JP2008143105A - Ultrasonic wave oscillation imparting apparatus for resin, and resin composition manufactured by using the ultrasonic wave oscillation imparting apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the kneadability and compatibility of a resin blend, and to improve the dispersion of an additive or a filler added to resin. <P>SOLUTION: This ultrasonic wave oscillation imparting apparatus which imparts ultrasonic wave oscillation to a molten resin has an oscillator for imparting ultrasonic wave oscillation to the resin or an oscillation transferring member which applies the oscillation of the oscillator to the resin. In part of a flow passage where the molten resin flows, there is formed an applying part 20 which the whole or part of the undersurface of the oscillator or an oscillation transferring member faces, and the width (b) of the undersurface 201 of the oscillator or the oscillation transferring member is made wider then the width (d) of the flow passage 11. Further, preferably, the width (d) of the flow passage 11 is 60-15% of the width 201(a) of the flow passage in the applying part 20. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ultrasonic vibration imparting device that imparts ultrasonic vibration to a molten and fluidized resin, and in particular, improves various physical properties and moldability of resins used for extrusion molding, injection molding, etc. The present invention relates to an apparatus for imparting ultrasonic vibration to a resin capable of obtaining a molded product, and a resin composition produced using the apparatus for imparting ultrasonic vibration.

  In kneading equipment, extrusion molding equipment, and injection molding equipment for melting and kneading plastics and other resins to form molded products of the desired shape, the functionality of the resin is improved, and when multiple types of resins are mixed, Improving kneadability or compatibility, improving dispersibility when an additive or filler is blended, or facilitating resin modification is extremely important for molding a high-quality molded product. Therefore, various proposals have been made in order to achieve these objects (see, for example, Patent Documents 1, 2, and 3).

The technique described in Patent Document 1 is a technique for adding an additive such as a compatibilizer to a resin in order to improve moldability and functionality.
The technique described in Patent Document 2 is a technique for improving the dispersibility of the filler in the resin in order to improve various physical properties and moldability.
The technique described in Patent Document 3 is a technique in which when a resin is modified by reactive extrusion, a considerable amount of a peroxide is added to the resin and the modifier, and then melted and kneaded.

  However, the technique described in Patent Document 1 adds a compatibilizing agent for compatibilization, and there is a problem that the compatibilizing agent tends to form a domain and is not efficient. In addition, there is a problem that the effect of improving various physical properties is limited. In addition, there is not always an optimum compatibilizer for various resins, and there is a problem that it takes a lot of labor to find an optimum compatibilizer every time the resin is different.

  In the technique described in Patent Document 2, strong kneading and multiple kneading are performed for the dispersion of the fine filler, but such a method has a problem in that there is a limit to improving the dispersibility of the filler. Also, kneading multiple times is inefficient. Furthermore, kneading above a certain level has a problem of deteriorating resin properties such as mechanical properties and color tone.

In the technique described in Patent Document 3 described above, a considerable amount of peroxide is added to the resin. However, such a method not only makes it difficult to control the amount of modification and molecular weight, but also results from the peroxide. New problems such as odor and coloration occur.
In addition, the techniques described in Patent Documents 1, 2, and 3 individually solve problems such as improved functionality, improved kneadability or compatibility, improved dispersibility of fillers, and ease of resin modification. Therefore, a technical method that can solve these problems all at once is eagerly desired.

  Therefore, for example, Patent Document 4 proposes an attempt to solve these problems using ultrasonic vibration. However, even in the technique described in Patent Document 4, there is a problem that the improvement of the dispersibility of the filler is not mentioned and the effect is limited.

In addition, in the present applicants, Patent Documents 5 to 7 use ultrasonic vibration to improve functionality, improve kneadability or compatibility, improve filler dispersibility, facilitate resin modification, and the like. Provides a predetermined effect.
However, further improvement of the effect is expected in the technology provided by the applicant.

JP-A-5-247282 Japanese Patent Laid-Open No. 10-101870 JP-A 63-1170008 US Pat. No. 6,528,554 Japanese Patent Laid-Open No. 3-47723 JP-A-8-47960 JP 2001-88194 A

The present invention has been made to solve the above problems, and by devising the shape of the application part of ultrasonic vibration, leakage of sound pressure to the periphery of the application part is reduced, and functionality such as moldability is achieved. In addition, it improves the kneadability and compatibility of the resin blend when two or more types of resins are mixed, and also breaks down the lump formed by agglomeration of fine fillers, making each fine filler individual size, originally manifested An object of the present invention is to provide an ultrasonic vibration imparting device that can be close to the function of a composition that can be dispersed and that can improve the dispersibility of a fine filler that has been difficult to disperse in a resin.
In addition, a composition produced using this ultrasonic vibration imparting device, in particular, excellent mechanical properties such as rigidity and impact resistance, appearance, adhesion to glass fibers, etc., and a high-quality molded product can be obtained. An object is to provide a resin composition.

In order to achieve the above object, an ultrasonic vibration applying device of the present invention is an ultrasonic vibration applying device that applies ultrasonic vibration to a molten resin, or a vibrator that applies ultrasonic vibration to the resin or the vibration. A vibration transmission member for applying the vibration of the child to the resin, and an application portion where the whole or a part of the lower surface of the vibrator or the vibration transmission member faces a part of the flow path through which the molten resin flows In addition, the width (a) of the flow path in the application unit is configured to be wider than the width (d) of the flow path.
The width (d) of the flow path is preferably 60% to 15% of the width (a) of the flow path in the application section, and further, the flow path width (a) in the application section, The relationship with the width (b) of the lower surface of the vibrator or vibration transmitting member is preferably 0.5 ≦ b / a ≦ 1.5.

  Here, the “vibrator” is a source of ultrasonic vibration, and the “vibration transmitting member” is, for example, attached to the tip of the vibrator to transmit the vibration of the vibrator to the resin. Refers to a member. Hereinafter, the vibrator or the vibrator and the vibration transmitting member may be collectively referred to as a “vibrator”.

In the present invention, the following operation is produced by making the width (a) of the flow path in the application section wider than the width (d) of the flow path. And this effect | action makes the width | variety (d) of a flow path 60 to 15% of the width | variety (a) of the flow path in an application part, Furthermore, the flow path width (a) in the said application part, By making the relationship with the width (b) of the lower surface of the vibrator or vibration transmitting member 0.5 ≦ b / a ≦ 1.5, it becomes more prominent.
That is, as in the present invention, the width (d) of the flow path is smaller than the width (a) of the flow path in the application unit. Specifically, the width (d) of the flow path is set to the width of the flow path ( If it is set to 60% to 15% of a), leakage of vibration from the application section in the flow path direction can be suppressed, and the reflected wave can be used effectively. Further, when the relationship between the flow path width (a) in the application unit and the width (b) of the lower surface of the vibrator or vibration transmission member is 0.5 ≦ b / a ≦ 1.5, the vibrator or It is possible to efficiently apply ultrasonic vibration from the vibration transmitting member to the molten resin.
As a result, it is possible to achieve an improvement in rigidity and impact resistance and an improvement in dispersibility of molded products that cannot be predicted from the prior art. This suppresses the leakage of vibration from the application section in the flow path direction, so that vibration is concentrated on the resin and pressure vibration due to cavitation and ultrasonic waves is effectively generated inside the resin. It is estimated that

Moreover, it is preferable that the present invention is formed so that vibration is applied to the resin from a direction orthogonal to the flow direction of the resin.
Further, in the present invention, the flow path is formed in any of a cylinder of an extrusion molding apparatus or an injection molding apparatus, a cylinder of an extruder or a kneading machine, a chamber, a die provided on the downstream side of the outlet of the cylinder, or a mold. It is preferable to do.

  The resin composition of the present invention is produced using any of the above ultrasonic vibration applying devices. In the resin composition thus produced, the average particle system of the filler alone is 1-1000 nm, and the residual ratio of filler aggregates (number of filler aggregates after ultrasonic kneading / number of filler aggregates before kneading) But very little.

  Here, the resin that imparts ultrasonic vibration is any one of a single type of resin and / or elastomer, a mixture of two or more types of resin and / or elastomer, and a mixture of resin and / or elastomer and filler. It may be either a thermosetting material or a thermoplastic material.

  According to the present invention, the dispersibility of fine additives and fillers in the resin is improved by defining the relationship between the application section for applying ultrasonic vibration to the molten resin and the flow path through which the molten resin flows. be able to. This makes it possible to produce polymer blends and alloys with improved physical properties.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of an ultrasonic wave imparting device of the invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view of a die of an extruder equipped with a horn of an ultrasonic oscillator according to an embodiment of the present invention. In the following description, “resin” means a resin including a thermoplastic elastomer as well as a narrowly defined resin unless otherwise specified.

  The resin heated and melted in the cylinder 2 of the extruder (not shown) is supplied to the nozzle 13 through the flow path 11 in the die 1 and pushed out from the tip of the nozzle 13. A vibrating body 3 is attached to the middle part of the die 1. The vibrator 3 includes a vibrator 31 connected to an ultrasonic supply source (not shown), and a horn 32 as a vibration transmission member attached to the tip of the vibrator 31. A horn insertion hole 12 is formed in the middle of the die 1 until it reaches the flow path 11. The horn 32 is inserted into the horn insertion hole 12, and the lower surface thereof forms a vibration applying unit 20.

An annular flange 33 extending to the peripheral edge of the opening of the horn insertion hole 12 (see FIG. 1) is formed on the middle portion of the horn 32. The flange 33 is fixed to the die 1 by the horn presser 15 and the packing 16 at the periphery of the opening.
The form of the horn is not limited to a cylindrical shape, and various types such as a ring shape, a cone shape, a truncated cone shape, a conical type, and an exponential type can be selected.

[Applying section]
The application unit 20 is formed in a portion where the whole or a part of the lower surface of the horn 32 faces. The application unit 20 is formed by a lower surface 201 of the horn 32 and a flow path 202 through which resin flows corresponding to the lower surface of the horn 32.
In addition, the width d of the flow channel 11 is made smaller than the width a of the flow channel 202 in the application unit 20. Specifically, the width d of the flow channel 11 is equal to the width a of the flow channel 202 in the application unit. It is preferable that it is 60%-15% of.
Furthermore, the relationship between the diameter (width) b of the lower surface 201 forming the application unit 20 of the horn 32 and the flow path 202 width a in the application unit 20 satisfies the condition of 0.5 ≦ b / a ≦ 1.5. It is preferable.

  In this way, the width d of the flow path 11 is made smaller than the width a of the flow path 202 in the application unit 20. Otherwise, the ultrasonic vibration acting on the resin is applied through the flow path 11 during application. This makes it easier to leak. If the ultrasonic vibration leaks and attenuates, the transmission of the reflected wave becomes worse, and the secondary and tertiary reflected waves cannot be used effectively.

The relationship between the diameter (width) b of the lower surface 201 forming the application unit 20 of the horn 32 and the width a of the flow path 202 in the application unit 20 satisfies the condition of 0.5 ≦ b / a ≦ 1.5. As the number of wall portions increases, the number of reflected waves (including secondary and tertiary reflected waves) also increases and the above effect can be enhanced.
On the other hand, when the relationship b / a between the diameter (width) b of the lower surface 201 forming the application unit 20 of the horn 32 and the flow path 202 width a in the application unit 20 is smaller than 0.5, the ultrasonic vibration is attenuated. When the reflected wave becomes weak and b / a exceeds 1.5, most of the vibration applied from the horn escapes to other than the resin portion, resulting in poor energy efficiency.

  Furthermore, when the width d of the flow path 11 is larger than 60% of the width a of the flow path 202 in the application section, the ultrasonic vibration applied from the horn 32 leaks from the flow path 11 and the flow path 202 of the application section 20 Less reflected waves from the wall. Further, if the width d of the flow path 11 is smaller than 15% of the width a of the flow path 202 in the application section, the resin flow in the flow path 11 is deteriorated.

FIG. 2 shows a first embodiment of the application unit.
As shown in the figure, in this embodiment, the lower surface 201 of the horn forming the application unit 20 is a perfect circle. Further, the flow path 202 forming the application unit 20 is also substantially the same shape as the horn lower surface 201, that is, a circle having substantially the same diameter as viewed from the plane.
Specifically, the diameter (width) b of the lower surface 201 of the horn 32 and the diameter (width) a of the flow path 202 in the applying unit 20 are substantially the same (b / a≈1) (FIG. 2B ), The directions of a and b are slightly shifted in order to facilitate understanding of the relationship between a and b). Further, the width d of the flow path 11 is approximately 1/3 (33%) of the width a of the flow path 202 in the application unit 20.

Second Embodiment FIG. 3 shows a second embodiment of the application unit.
As shown in the figure, the part that forms the application unit 20 that applies vibration to the molten resin includes the diameter (width) b of the lower surface 201 of the horn 32 and the diameter (width) b of the flow path 202 in the application unit 20. However, b / a≈1.5. Therefore, in this embodiment, a part of the lower surface of the horn 32 forms the application unit 20.
In addition, the width d of the flow path 11 is approximately ½ (50%) of the width a of the flow path 202 in the application unit 20.

  The shape of the application unit 20 is not limited to a perfect circle as seen from the plane shown in the first and second embodiments. That is, the diameter (width) a of the lower surface 201 of the horn 32 and the diameter (width) b of the flow path 202 in the application unit 20 are the entire circumference of the lower surface 201 of the horn 32 in the application unit 20 and the flow path 202 in the application unit 20. Any shape can be used as long as it satisfies the condition of 0.5 ≦ b / a ≦ 1.5, for example, an elliptical shape having a long diameter portion in the flow direction of the resin in the flow path 11. You can also.

On the other hand, as shown in FIG. 4, the width (diameter) b of the lower surface 201 of the horn 32, the width a of the flow path 202, and the width d of the flow path 11 are substantially the same. ing. That is, the diameter (width) a of the lower surface 201 of the horn 32 and the diameter (width) b of the flow path 202 in the application unit 20 are b / a≈1.0, and the width d of the flow path 11 is It is almost 100% of the width a of the flow path 202 in the application unit 20.
With such a configuration, although the effect of ultrasonic vibration applied from the lower surface of the horn 32 can be expected, vibration acting on the resin when ultrasonic waves are applied is likely to leak through the flow path 11, The effect of the reflected wave from the road wall cannot be expected.

Furthermore, as shown in FIG. 5, the diameter (width) a of the lower surface 201 of the horn 32 and the diameter (width) b of the flow path 202 in the applying unit 20 are b / a≈2.0. The width d of the path 11 is almost 100% of the width a of the flow path 202 in the application unit 20.
With such a configuration, ultrasonic waves are not efficiently applied from the lower surface of the horn 32, and vibrations that act on the resin when ultrasonic waves are applied are likely to leak through the flow path 11.

[Ultrasonic vibration]
As described above, the ultrasonic vibration applied to the resin from the horn 32 is orthogonal to the direction in which the molten resin flows substantially perpendicularly. The vibrator 31 is vibrated by an ultrasonic oscillator (not shown). The ultrasonic oscillator is preferably an automatic frequency tracking type oscillator with an amplitude control circuit in order to cope with a change in resonance frequency accompanying a change in temperature or an acoustic load change accompanying a change in conditions.

  If the necessary ultrasonic output does not reach the required value for one transducer 31, a plurality of transducers 31 can be used. In that case, the necessary number of vibrators 31 having the same vibration characteristics may be prepared and attached to the outer peripheral surface of the horn 32.

  As the frequency and amplitude of the ultrasonic vibration, it is preferable to select one that can effectively generate pressure vibration by cavitation or ultrasonic waves inside the molten resin flowing through the flow path 11. The specific frequency and amplitude vary depending on the type of resin and need to be selected from experiments and empirical values. In general polymers or copolymers, the frequency is in the range of 10 to 100 kHz, preferably in the range of 15 KHz to 25 KHz. The amplitude may be selected within the range of 1 μm to 50 μm.

[Horn]
The horn 32 constitutes a part of the flow path 11 in the application unit 20, and applies vibration in contact with the resin flowing in the flow path 11. The horn 32 is preferably highly adherent to the molten resin. If the adhesion is low, the improvement of the physical properties of the resin cannot be enhanced. This is probably because the resin does not follow the vibration of the horn 32, and pressure vibration due to cavitation or ultrasonic waves does not occur effectively.

  Therefore, as the material of the horn 32, a material having sufficient durability against ultrasonic vibration and having good adhesion to the molten resin is selected as long as the transmission loss of vibration is small. When the resin is a material containing a resin modified with carboxylic anhydride or its anhydride, examples of horn materials having good adhesion include steel materials such as duralumin, titanium, stainless steel, carbon steel and alloy steel, and soft iron. Etc.

  Further, a material having good resin adhesion may be plated on the end face of the horn 32, or a metal having good adhesion may be melted and sprayed on the horn 32 at high speed to form a surface of the metal constituting the horn 32. May be modified. As a metal to be plated or sprayed, a metal having high adhesion to the resin may be selected. The surface polishing performed after the thermal spraying process or after plating may be adjusted to leave unevenness, thereby improving the adhesion of the resin.

  Further, in order to improve the adhesion of the horn 32 to the resin, fine irregularities may be formed on the end surface of the horn 32 by sandblasting or etching, or grooves may be formed by machining or laser processing. Moreover, you may apply | coat the adhesive improvement agent for improving adhesiveness. Such an adhesion improver varies depending on the type and properties of the resin, but in the case of a general polymer or copolymer, for example, maleic anhydride or a maleic acid composition can be exemplified.

[Vibration transmission suppression means]
The vibration of the horn 32 is preferably prevented from being transmitted to other members other than the resin flowing in the flow path 11, for example, the die 1 and the cylinder 2. When the ultrasonic vibration is transmitted to the other member other than the resin, not only is the energy of the ultrasonic vibration consumed unnecessarily, but the other member forming the flow path 11 is not connected to the vibrator 31. May vibrate at a different frequency and impair the effect of ultrasound. In addition, the die 1 and the cylinder 2 may be damaged.

  In this embodiment, a packing 16 that absorbs vibration is interposed between the horn 32 and the die 1 to suppress vibration transmission. Further, as will be described later, a gap G having a certain size is provided between the horn 32 and the inner peripheral surface of the horn insertion hole 12 of the die 1. This gap G also functions as vibration transmission suppressing means.

  The packing 16 as vibration transmission suppressing means is provided between the horn presser 15 and the flange 33. The elasticity (longitudinal elasticity coefficient or transverse property coefficient) E of the packing 16 is such that E <0.3Eh, preferably E <0.1Eh, when the elasticity of the horn 32 is Eh. . As long as this elastic condition is satisfied and heat resistance is provided, the packing 16 may be made of rubber, resin, a paper member impregnated with resin, metal, or the like.

  The size of the gap G between the inner periphery of the horn insertion hole 12 and the lower outer peripheral surface of the horn 32 may be appropriately selected within a range of more than 0.05 mm and less than 0.5 mm. If the size of the gap G is 0.05 mm or less, the gap G is too small and the vibration of the horn 32 is easily transmitted to the die 1, and the die 1 is vibrated. In addition, even when the gap G is larger than 0.5 mm, when there is no concern that the resin leaks from the gap G, or when measures are taken to prevent resin leakage at a portion other than the gap G, the gap G is It may exceed 0.5 mm.

[Resin composition]
By applying ultrasonic vibration with the ultrasonic vibration applying apparatus having the above-described configuration, a resin composition with improved dispersibility of fine additives and fillers can be generated. For example, a resin composition in which the average particle system of the filler alone is 1-1000 nm and the residual ratio of filler aggregates (the number of filler aggregates after ultrasonic kneading / the number of filler aggregates before kneading) is reduced is generated. Can do.

  Examples of the resin constituting such a resin composition include polystyrene resins (for example, polystyrene, butadiene / styrene copolymers, acrylonitrile / styrene copolymers, acrylonitrile / butadiene / styrene copolymers, etc.), B / AS resin, polyethylene, polypropylene, ethylene-propylene resin, ethylene-ethyl acrylate resin, polyvinyl chloride, polyvinylidene chloride, polybutene, polycarbonate, polyacetal, polyphenylene oxide, polyvinyl alcohol, polymethyl methacrylate, saturated polyester resin (for example, polyethylene Terephthalate, polybutylene terephthalate, etc.), biodegradable polyester resins (for example, hydroxycarboxylic acid condensates such as polylactic acid, polybutylene succinate) Such as condensates of diol and dicarboxylic acid) such as polyamide resin, polyimide resin, fluororesin, polysulfone, polyethersulfone, polyarylate, polyetheretherketone, liquid crystal polymer, polyolefin elastomer, polyester elastomer, styrene elastomer, etc. One kind or a mixture of two or more kinds may be mentioned. Among these thermoplastic resins, polystyrene resins and polyolefin resins are preferable, and polystyrene and polypropylene are particularly preferable.

  The resin has a melt flow index measured in the vicinity of the processing temperature of 0.05 to 1000 g / 10 minutes, preferably 0.1 to 1000 g / 10 minutes, and more preferably about 1 to 1000 g / 10 minutes. It is good to be in.

Examples of the filler added and dispersed in the resin include spherical fillers such as titanium oxide, silica, calcium carbonate, and glass beads, plate-like fillers such as talc, mica, and clay, and fibers such as carbon nanotubes, carbon fibers, and glass fibers. Or a rod-like filler.
In addition, a material that is in a molten state at the time of extrusion kneading and is solid at room temperature, such as a low melting point alloy, is also included. The particle diameter is not particularly limited, but the present invention can be applied to a particle diameter of 1 μm or less, particularly 0.1 μm or less. The blending amount of the filler is not particularly limited, but it can be applied from a very low blending ratio of about 0.1 wt% to a high blending ratio of several tens wt%.

[Examples and Comparative Examples]
[conditions]
(1) Extruder: A TEX30H twin screw extruder manufactured by Nippon Steel Works was used, and the cylinder temperature was 280 ° C. and the die temperature was 280 ° C. The discharge amount was 7 kg / hr, and the screw rotation speed was 200 RPM.
(2) Ultrasound: A die equipped with a horn for applying vibration in a direction perpendicular to the resin composition was attached to the outlet of the twin screw extruder.
Frequency: 19.5kHz
Amplitude: 7 μm
Horn material: Duralumin Eh = 7 × 10 ^ 10Pa
(3) Composition material:
Polycarbonate (PC = FN1900A manufactured by Idemitsu Kosan Co., Ltd.)
TiO ₂ (Ishihara Sangyo Co., Ltd. average particle size 220nm)

(1) Example 1
In Example 1, melting and kneading were performed using a die having a structure having an application section shown in FIG. That is, the diameter b of the lower surface 201 of the horn 32 in the application unit 20 and the width a of the flow channel 202 are b / a≈1.0, and the width d of the flow channel 11 is larger than the width a of the flow channel 202 in the application unit 20. Melting and kneading were performed using a 33% die.
According to Example 1, the number of aggregates was small, and the reflectance of light was improved. The results are shown in Table 1.

(2) Example 2
In Example 2, melting and kneading were performed using a die having a structure having an application section shown in FIG. 3 under the above conditions. That is, the diameter b of the lower surface 201 of the horn 32 in the application unit 20 and the width a of the flow channel 202 are b / a≈1.5, and the width d of the flow channel 11 is larger than the width a of the flow channel 202 in the application unit 20. Melting and kneading were performed using a 50% die.
According to Example 2, the aggregate content was small, and the reflectance of light was improved. The results are shown in Table 1.

(3) Comparative Example 1
In Comparative Example 1, melting and kneading were performed using a die having a structure having an application portion shown in FIG. That is, the diameter b of the lower surface 201 of the horn 32 in the application unit 20 and the width a of the flow channel 202 are b / a≈1.0, and the width d of the flow channel 11 is larger than the width a of the flow channel 202 in the application unit 20. Melting and kneading were performed using a 100% die (the same width in which the flow path 202 in the application unit 20 does not have a swelled portion relative to the flow path 11).

(4) Comparative Example 2
In Comparative Example 2, melting and kneading were performed using a die having a structure having an application section shown in FIG. That is, the diameter b of the lower surface 201 of the horn 32 and the width a of the flow channel 202 in the application unit 20 are b / a≈2.0, and the width d of the flow channel 11 is larger than the width a of the flow channel 202 in the application unit 20. Melting and kneading were performed using a 100% die.
In Comparative Examples 1 and 2, the content of aggregates was large and no improvement in the reflectance of light was observed. The results of Comparative Example 1 and Comparative Example 2 are shown in Table 1.

here,
The degree of improvement in the reflectance of light (ΔY) refers to the difference between the reflectance Y when an ultrasonic wave is applied and the reflectance Y when no ultrasonic wave is applied. Therefore, the greater the ΔY, the greater the improvement in reflectivity.
In addition, the reflectance was measured by injection molding the kneaded resin material and using a spectrophotometer using the injection molded product.
In addition, the aggregate is a so-called submicron particle or nano-sized particle having an average particle diameter of 1 to 1000 nm of a filler alone, which is aggregated by van der Waals force or physical force to form a lump. An aggregate that is larger than this. For measurement of the aggregate, the sample was observed with a scanning electron microscope and photographed, and the number of aggregates of 3 μm or more was quantified.

As can be seen from the results in Table 1 above, the compositions produced in Example 1 and Example 2 had a small number of aggregates and a high light reflectance.
In Comparative Example 1, the sound pressure leaks in the direction of the flow path, and in Comparative Example 2, since the vibration is not sufficiently applied to the resin in the flow path, the number of aggregates is large and the light reflectance is high. It was low.

As shown in FIG. 6, the reflectance Y is improved only slightly even if the amount of TiO ₂ is increased. That is, even if the amount of TiO ₂ is increased from 15% to 20%, the degree of improvement ΔY in reflectance is only about 0.3%. Therefore, it can be said that the improvement degree ΔY of the reflectance in Examples 1 and 2 is 0.3 and 0.2 is a considerable effect.

The present invention is effective for the production of a filler-filled polymer composite material, a polymer blend or a polymer alloy. In particular, a resin composition containing a filler that is difficult to disperse in sub-micron and nano-order, such as a PC / TiO ₂ liquid crystal module reflector material excellent in light reflection characteristics, PC / excellent in both flame retardancy and transparency. It is suitable for the production of nano-silica materials, optical wavelength control materials such as PC / TiO ₂ , ZnO, Fe ₂ O ₃ , Lb / a ₆ , ITO, ATO, and carbon nanotube-containing resin materials having excellent conductivity and chargeability.

It is sectional drawing of the die | dye concerning one Embodiment of this invention which mounted | wore the die | dye of the extruder with the horn of the ultrasonic oscillator. BRIEF DESCRIPTION OF THE DRAWINGS It is principal part schematic which shows the relationship between the horn concerning 1st Example of this invention, and a flow path, (A) is a perspective view, (B) is a top view, (C) is II sectional drawing in (B). It is. It is a principal part schematic diagram which shows the relationship between the horn concerning 2nd Example of this invention, and a flow path, (A) is a perspective view, (B) is a top view, (C) is II sectional drawing in (B). It is. It is a principal part schematic diagram which shows the relationship between the horn concerning the 1st comparative example of this invention, and a flow path, (A) is a perspective view, (B) is a top view, (C) is II sectional drawing in (B). It is. It is a principal part schematic diagram which shows the relationship between the horn concerning 2nd comparative example of this invention, and a flow path, (A) is a perspective view, (B) is a top view, (C) is II sectional drawing in (B). It is. Is a graph showing the relationship between reflectance Y and the content of TiO _2.

Claims (6)

In an ultrasonic vibration applying device that applies ultrasonic vibration to a molten resin,
A vibrator that applies ultrasonic vibration to the resin or a vibration transmission member that applies vibration of the vibrator to the resin;
In the middle of the flow path through which the molten resin flows, an application portion is formed in which all or a part of the lower surface of the vibrator or the vibration transmitting member faces,
And the width | variety (a) of the flow path in the said application part was made wider than the width | variety (d) of the said flow path. The ultrasonic vibration provision apparatus to resin characterized by the above-mentioned.   The apparatus for applying ultrasonic vibrations to a resin according to claim 1, wherein the width (d) of the flow path is 60% to 15% of the width (a) of the flow path in the application section. The relationship between the width (a) of the flow path in the application section and the width (b) of the lower surface of the vibrator or vibration transmitting member is 0.5 ≦ b / a ≦ 1.5. An apparatus for imparting ultrasonic vibration to a resin according to claim 1 or 2.   The apparatus for applying ultrasonic vibration to a resin according to any one of claims 1 to 3, wherein the application unit is formed so as to apply vibration to the resin from a direction orthogonal to the flow direction of the resin. .   The flow path is formed in any of a cylinder of an extrusion molding apparatus or an injection molding apparatus, a cylinder of an extruder or a kneading machine, a chamber, a die provided on the downstream side of the outlet of the cylinder, or a mold. The apparatus for imparting ultrasonic vibration to a resin according to any one of claims 1 to 4.   A resin composition produced using the ultrasonic vibration applying device according to claim 1.

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