by the screw feeder 5 and the screw feeder 22. Third kneading zone K3
In, the inside of the apparatus body 20 is controlled to the third temperature T3.

The seventh cylinder 217 and the eighth cylinder 218, the seventh rotating disk 237 and the eighth rotating disk 238, the sixth fixed disk 246 and the seventh fixed disk 24
The fourth kneading zone K4 is formed in a space surrounded by the screw feeder 7 and the screw feeder 22. Fourth kneading zone K4
In, the inside of the apparatus main body 20 is controlled to the fourth temperature T4.

The ninth cylinder 219 and the tenth cylinder 2110, the ninth rotating disk 239 and the tenth rotating disk 2310, the eighth fixed disk 248 and the ninth fixed disk 249, and the screw feeder 22. A fifth kneading zone K5 is formed in the space. In the fifth kneading zone K5, the inside of the apparatus main body 20 is controlled to the fifth temperature T5.

The extrusion zone P is formed in a space surrounded by the inner peripheral surface of the product discharge cylinder 41 and the outer peripheral surface of the product extrusion shaft 43.
Are formed. The inside of the extrusion zone P is controlled to the sixth temperature T6. A product discharge zone V for discharging the functional resin G1 as a product out of the system is formed in the die member 42 on the most downstream side. This product discharge zone V is controlled to the seventh temperature T7.

In the present embodiment, the kneading and dispersing step (see FIG. 1) in which the secondary particles of the ultrafine powder U are crushed by the first to fifth kneading zones K1 to K5 and uniformly dispersed in the raw material resin G 6) is formed and the extrusion zone P
An extruding step (FIG. 6) for extruding the functional resin G1 obtained in the kneading and dispersing step out of the system by the product discharge zone V is formed.

In this embodiment, the second kneading zone K2 and the fourth kneading zone K4 form the crushing process according to the present invention, and the first kneading zone K1, the third kneading zone K3, Fifth kneading zone K
5, the dispersion processing step according to the present invention is formed.

In order to control the temperature of the raw material resin G in the apparatus main body 20, the above-mentioned temperature control structure is provided in the present invention. As shown in FIG. 7 (note that FIG. 7 is for describing the operation control of the kneading apparatus 10 described later in detail), the temperature control structure is provided in each kneading zone K1 to K5 and the product discharge zone V. 20 and an electric heating jacket 90 provided on the outer peripheral surface of the product discharge section 40 (FIG. 1), respectively, and a refrigerant supply device 60 for cooling the respective kneading zones K1 to K5 and the product discharge zone V. .

The electric heating jacket 90 is provided with an annular casing in which an electric heating element such as a nichrome wire or silicon carbide is provided. When the casing is externally fitted to the apparatus main body 20, the inside of the apparatus main body 20 and the inside of the product discharge section 40 are heated by the heat generated by the current-carrying heating element.

As such an electric heating jacket 90,
First jacket 91 provided in first kneading zone K1
And a second jacket 9 provided in the second kneading zone K2.
2, a third jacket 93 provided in the third kneading zone K3, a fourth jacket 94 provided in the fourth kneading zone K4, a fifth jacket 95 provided in the fifth kneading zone K5, and an extrusion zone. Seven units, a sixth jacket 96 provided in P and a seventh jacket 97 provided in the product discharge zone V, are employed.

In each of the electric heating jackets 91 to 97,
A predetermined amount of electric power is supplied from the power supply device 99, and the kneading zones K1 to K5, the extrusion zone P, and the product discharge zone V are separately heated to predetermined temperatures by the heat generated by the energizing heating elements. I have.

The kneading zone K1 of the above zones is used.
As for K5 to K5, precise temperature control is necessary, so that each of the kneading zones K1 to K5 is operated in cooperation with the refrigerant supply device 60 described in detail below.
5 is controlled. On the other hand, as for the temperatures of the extrusion zone P and the product discharge zone V, it is sufficient that the functional resin G1 is higher than the resin resin melting temperature Tm (FIG. 6). Precise temperature control using 60 is not performed.

The electric heating jacket 90 is supplied with electric power from a power supply device 99 provided near the kneading device 10. In the present embodiment, unique electric power is supplied to the first to fifth jackets 91 to 95, respectively. Each kneading zone K1 to K5
Is controlled by controlling the amount of electric power supplied to the first to fifth jackets 91 to 95 and controlling the amount of refrigerant supplied from the refrigerant supply device 60 to the heat medium passages 27 and 28. On the other hand, the temperature control of the extrusion zone P and the product discharge zone V is performed only by controlling the power supply to the sixth and seventh jackets 96 and 97.

The refrigerant supply device 60 has therein a cold heat source such as a refrigerator or the like, and a plurality of refrigerant delivery pumps for delivering a coolant such as water or cooling oil cooled by the cold heat source. .

Then, the refrigerant delivery pump corresponding to the first kneading zone K1 and the cooling medium flow passage 2 of the first kneading zone K1
7 and 28, a first outward pipe 61 is provided, and a second outgoing line 61 is provided between the refrigerant delivery pump corresponding to the second kneading zone K2 and the cooling medium flow passages 27 and 28 of the second kneading zone K2. An outgoing line 62 is provided, and a refrigerant delivery pump corresponding to the third kneading zone K3 and the cooling medium flow passage 2 of the third kneading zone K3
A third outward pipe 63 is provided between the fourth kneading zone K4 and the cooling medium flow passages 27 and 28 of the fourth kneading zone K4. An outgoing line 64 is provided, and a refrigerant delivery pump corresponding to the fifth kneading zone K5 and the cooling medium flow passage 2 of the fifth kneading zone K5.
A fifth outgoing line 65 is provided between the first and second lines 7 and 28.

In the kneading zones K1 to K5, the main unit 2
The refrigerant that has been used for adjusting the temperature of the mixture of the ultrafine powder U and the raw material resin G in 0 is collected in one return line 66, returned to the refrigerant supply device 60, and used for circulation. It has become so. The return pipe 66 is provided with a heat exchanger 67 for cooling the refrigerant by heat exchange with the outside air, and the refrigerant heated in the apparatus main body 20 is once cooled to a temperature slightly higher than normal temperature. After that, it is returned to the refrigerant supply device 60.

Then, the refrigerant returned to the refrigerant supply device 60 is cooled to a predetermined temperature by a cold heat source, and then passes through control pipes 61a to 65a, which will be described later, and passes through outgoing pipes 61 to 65 again to return to each other. The mixture is sent out to the kneading zones K1 to K5 and is circulated.

The first outgoing line 61 has a first control valve 61a.
However, the second control valve 62a is provided in the second outgoing line 62, the third control valve 63a is provided in the third outgoing line 63, the fourth control valve 64a is provided in the fourth outgoing line 64, and the fifth outgoing line is provided. A fifth control valve 65 is provided in the line 65.
a are provided respectively, and these control valves 61a to 65a
Adjustment of the refrigerant flow rate by opening and closing operations of the heat medium flow passage 2
The control of the amount of power supply to each of the kneading zones K1 to K7
The temperature of K5 is controlled.

FIG. 6 is a graph showing the temperature transition of each of the kneading zones K1 to K5, the extrusion zone P and the product discharge zone V. The horizontal axis indicates the distance from the starting point of the first kneading zone K1. The temperature is set on the vertical axis.
The curves of the temperature transition in this graph include those that change at a high rate and those that change at a low rate.
Is driven. Which temperature transition is adopted is determined by the type of the raw material resin G.

Such temperature control is performed for the following reason. In other words, each of the ultrafine powders U has a very small diameter of nano-order, but many of them are aggregated by van der Waals force to form so-called secondary particles. However, since the secondary particles behave as if they were one particle, even if the ultrafine powder U, which is an aggregate of such secondary particles, is simply supplied to the raw material resin G in a molten state and kneaded, Only the secondary particles are dispersed in the raw material resin G, and the secondary particles are not disintegrated and individual fine particles (primary particles) are not uniformly dispersed in the raw material resin G.

Therefore, in the present embodiment, the raw material resin G is heated and melted to a liquid state, and once the liquid raw material resin G
The secondary particles are evenly dispersed in the resin resin G, and thereafter, the temperature is precisely controlled to change the state of the raw material resin G between the softened state and the semi-solid state a plurality of times. The secondary particles dispersed in the raw material resin G are broken and broken by the shearing force generated between the rotating disk 23 and the cylinder 21 and the fixed disk 24, and the rotary disk 2 is in a semi-molten state.
The secondary particles pulverized by the rotation of No. 3 are uniformly dispersed in the raw material resin G, and by repeating the shearing treatment and the dispersion treatment of the secondary particles, each of the particles of the ultrafine powder U (ie, The primary particles) are uniformly dispersed in the raw material resin G. For this purpose (ie, in order to set the raw material resin G into a semi-molten state and a semi-solidified state in order), a kneading zone in the apparatus main body 20 is used. Precise temperature control is required every time.

The temperature control is performed by controlling the power from the power supply 99 supplied to the energizing heating element of the electric heating jacket 90, the first cooling medium flow passage 27 (FIG. 2) of the casing 25 and the second cooling medium of the fixed disk 24. This is performed by controlling the flow rate of the refrigerant supplied to the flow passage 28.

In the present embodiment, based on the resin melting temperature Tm, which is the melting point of the raw resin G, when the ultrafine powder U is dispersed in the raw resin G, the temperature of the raw resin G is set to the resin melting temperature Tm. The temperature of the raw resin G is controlled so as to be in the vicinity of, while the secondary resin fixed in the semi-solid raw resin G by crushing the raw resin G into a semi-solid state is sheared. Is controlled so that the temperature of the resin becomes a temperature near the resin heat deformation temperature Tm ′ lower than the resin melting temperature Tm. The resin melting temperature Tm is a temperature at which the raw resin G is completely melted and becomes liquid when the raw resin G is heated, and the resin thermal deformation temperature Tm 'is a semi-solid state in which the raw resin is thermally deformed. Temperature. In a temperature range higher than the resin melting temperature Tm, a melt phase shearing range is set as shown in FIG.

The resin thermal deformation temperature Tm 'will be described in more detail. Resin thermal deformation temperature Tm 'is ASTM
(American Society of Test
ingMaterisl: American National Standards Institute) Test Method D-
This is the temperature at which the resin begins to thermally deform under a load of 18.6 kg / cm ² , obtained in the test according to 647. In the vicinity of this temperature, the raw material resin G easily undergoes plastic deformation when a force is applied, but becomes a so-called semi-solid state showing almost no fluidity. A cooling solid-phase shearing region, which is a temperature region where the secondary particles in G are crushed, is set.

Incidentally, the resin thermal deformation temperature Tm 'differs depending on the type of the resin.
80 ° C., polyethylene is 43 ° C. to 52
32 ° C to 41 ° C for medium density, 2 for low density
4 ° C to 32 ° C.

The first to fifth temperatures T1 to T5, which are the temperatures of the first to fifth kneading zones K1 to K5, and the sixth temperature T, which is the temperature of the extrusion zone P in the present embodiment.
6 and a seventh temperature T7 which is the temperature of the product discharge zone V
Is set as follows based on the resin melting temperature Tm and the resin thermal deformation temperature Tm ′ of the raw material resin G (see FIG. 7). First kneading zone K1 T1 = Tm to (Tm + α) ° C. Second kneading zone K2 T2 = (Tm′−20) to (T
m ′ + β) ° C. Third kneading zone K3 T3 = (Tm ′ + γ) to Tm ° C. Fourth kneading zone K4 T4 = (Tm′−20) to (T
m ′ + β) ° C. Fifth kneading zone K5 T5 = Tm to (Tm + δ) ° C. Extrusion zone PT6 = Tm to (Tm + α) ° C. Product discharge zone V T7 = Tm to (Tm + ε) ° C.

In the present embodiment, the above “α” is approximately 35 ° C., and the above “β” is approximately 25 ° C., and the above “γ”
About 20 ° C., about 22 ° C. as “δ”, and about 40 ° C. as “ε”. Such values of “α” to “ε” are empirical values obtained by accumulating many tests.

Further, in particular, the temperature of the second kneading zone K2 and the fourth kneading zone K4 is set at 20 degrees from the resin thermal deformation temperature Tm '.
The lower temperature is defined as the temperature of the second and fourth kneading zones K2 and K4 (the second and fourth temperatures T2 and K4).
If T4) is set to be lower than this lower limit, the raw material resin G is completely solidified, very much energy is consumed to divide the raw material resin G, and the energy efficiency is reduced. In order to avoid such inconvenience, the set lower limit of the second and fourth temperatures T2 and T4 is set to a temperature lower by 20 ° C. than the resin heat deformation temperature Tm ′.

Then, the ultrafine powder U and the raw resin G introduced from the ultrafine powder hopper 31 (FIG. 1) and the raw resin hopper 33 into the first kneading zone K1 of the apparatus main body 20.
Is heated to a first temperature T1 adjusted by the heat generated by the first jacket 91 and the cold heat from the refrigerant flowing through the first cooling medium passage 27 and the second cooling medium passage 28. The raw resin G is in a molten state. Then, the molten raw material resin G is obtained by the rotation of the rotary disk 23 (the first rotary disk 231 and the second rotary disk 232) while moving to the downstream side by obtaining the propulsive force directed downstream by the rotation of the screw feeder 22. Kneaded with ultra fine powder U,
As a result, the secondary particles of the ultrafine powder U are uniformly dispersed in the raw material resin G.
A kneaded product of secondary particles dispersed therein is obtained.

This secondary particle dispersion kneaded material is treated at the second temperature T2 in the second kneading zone K2. By the second temperature T2, the raw material resin G which has been in a molten state until now is
Becomes a semi-solid state. The secondary particles of the ultrafine powder U are uniformly dispersed in the raw resin G in the semi-solid state by the dispersion treatment in the first kneading zone K1. Then, the raw resin G in the semi-solid state is supplied to the rotating disk 23 (the third rotating disk 233 and the fourth rotating disk 23).
By the rotation of 4), the ridge 23b and the saw-tooth protrusion 2 are formed.
1d (FIG. 3), the raw resin G
The secondary particles of the ultrafine powder U in the inside are divided, and by repeating this, the secondary particles are effectively broken.

The mixture of the ultrafine powder U in which the secondary particles are crushed and the raw material resin G is heated to the third temperature T3 in the next third kneading zone K3, whereby the raw material resin G is in a softened state. It is said. In this state, the mixture is supplied to the rotating disk 23 (the fifth rotating disk 235 and the sixth rotating disk 2).
36), the second kneading zone K
The secondary particles of the ultrafine powder U that has been crushed and reduced in Step 2 are dispersed in the raw material resin G.

Next, in the fourth kneading zone K4,
In the environment of the fourth temperature T4, the raw material resin G is subjected to the same secondary particle crushing treatment as in the second kneading zone K2,
It is assumed that there are almost no secondary particles. And
The mixture in which the disintegration of the secondary particles has been substantially completed is introduced into the fifth kneading zone K5 set at the fifth temperature T5, whereby the raw material resin G becomes completely liquid. The liquid raw material resin G is stirred by the rotation of the rotating disk 23 (the ninth rotating disk 239 and the tenth rotating disk 2310),
Each fine particle of the ultrafine powder U is evenly dispersed in the raw resin G to become the functional resin G1 in a molten state.

The functional resin G1 thus obtained
Is discharged from the tenth cylinder 2110 toward the extrusion zone P in the product discharge cylinder 41, and further heated by the seventh jacket 97 at the die member 42 to the seventh temperature T7 which is higher than the sixth temperature T6. It is discharged out of the system. The reason for this is to reduce the extrusion resistance of the functional resin G1 at the base of the die member 42,
This is for preventing the functional resin G1 from being exposed to the outside air after being discharged to the outside and suddenly dropping in temperature to be solidified.

FIG. 7 is a block diagram showing an embodiment of the operation control of the kneading apparatus 10. As shown in FIG. As shown in this figure, a control device 70 is provided near the kneading device 10 for controlling the operation of the kneading device 10. The control device 70 includes a central processing unit (CPU) (central pro
sessing unit) 71, an input / output device 72 attached to the CPU 71, and a RAM (random access memory) for temporarily storing necessary data.
ry) 73 and a ROM (re
ad only memory) 74.

The input / output device 72 inputs data such as various operating conditions necessary for the operation of the kneading apparatus 10 to the CPU 71, and also calculates the results of predetermined calculations performed by the CPU 71 and the kneading apparatus currently being implemented. The device 10 outputs an operation status and sometimes an alarm, and includes an input device such as a keyboard and a mouse, a display device for displaying various information on a screen, a printer for printing and outputting various information, and the like.

On the other hand, a first temperature sensor 81 is located at an appropriate location in the first kneading zone K1, a second temperature sensor 82 is located at an appropriate location in the second kneading zone K2, and a third temperature sensor is located at an appropriate location in the third kneading zone K3. 83, a fourth temperature sensor 84 in an appropriate place in the fourth kneading zone K4, a fifth temperature sensor 85 in an appropriate place in the fifth kneading zone K5, a sixth temperature sensor 86 in an appropriate place in the extrusion zone P, Seventh temperature sensors 87 are provided at appropriate places in the discharge zone V, and these temperature sensors 81
The temperature detection signals from 〜87 to ８７87 are input to the CPU 71 one by one, and a control signal based on this is output to each of the control valves 61a to 65a, and the opening degree of the control valves 61a to 65a is adjusted by the feedback control. Each of the kneading zones K1 to K1 heated by the electric heating jacket 90 by adjusting the flow rate.
The temperature of K5 is precisely controlled.

The detection signals of the cut-out flow rates of the ultrafine powder U and the raw material resin G by the ultrafine powder side weighing sensor 37c and the raw resin side weighing sensor 38c are also sequentially transmitted to the CPU 71.
And a control signal based on this is output to the ultrafine powder side drive motor 32a and the raw material resin side drive motor 34a, and the number of revolutions of each drive motor 32a, 34a is adjusted by feedback control, whereby the ultrafine powder is adjusted. The cutting flow rate of the powder U and the raw material resin G is controlled.

Hereinafter, the operation control of the kneading device 10 by the control device 70 will be described in more detail. In the operation of the kneading apparatus 10, electric power is supplied to the energizing heating elements of each of the electric heating jackets 91 to 97 in advance by a control signal from the CPU 71 via the power supply device 99, whereby each of the kneading zones K1 to K5, the extrusion zone P and The product discharge zone V is heated to a predetermined temperature. Also, a predetermined amount of the ultrafine powder U and the raw resin G are previously stored in the ultrafine powder hopper 31 and the raw resin hopper 33, respectively.
Are loaded respectively.

In this state, the set cut-out amount of the ultrafine powder U and the raw material resin G and the set temperatures of the kneading zones K1 to K5 and the product discharge zone V are input to the input / output device 72 in this state. Then, when a drive signal is output from the CPU 71 to the drive unit 26 and each of the drive motors 32a and 34a, the screw feeder 22 is rotated, and the conveyors 32 and 34 are also rotated so that the hoppers 31 and 33 transmit ultra-fine signals. Powder U and raw resin G are cut out.

At this time, the detection signals from the respective weighing sensors 37c and 38c are input one by one to the CPU 71, and the value of the detection signal is compared with the value of the preset cut-out flow rate which is input in advance. Drive motor 32 when small
A signal for increasing the number of rotations of the drive motors 32a and 34a is output from the CPU 71.
The CPU 71 outputs a signal for reducing the number of rotations of a, whereby appropriate amounts of the ultrafine powder U and the raw material resin G are always cut out from the hoppers 31 and 33 by the respective conveyors 32 and 34.

The ultrafine powder U and the raw material resin G cut out by the respective conveyors 32 and 34 are connected to the relay cylinder 35.
And the raw material resin G is introduced into the first kneading zone K1 of the apparatus main body 20 via the raw material charging hopper 36, and the mixture of the raw material resin G and the melted resin is fed to the screw feeder 22.
Is moved toward the downstream side by the driving rotation of the rotating disk 2 in each of the kneading zones K1 to K5, as described in detail above.
By the rotation of 3, the disintegration and diffusion of the secondary particles of the ultrafine powder U in the mixture are repeated to form the functional resin G1.

The temperature control in the apparatus main body 20 in the kneading zones K1 to K5 will be described by taking the first kneading zone K1 as an example. When the detection signal from the first temperature sensor 81 is input, the CPU 71 determines the value of the detection signal and the value of the preset temperature (first temperature T).
If the value of the detection signal is higher than the set temperature, a signal for increasing the opening of the valve is output to the first control valve 61a. As a result, the flow rate of the cooling medium in the first kneading zone K1,
The amount of heat transfer of the refrigerant to the mixture via 28 increases, and the temperature of the first kneading zone K1 decreases toward the first temperature T1.

On the other hand, when the value of the detection signal of the first temperature sensor 81 is lower than the first temperature T1, the CPU 71 outputs a control signal to the first control valve 61a to decrease the opening of the valve, thereby causing the refrigerant to flow. With the decrease in the flow rate, the supply of cold heat to the mixture in the first kneading zone K1 decreases, and the temperature of the first kneading zone K1 increases toward the first temperature T1.

By performing such feedback control in each of the kneading zones K1 to K5, each of the kneading zones K1 to K5 can precisely maintain a preset temperature within a predetermined allowable temperature range. Thus, the semi-solid state and the softened state at a predetermined temperature of the raw material resin G can be exhibited, and the crushing and dispersion of the secondary particles of the ultrafine powder U are appropriately performed as described above. The functional resin G1 in which the unit particles of the ultrafine powder U are uniformly dispersed in the raw resin G can be obtained.

In the extrusion zone P and the product discharge zone V, a control signal is output from the CPU 71 to the power supply 99 based on the detection signals of the sixth temperature sensor 86 and the seventh temperature sensor 87, and the power supply 99 The inside of the extrusion zone P and the product discharge zone V are always set to the set temperatures (the sixth temperature T6 and the seventh temperature T7) within a predetermined allowable temperature range by turning on / off the power supply to the sixth jacket 96 and the seventh jacket 97 from the apparatus. Is controlled so that

As described in detail above, the kneading apparatus 10 of the present embodiment comprises a screw feeder 22 mounted concentrically in a cylinder 21 and a plurality of rotary feeders concentrically mounted on the screw feeder 22 so as to be integrally rotatable. Disk 23
It is assumed that a kneading apparatus 10 having a plurality of fixed disks 24 concentrically mounted on a cylinder 21 so as to face the side surface of the rotating disk 23 is used. Multiple kneading zones K with temperature
1 to K5, and each kneading zone K1 to K5
In the semi-solid state, the ultrafine powder U and the raw resin G are sequentially passed through a plurality of kneading zones K1 to K5 by driving the screw feeder 22 so that the height becomes higher and lower in the vicinity of the reference temperature. And the softened state are repeated, the mixture of the ultrafine powder U and the raw material resin G contains the surface of the rotating disk 23 rotating by the drive of the screw feeder 22, the inner peripheral surface of the cylinder 21, and While moving between the surface of the fixed disk 24 and the downstream side, the kneading / shearing is performed by the shear force acting on the mixture between them.
It is kneaded.

A plurality of kneading zones K1 to K5 are formed in the apparatus main body 20 so as to sequentially rise and fall near a reference temperature. In the first kneading zone K1, the raw material resin G is in a molten state. In the second kneading zone K2 and the fourth kneading zone K4, the temperature is set so that the raw material resin G is in a semi-solid state, while in the third kneading zone K3 and the fifth kneading zone K5, the raw material resin G is in a softened state. Therefore, the second kneading zone K2 and the fourth kneading zone K4
In this case, the secondary particles formed by agglomeration of the ultrafine powder U by the van der Waals force are in a state of being confined in the semi-solidified raw material resin G. The particles are simultaneously disintegrated when the semi-solidified raw material resin G is cut by receiving the shearing force by the rotation of the rotating disk 23, and in the third kneading zone K3 downstream of the second kneading zone K2, The crushed secondary particles are dispersed in the softened raw material resin G, and the raw material resin G is again brought into a semi-solid state in the fourth kneading zone K4, and the secondary particles are crushed by shearing force.

Therefore, the ultrafine powder U and the raw material resin G are
Each kneading zone K1 composed of a plurality of formed high and low temperatures
Through K5, the crushing of the secondary particles and the subsequent dispersion are repeated, and finally the unit particles of the ultrafine powder U are evenly distributed in the raw material resin G. A dispersed functional resin will be formed.

As a result, as conventionally performed,
In a kneading method in which the raw resin G is heated to a temperature higher than the melting temperature to make it completely liquid, and the ultrafine powder U is mixed into the liquid raw resin G and the mixture is simply stirred, a fan is used. -It is difficult to disintegrate the secondary particles of the ultrafine powder U that has been strongly agglomerated by the Del Waals force, and the ultrafine powder U can be dispersed in the raw resin G in the form of primary particles. Therefore, a high-quality functional resin could not be produced. However, in the present invention, such inconvenience is conventionally solved, and the ultrafine powder U is converted into the raw material resin G in units of particles.
It is possible to easily and uniformly disperse the resin therein, and a high-quality functional resin can be easily manufactured at low cost.

The present invention is not limited to the above embodiment, but includes the following contents.

(1) In the above embodiment, each of the kneading zones K1 to K5 has two rotating disks 23,
Although a fixed disk 24 and a cylinder 21 corresponding to these are provided, the present invention is not limited to the kneading zones K1 to K5 each being constituted by two rotating disks 23, but one. Or three or more.

(2) In the above embodiment, five kneading zones, that is, the first kneading zone K1 to the fifth kneading zone K5 are formed as kneading zones. However, in the present invention, there are five kneading zones. However, the number is not limited to four, and may be four or less, or six or more.

(3) In the above embodiment, the kneading device 10 is provided with the ultrafine powder hopper 31 and the raw resin hopper 33 for storing the ultrafine powder U and the raw resin G, respectively. The ultrafine powder U and the raw resin G are supplied from the apparatus
The two are mixed together for the first time in the apparatus main body 20 by being cut out toward the same. However, the present invention relates to mixing the ultrafine powder U and the raw material resin G in the apparatus main body 20. The present invention is not limited to this. A mixture of the ultrafine powder U and the raw material resin G is prepared in advance in another device independent of the kneading device 10, and the two are mixed to disperse the secondary particles. And the granular material may be supplied to the apparatus main body 20. In this case, in the kneading apparatus 10 of the above embodiment, the first kneading zone K
1 can be omitted and the kneading process can be started from the second kneading zone K2, so that the size of the apparatus can be reduced because the first kneading zone K1 can be omitted, and equipment costs and operation costs can be reduced. Can be reduced.

(4) In the above embodiment, the refrigerant used for adjusting the temperature of each of the kneading zones K1 to K5 is a refrigerant cooled by a cold source such as a refrigerator in the refrigerant supply device 60 and is circulated. However, the present invention is not limited to the circulating use of the refrigerant. For example, tap water or industrial water may be used as the refrigerant, and the refrigerant may be used disposably.

(5) In the above embodiment, the electric heating jacket 90 is used to heat each of the kneading zones K1 to K5, the extrusion zone P, and the product discharge zone V. It is not limited to adopting the electric heating jacket 90 for heating of K1 to K5, P, V, a steam jacket for passing heated steam,
A device using a heating medium such as an oil jacket through which heating oil passes as a heat source may be employed.

(6) In the above embodiment, the extrusion zone P and the product discharge zone V are the sixth jacket 96
The temperature is controlled by heating only the seventh jacket 97, but instead of this, the refrigerant from the refrigerant supply device 60 is also supplied to the extrusion zone P and the product discharge zone V as in the kneading zones K1 to K5. The temperature of the extrusion zone P and the product discharge zone V may be controlled in cooperation with the refrigerant and the sixth and seventh jackets 96 and 97.

(7) In the above embodiment, the kneading and dispersing step is formed by the first to fifth kneading zones K1 to K5. However, according to the present invention, the kneading and dispersing step is performed by the first to fifth kneading zones K1 to K5. It is not limited to the formation by K5, and various combinations of each zone are possible.

That is, as a minimum combination, a second kneading zone K2 for setting the raw material resin G to a temperature near the resin melting temperature Tm and a fifth kneading zone K5 for setting the raw material resin G to a temperature exceeding the resin melting temperature. And a third kneading zone K3 for setting the temperature of the raw material resin G to a temperature lower than the resin melting temperature.
Any of the combinations consisting of

When the kneading zones K2 and K5 are employed, the secondary particles of the ultrafine powder U contained in the raw material resin G are first crushed in the second kneading zone K2 by a shearing force, and Since the ultrafine powder U crushed in the five kneading zone K5 is uniformly dispersed in the raw material resin G in a fluidized state, a uniform functional resin G1 can be obtained.

When the kneading zones K2 and K3 are employed, the raw material resin G is subjected to a larger shearing force in the fifth kneading zone K5 in the third kneading zone K3, so that the secondary resin Dispersion and disintegration of particles are performed more favorably.

In the above combination, a combination in which a third kneading zone K3 is interposed between the second kneading zone K2 and the fifth kneading zone K5 may be adopted. By employing the three kneading zones K2, K3, and K5, the third kneading zone K3 is in the middle of the transition of the mixture of the ultrafine powder U and the raw material resin G from the second kneading zone K2 to the fifth kneading zone K5. In the fifth kneading zone K5, a larger shear force is applied, and the ultrafine powder U crushed in the last fifth kneading zone K5 is dispersed well in the raw material resin G.
A more homogeneous functional resin G1 can be obtained.

The following is a list of examples of these combinations and other combinations. In the following, only symbols such as K1 and K2 are used to indicate each zone for a simple description. Also,
Since the second kneading zone K2 and the fourth kneading zone K4 have exactly the same temperature conditions, only K2 is used without using K4. K2 + K5 K2 + K3 K2 + K3 + K5 K2 + K3 K1 + K2 + K2 + K2 + K2 + K2 + K2 + K2 + K2 + K2 + K2 It is. By doing so, the secondary particles of the ultrafine powder U are satisfactorily dispersed in the raw resin G in advance, so that a more uniform secondary particle crushing process is realized in the second kneading zone K2. The combination of the kneading zones is appropriately selected according to the type of the ultrafine powder U and the raw resin G, and further, the required quality of the functional resin G1.

(8) In the above embodiment, a so-called stone-mill type kneading device 10 is used, in which a screw feeder 22, a rotating disk 23 and a fixed disk 24 are provided on a cylinder 21 as a single-shaft kneading device. However, the kneading method of the present invention is not limited to adopting a uniaxial type as a kneading device, but two kneading shafts provided with spiral kneading blades on the outer peripheral surface, the rotating blades contact each other. A so-called twin-screw kneading device may be employed.

(9) In the above embodiment, one kind of the ultrafine powder U is employed.
The type of the ultrafine powder U to be mixed with the raw material resin G is not limited to one type, but may be plural types.

[0131]

EXAMPLES (First Example) Polyvinyl chloride is used as the raw material resin G, and the ultrafine powder U has a particle size of 0.02 to 0.05 μm, which is a red or blue colorant.
Of quinacridone red or phthalocyanine blue, and 40% by weight of ultrafine powder U
The mixture to which (some stabilizers, lubricants and plasticizers were added) was heated to 170 ° C. to be once in a molten state, and then granulated while cooling to 60 ° C. with a cooling mixer. Things were manufactured first.

Next, the granulated material was sequentially loaded into the apparatus main body 20 of the above embodiment in a predetermined cut-out amount, and a colored resin as the functional resin G1 was prototyped. In this prototype,
The temperature of the first kneading zone K1 (first temperature T1) is raised by 16 ° C. higher than the melting point (150 ° C.) of polyvinyl chloride.
At 0 ° C., the second kneading zone K2 and the fourth kneading zone K4
(The second temperature T2 and the fourth temperature T4) at 60 ° C.
The temperature of the third kneading zone K3 (third temperature T
3) was set to 110 ° C. lower by 40 ° C., and the temperature of the fifth kneading zone K5 (fifth temperature T5) was set to 165 ° C.

Incidentally, the kneading device 10 used in the above-mentioned trial production was used.
The screw feeder 22 in the casing 25
Has an outer diameter of 150 mm, an outer diameter of the screw feeder 22 in the kneading zones K1 to K5 is 140 mm, an outer diameter of the rotary disk 23 is 180 mm, an outer diameter of the product pushing shaft 43 is 100 mm, and an annular shape of the die member 42. Discharge hole 42a
Has a hole diameter of 1.8 mm and an output of driving the screw feeder 22 of the driving device 26 to rotate is 75 kW.

By operating the kneading apparatus 10, a trial production of the colored resin in the molten state as the functional resin G1 was made at a rate of 150 kg per hour. By subjecting this colored resin to cutting treatment with a hot cutter, a granulated pellet master batch pigment could be obtained.

In the obtained granulated pellet master batch pigment, an ultrafine powder of quinacridone red or phthalocyanine blue was uniformly dispersed in polyvinyl chloride in a state where secondary particles were crushed, and the pigment was excellent. Was confirmed. (Second Example) While a binder polymer composed of a styrene-acryl copolymer, a polyester resin, an epoxy resin or the like is used as the raw material resin G, a black colorant having a particle size of 16 nm to 25 nm is used as the ultrafine powder U. Using carbon black, 40 to 95% by weight of raw resin G, 3
A mixture obtained by heating a mixture containing １５15% by weight, an antistatic agent and a release agent into a molten state once, and then cooling the mixture to 60 ° C. with a cooling mixer to produce granules first.

Then, the granules were sequentially loaded into the apparatus main body 20 of the above embodiment in a predetermined cut-out amount, and a black toner for electrophotography, which is the functional resin G1, was prototyped. In this prototype, the temperature of the first kneading zone K1 (first temperature T1) was set to 120 ° C., and the temperatures of the second kneading zone K2 and the fourth kneading zone K4 (second temperature T2 and fourth temperature T1) were set.
4) was set to 65 ° C, the temperature of the third kneading zone K3 (third temperature T3) was set to 80 ° C, and the temperature of the fifth kneading zone K5 (fifth temperature T5) was set to 110 ° C.

Incidentally, the kneading device 10 used in the above-mentioned trial production was used.
The same one as used in the first example was used. The output of the driving device 26 for rotating the screw feeder 22 was set to 90 kw. The rotation speed of the rotating disk 23 was set to 75 rpm.

By operating the kneading apparatus 10 under such conditions, the black resin in the molten state, which is the functional resin G1, is reduced by one.
A prototype could be produced at a rate of 110 kg per hour.

The obtained black toner shows that carbon black, which is an ultrafine powder, is uniformly dispersed in a binder polymer in a state where secondary particles are crushed, and is excellent as a black toner. I was able to confirm. Also,
The yield of the black toner was 85% to 92%, and considering that the conventional yield was 60% to 65%, it was confirmed that the yield of the present invention can be significantly improved by the method of the present invention. We were able to.

[0140]

According to the first aspect of the present invention, the ultrafine powder in the raw material is applied by applying a shearing force to the raw material in the resin solidification zone set at a temperature near the resin thermal deformation temperature at which the resin maintains a solid state. A crushing treatment step of crushing the resin, and applying a shearing force to the raw material in a resin dispersion zone set at a temperature near a resin melting temperature at which the resin becomes a rubber viscoelastic state or a molten state, thereby forming an ultrafine powder in the raw material. And a dispersion treatment step of dispersing, and at least one dispersion treatment step is performed after the crushing treatment step, so that the ultrafine powder is aggregated by van der Waals force in the resin solidification zone. The formed secondary particles are in a state of being confined in the semi-solidified raw material resin, and the secondary particles in the confined state are separated by the raw resin around the solid state being subjected to high shearing force. While being disintegrated at the same time were, secondary particles disintegrated in the resin dispersion zone on the downstream side can be dispersed in the raw material resin.

Therefore, by passing the ultrafine powder and the raw material resin through the resin solidification zone and the resin dispersion zone, the secondary particles are surely crushed and then dispersed to finally form the ultrafine powder. Functional resin in which the unit particles are uniformly dispersed in the raw material resin, and high quality by easily and uniformly dispersing the ultrafine powder in the raw resin in particle units Can be continuously produced in large quantities at low cost.

According to the second aspect of the present invention, since the crushing process and the dispersion process are repeated a plurality of times, the crushing and dispersion of the secondary particles can be more reliably performed by the repetition process. it can.

According to the third aspect of the present invention, since the temperature of the resin dispersion zone in the dispersion treatment step performed during a plurality of crushing treatment steps is set to be equal to or lower than the resin melting temperature, The temperature in the dispersion treatment step performed between the multiple crushing treatment steps is set to a temperature equal to or lower than the resin melting temperature to be in a rubber viscoelastic state, and the temperature difference between the dispersion treatment step and the crushing treatment step The heat loss is suppressed without increasing the size, and a uniform and efficient kneading process can be realized.

According to the fourth aspect of the present invention, since the dispersion treatment step is carried out even before the first crushing treatment step, the secondary particles of the ultrafine powder are removed from the first crushing treatment step. The secondary particles are dispersed in the dispersion treatment step before the crushing, and the secondary particles can be uniformly and effectively crushed in the next crushing treatment step.

According to the fifth aspect of the present invention, the temperature of the resin dispersion zone in the dispersion treatment step performed before the first crushing treatment step is set to a temperature equal to or higher than the resin melting temperature. Can be easily discharged, the production efficiency can be improved, and the kneading device can be used as it is as an injection molding device.

According to the sixth aspect of the present invention, since the temperature of the resin dispersion zone in the last dispersion treatment step is set to be equal to or higher than the resin melting temperature, the ultrafine powder is added to the resin in the last dispersion treatment step. The final finishing of the dispersion treatment is performed, and the functional resin as a product can be discharged out of the system in a fluidized state.

According to the seventh aspect of the present invention, the mixture of the ultrafine powder and the raw material resin is mixed with the surface of the rotating disk rotating by driving the screw feeder, the inner peripheral surface of the cylinder and the surface of the fixed disk. While moving toward the downstream side, the kneading and shearing force acts on the mixture between them.
By kneading, the same operation as the first aspect of the invention can be obtained.

In particular, since the raw material resin is kneaded by a stone mill effect by shearing action while being held between the rotating disk and the fixed disk, the raw material resin is dispersed in the raw material resin as compared with the twin-screw kneading apparatus. Secondary particles can be more efficiently disintegrated.

According to the eighth aspect of the present invention, the temperature of the resin in each zone can be adjusted by the temperature adjusting means provided with the heating means and the cooling means. When the resin is cooled by the cooling means when the temperature is lower than the target temperature, the resin can be quickly returned to the target temperature by heating by the heating means, and the temperature by one of the heating means and the cooling means. As compared with the adjustment, it is possible to realize quick and accurate temperature adjustment while increasing the degree of freedom of the temperature adjustment.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a side sectional view showing an embodiment of a kneading apparatus according to the present invention.

FIG. 2 is a partial sectional view showing a part of the apparatus main body.

FIG. 3 is a sectional view taken along line AA of FIG. 2;

FIG. 4 is an enlarged sectional view of a portion surrounded by a dashed line in FIG. 2;

FIG. 5 is a partial cross-sectional perspective view of a serrated projection of a casing.

FIG. 6 is a graph showing the temperature transition of each kneading zone, extrusion zone and product discharge zone, in which the horizontal axis indicates the distance from the starting point of the first kneading zone, and the vertical axis indicates the temperature. I have.

FIG. 7 is a block diagram showing one embodiment of operation control of the kneading apparatus.

[Explanation of symbols]

 U Ultrafine powder G Raw material resin G1 Functional resin K1 to K5 First to fifth kneading zone P Extrusion zone V Product discharge zone 10 Kneading device 20 Main unit 21 Cylinder 211 to 219 First to ninth cylinder 21a Thin portion 21b Thick portion 21c Mounting hole 21d Serrated protrusion 21e Arc concave portion 21f Chord portion 21g Inclined portion 21h Corner 22 Screw feeder 22a Screw 23 Rotating disk 231 to 2310 First to tenth rotating disk 23a Serrated protrusion 23b Mountain-shaped protrusion 23c Valley-shaped concave portion 24 Fixed disk 241 to 2410 First to tenth fixed disk 24a Thick portion 24b Thin portion 24c Through hole 25 Casing 25a Raw material charging hole 26 Drive unit 26a Spline shaft 26b Spline strip 27 First cooling medium passage 28 Second cooling medium flow passage 29 Tie rod 30 Raw material supply unit DESCRIPTION OF SYMBOLS 1 Ultrafine powder hopper 32 Conveyor 32a Ultrafine powder side drive motor 33 Raw material resin hopper 34 Conveyor 34a Raw material resin side drive motor 35 Relay tube 36 Raw material input hopper 37 Ultrafine powder weigher 38 Raw material resin weigher 37a, 38a Support points 37b, 38b Balance rod 37c Ultrafine powder side weighing sensor 38c Raw material resin side weighing sensor 40 Product discharge part 41 Product discharge cylinder 41a Flange 42 Die member 42a Annular discharge hole 43 Product extrusion shaft 23a, 25d Serrated protrusion 27, 28 Medium flow passage 60 Refrigerant supply device 61 Outgoing line 61a Control valve 61-65 First to fifth outgoing line 61a-65a First to fifth control valve 66 Return line 67 Heat exchanger 70 Control device 71 CPU 72 Output device 73 RAM 74 ROM 81 to 86 First to sixth temperature sensors 90 Electric heating jaws Kette 91-97 First-seventh jacket 99 Power supply

Claims (8)

[Claims] 1. A kneading method for kneading an ultrafine powder and a resin while moving a raw material containing the ultrafine powder and a resin to a downstream side, the method comprising: A crushing step of crushing the ultrafine powder in the raw material by applying a shearing force to the raw material in a resin solidification zone set at a temperature; and a temperature near a resin melting temperature at which the resin is in a rubber viscoelastic state or a molten state. A dispersing step of dispersing the ultrafine powder in the raw material by applying a shearing force to the raw material in the resin dispersion zone set in the above, wherein at least one dispersion processing step is performed after the crushing processing step. A method of kneading an ultrafine powder and a resin. 2. The method according to claim 1, wherein the crushing step and the dispersion step are repeated a plurality of times. 3. The ultrafine powder and resin according to claim 2, wherein the temperature of the resin dispersion zone in the dispersion treatment step performed between the plurality of crushing treatment steps is set to a resin melting temperature or lower. And kneading method. 4. The method for kneading ultrafine powder and resin according to claim 1, wherein a dispersion treatment step is performed before the first crushing treatment step. 5. The ultrafine particle according to claim 1, wherein the temperature of the resin dispersion zone in the dispersion treatment step performed before the first crushing treatment step is set to be equal to or higher than the resin melting temperature. Kneading method of powder and resin. 6. The method for kneading ultrafine powder and resin according to claim 1, wherein the temperature of the resin dispersion zone in the last dispersion treatment step is set to a temperature equal to or higher than the resin melting temperature. . 7. A kneading apparatus for kneading an ultrafine powder and a resin while moving a raw material containing the ultrafine powder and a resin to a downstream side, wherein the ultrafine powder and the raw material resin are loaded. A cylinder, a screw feeder concentrically housed in the cylinder, a plurality of rotating disks concentrically and integrally rotatably mounted on the screw feeder, and concentrically mounted on the cylinder so as to face a side surface of the rotating disk. A plurality of fixed disks are provided, and a resin solidification zone is set at a temperature near a resin heat deformation temperature at which the resin maintains a solid state in a cylinder, and a temperature around a resin melting temperature at which the resin is in a rubber viscoelastic state or a molten state. A resin dispersion zone to be set in each zone, and a temperature adjusting means for adjusting the temperature of the raw material resin in each zone is provided. Place. 8. The kneading apparatus according to claim 7, wherein said temperature adjusting means includes a heating means and a cooling means.