JP4745684B2 - Method for producing polymer blend material - Google Patents

Description

The present invention relates to a method for producing a polymer blend material for carrying out a shear molding process by rotating 2 to 5 g of a polymer material in a molten state at a high speed with an internal feedback screw.

Specifically, when one polymer component is used as a matrix, a microscopic dispersion structure in which the dispersed phase size of the other polymer component is controlled to several tens of nanometers, or both polymer components are microscopically interrelated. The present invention provides a method for producing a polymer blend material that enables the production of a polymer blend film having a structure (co-continuous structure) or the like continuously connected to each other. Conventionally, even in the case of a blend that is incompatible with each other in a stationary field (incompatible), if the method for producing a polymer blend material according to the present invention is used, an extra additive such as a compatibilizer is not added, The above structure can be realized. More specifically, for example, ferroelectric materials, electronic and electrical parts such as connectors and electronic circuit boards, heat resistant structural materials, vibration damping materials, heat resistant materials that can be used as materials used in the field of acoustic materials, machinery This is a method for producing a polymer blend material for experimentally producing a blend extrudate excellent in mechanical properties, dimensional stability, etc., with a small amount of sample.

In addition, the present invention melts and kneads an incompatible polymer blend using a shear molding machine equipped with an internal feedback screw capable of easily rotating a screw at 1000 rpm or more, so that one polymer component is used as a matrix. In this case, a nanodispersed polymer blend extrudate (including a film or a sheet) having a microscopically dispersed structure in which the dispersed phase size of the other polymer component is controlled to a level of several tens of nanometers is produced .

Conventionally, even with blend systems that do not melt together in a stationary field (incompatible), if the method according to the present invention is used, shear molding with an internal feedback screw is added without adding extra additives such as a compatibilizer. A polymer blend extrudate having the above structure, that is, a dispersed phase of several tens of nanometers, can be easily realized by rotating the screw at 1000 rpm or more and performing melt kneading for several minutes using a processing machine . More specifically, for example, heat resistance that can be used as a material used in the fields of electronic and electrical parts such as ferroelectric materials, piezoelectric materials, pyroelectric materials, heat resistant structural materials, sound insulation materials, acoustic materials, etc. , To produce a polymer blend extrudate excellent in mechanical properties, adhesiveness, motility and the like.

  Conventionally, regarding the size of the dispersed phase in the incompatible polymer blend system, the minimum dispersed particle diameter (D) of the dispersed phase placed in the steady shear flow field is the interfacial tension (Γ) between two components, shear rate ( S) is defined by the balance between the viscosity (η) by Taylor, and it is reported that it is formulated as in equation (1) (Non-Patent Document 1 (GITaylor, Proc. R) Soc. London, A138, 41 (1932), Non-Patent Document 2 (GITaylor, Proc. R. Soc. London, A146, 501 (1934))).

Here, η _r is the ratio of the viscosity of the two-component system, and η _m is the viscosity of the matrix phase. After that, although applied to many incompatible polymer blends by Wu and the formula (1) was improved in order to reproduce the measured value of D, the physical quantity involved is basically unchanged (Non-patent Document 3). (S. Wu, Polym. Eng. Sci., 27, 335 (1987))).

For example, the reactive processing technique lowers the interfacial tension due to the formation of a copolymer at the interface, so that it can be understood from the equation (1) that the particle size of the dispersed phase is reduced. By such a formulation, the theoretical limit of the disperse phase size in the incompatible polymer blend system is also determined by Macosko et al. (U. Sundararaj and CW Macosko, Macromolecules, 28, 2647, (1995)) (Non-patent Document 4). 1, the steady shear rate (S) is limited to a range (S = 10 to 80 sec ⁻¹ ) that can be generated by a normal kneading extruder. That is, when formula (1) is reconsidered, the theoretical limit of D depends on the balance between the shear rate and the viscosity, but it is easily assumed that the use of a higher shear rate region contributes to the reduction of the dispersed phase size. The In fact, it has recently been reported that incompatible fields, incompatible polymer blend systems are compatible under high shear conditions. For example, it has been reported that poly (p-phenylene sulfide) and nylon 46 system are compatibilized only in the region on the nylon rich side under a shear flow field (S = 189 sec ⁻¹ ) (Non-Patent Document 5 (JB An , T. Suzuki, T. Ougizawa, T. Inoue, K. Mitamura, and K. Kawanishi, J. Macromol. Sci., -Physics, B41, 407 (2002).)).

Therefore, in the past, in order to express the performance of the desired blend to some extent, blending was performed using a compatibilizing agent having affinity or adhesion with one or both of the blend components. Because they are not mutually soluble at the level, their performance and function could not be enhanced to the limit. Reactive processing technology discovered 30 years ago (Non-Patent Document 6 (F. Ide and A. Hasegawa, J. Appl. Polym. Sci., 18,963 (1974).)) Is expected to reduce the size of the dispersed phase, but there is a drawback that it cannot be realized if there is no reactive group between the two components. Therefore, in order to compatibilize an incompatible polymer blend system without using an extra additive such as a compatibilizer, a blending technique in a high shear region, that is, a high shear molding process is required. is there. Actually, depending on the screw structure, etc., the correspondence between the screw rotation speed and the shear rate in the molding machine is not uniquely determined, but the screw rotation speed in a normal molding machine is 100 to 300 rpm. Since the corresponding shear rate is estimated to be around 100 sec ⁻¹ at the most, it is considered that a significant increase in the screw rotation speed (500 rpm or more) first leads to a dramatic increase in the shear rate.

  Conventionally, when simple mechanical mixing of an incompatible polymer blend system is performed using a normal kneading extruder (screw rotation speed of about 300 rpm), the theoretical and experimental limits on the dispersed phase size of one polymer component Is reported in Non-Patent Document 4 as 350 nanometers (nm) by Macosko et al. Therefore, in order to express the performance and function of a desired polymer blend as a synergistic effect, conventionally, kneading has been performed using a compatibilizer having affinity or adhesiveness with one or both of the blend components. Because of the fact that they are not essentially dissolved in each other at the molecular level, when one polymer component is used as a matrix, the polymer phase is extruded with the dispersed phase size of the other polymer component being on the order of several microns to submicrometers. Only the thing was obtained, and those performance and functions could not be enhanced to the limit. In addition, reactive processing technology (Non-Patent Document 6) discovered 30 years ago is a technique that reduces the interfacial tension by causing a reaction between functional groups existing between blend components, thereby reducing the size of the dispersed phase. Yes, we have succeeded in reducing the dispersed phase size of polymer blends to sub-micrometer to tens of nanometer level, but technically because there is no reactive group between the two components. It has become a major obstacle.

  Therefore, when blending with the aim of expressing the synergistic effect of the incompatible polymer blend system, it is necessary to control the dispersed phase at a size close to the molecular level. It was difficult to produce a nano-dispersed polymer blend. In addition, admixtures of additives such as compatibilizers and reaction products generated by reactive processing methods are structural defects in optical materials and electronic / electrical materials that require a continuous and pure microstructure. In other words, it is a “foreign substance”, which has a drawback that it becomes a large obstacle in practical use.

  Against this background, the inventor has invented and manufactured a micro-high shear molding machine equipped with an internal feedback screw that can rotate a screw at 1000 rpm or more (maximum output 3000 rpm). This apparatus is already on the market under the name of “trace type high shear molding machine HSE3000mini”. The present invention can be realized for the first time by using the trace type high shear molding machine.

G.I.Taylor, Proc.R.Soc.London, A138,41 (1932) G.I.Taylor, Proc.R.Soc.London, A146,501 (1934) S. Wu, Polym.Eng.Sci., 27,335 (1987) U. Sundararaj and C. W. Macosko, Macromolecules, 28, 2647, (1995) J-B An, T. Suzuki, T. Ougizawa, T. Inoue, K. Mitamura, and K. Kawanishi, J. Macromol. Sci., -Physics, B41, 407 (2002) F.Ide and A.Hasegawa, J.Appl.Polym.Sci., 18,963 (1974) H. Shimizu, K. Komori, and T. Inoue, Transactions of the Materials Research Society of Japan, 29, 263 (2004).

  The object of the present invention is to melt the blend in a high shear region without adding an extra additive such as a compatibilizing agent to a blend that has not been incompatible with each other in a static place (incompatible). A structure in which the components are dissolved at the molecular level by kneading. When one polymer component is used as a matrix, the dispersed phase size of the other polymer component is controlled to a size of several tens of nanometers. An object of the present invention is to provide an apparatus for producing a polymer blend film having a dispersed structure or a structure (co-continuous structure) in which both polymer components are continuously connected microscopically.

  One of the inventors found that there is a region where blends of systems that are not compatible with each other (non-compatible) in a stationary field are compatible under a high shear flow field, and have reported the basic data. (Non-Patent Document 7 (H. Shimizu, K. Komori, and T. Inoue, Transactions of the Materials Research Society of Japan, 29, 263 (2004).)). Therefore, the inventors need to manufacture a molding machine capable of generating a high shear flow field, that is, capable of high-speed screw rotation, in order to utilize the basic knowledge in the high shear region as a molding process condition. I noticed that there is.

  First of all, a molding machine that can stably operate at high speeds of the screw is necessary, but at the same time, kneading time is also an important factor. With normal screw shapes, when operating at high speeds, the blend is extruded instantaneously. This is equivalent to significantly shortening the kneading time.

  As a result of intensive studies to solve the above-mentioned problems, the present invention has found the following matters. First, the screw 1 is designed to be an internal feedback type, and the sample introduced from the rear stage is sufficiently kneaded while being fed to the front stage by the screw 1, and the sample that has reached the most advanced portion 20 is opened at the center of the screw 1. By returning to the subsequent stage through the cavity, the sample was circulated and the kneading process could be repeated. With this structure, the kneading time can be changed arbitrarily. The degree of kneading can be adjusted by the distance (gap 22) between the most advanced portion 20 and the screw front stage 21 and the inner diameter 23 of the screw 1 cavity. That is, the degree of kneading can be increased by narrowing the gap 22 and narrowing the screw inner diameter 23. In this way, by circulating the sample under high shear, the kneading degree can be arbitrarily controlled without shortening the kneading time, and the above-mentioned problems can be solved.

  By applying this operation, the structure is mutually soluble at the molecular level (compatible). When one polymer component is used as a matrix, the size of the dispersed phase of the other polymer component is controlled to a size of several tens of nanometers. A polymer blend film having a visually dispersed structure or a structure in which both polymer components are continuously connected microscopically (co-continuous structure) is obtained. Further, the narrower the gap 22 and the smaller the screw inner diameter 23, the higher the degree of kneading. However, it is necessary to optimize the gap 22 and the screw inner diameter 23 depending on the viscosity of the sample.

Further, the present invention is to provide immiscible polymers blend system, without adding any extra additives such as compatibilizers, but placed internal feedback type screw mounted capable screw rotation than 1000rpm sectional molding A polymer blend extrudate having a microscopic dispersion structure in which the dispersion phase size of the other polymer component is controlled to several tens of nanometers when one polymer component is used as a matrix by melt-kneading with a processing machine (including a film or sheet-like) and the manufacturing to Rukoto of the extrudate as its object.

The present invention is a method for producing a polymer blend material in which a polymer blend material is produced by rotating an internal feedback screw having a cavity, kneading a polymer material in a molten state, and performing shear molding. Then, without adding a compatibilizing agent, an incompatible polymer blend-based polymer material is disposed in the cylinder and is introduced into the subsequent stage of the internal feedback screw having a hollow portion inner diameter of 1 mm to 5 mm. A step of rotating the internal feedback screw at 500 rpm to 3000 rpm to increase the shear flow field, and kneading the charged polymer material while feeding it to the previous stage by the internal feedback screw; Reach the cutting edge, fill the gap between this cutting edge and the tip of the internal feedback screw, and fill this gap And the polymeric material through the cavity of the internal feedback screw, by repeating then bringing it above the rear stage in the cylinder, a step of kneading repeatedly by circulating the polymer material, the repeating step of kneading A step of discharging the polymer blend obtained from the cylinder from the cylinder, wherein the polymer blend is a dispersed phase in which one polymer component is a matrix and the other polymer component is several tens of nanometers in size. It is a manufacturing method of the polymer blend material characterized by these.

The above is a polymeric material immiscible polymers blend system, in the step of the repeating kneading strength or the degree of kneading of the shear flow field, the tip of the cutting edge portion and the inner feedback type screw of the cylinder And / or the diameter of the cavity of the internal feedback screw . In addition, the present invention is characterized in that it includes a step of maintaining a temperature rise due to shear heating generated in the repeated kneading step at a set temperature by cooling the cylinder .

Upper SL internal feedback screw is adjustable to the speed of the range of 50Rpm～3000rpm.

In the method for producing a polymer blend material of the present invention, the polymer blend material is characterized in that one polymer component is a matrix and the other polymer component is a dispersed phase of several tens of nanometers .

The upper SL polymeric blend material, Ru provided with a co-continuous structure in which the polymer component leads to another continuously.

In addition, the internal structure of the blend extrudate is a phase-separated structure only by melt-kneading an incompatible polymer blend using a conventional molding machine (screw rotation speed of about 300 rpm), that is, one polymer component is used as a matrix. In this case, the dispersed phase size of the other polymer component becomes several tens of micrometers, and the synergistic effect of the blend is lost, and the desired performance and function cannot be exhibited. In addition, if extra additives such as compatibilizers are added, even if a dispersed phase size of submicron level can be realized, an optical element that requires a continuous and pure fine structure because impurities are mixed in. It was a method that became a major obstacle to practical use for materials and electronic / electrical materials.

Therefore, a shear molding machine used for carrying out the present invention includes a cylinder provided with a material input part for supplying a polymer material, a kneading part heater attached to the cylinder, and a hollow part disposed in the cylinder. An internal feedback screw for rotating and generating a shear flow field provided, and a discharge port for taking out a polymer blend material obtained by kneading the polymer material, the polymer material comprising: The internal feedback screw is introduced from the rear stage, and is kneaded in a molten state while being fed to the front stage by the rotation of the internal feedback screw, and reaches the most advanced part of the cylinder. The gap with the tip of the feedback screw is filled, and the polymer material filled in the gap is the cavity of the internal feedback screw. Be returned again to the subsequent stage through the by repeated within said cylinder, said polymeric material is intended to be repeatedly kneaded circulated.

Further, the strength of the shear flow field or the degree of kneading for repeatedly kneading the polymer material is the gap between the tip of the cylinder and the tip of the internal feedback screw, and / or the internal feedback type. is regulated by the diameter of the hollow portion of the screw becomes Rukoto.

Further, the temperature rise due to shear heating that occurs when the polymer material is repeatedly kneaded is held by a cooling means that holds the set temperature by cooling the cylinder .

The method of manufacturing high-molecular blend material of the present invention, by using a shear processing machine used to implement the present invention, even a material incompatible blend system, when the one of the polymer components and the matrix, the other A highly dispersed structure in which the dispersed phase size of the polymer component is controlled to a size of several tens of nanometers, or a structure in which both polymer components are microscopically connected to each other (co-continuous structure). A molecular blend film can be produced. In a material having such a structure, one of the blend components is microscopically mixed with the other at the level of several tens of nanometers, so the conventional dispersed phase size is large (several micrometers or more) sea / island structure Compared to the material, the original properties of the polymer constituting the blend can be synergistically exhibited, so that it is possible to create a material with extremely high performance and high functionality and high added value. Further, the shear molding machine used for carrying out the present invention can perform molding with a sample amount of 2 to 5 g at a time, and a large amount of samples are obtained before obtaining the above microscopic dispersion structure. The molding process conditions can be optimized without wasting.

Further, according to the present invention, even in an incompatible blend material, when one polymer component is a matrix, a microscopic dispersion structure in which the dispersed phase size of the other polymer component is controlled to several tens of nanometers, Alternatively, it is possible to produce a polymer blend extrudate (including a film or a sheet) having a structure in which both polymer components are continuously connected to each other microscopically (co-continuous structure). In a material having such a structure, one of the blend components is microscopically mixed with the other at a level of several tens of nanometers, so that conventionally, the phase is separated and the dispersed phase size is large (several micrometers or more). Compared to materials with a sea / island structure, the inherent properties of the polymers that make up the blend can be demonstrated synergistically, making it possible to create materials with extremely high performance and functionality that have high added value. . In addition, if the method for producing the polymer blend material of the present invention or the shear molding machine used for carrying out the present invention is used , it becomes simple simply to perform melt-kneading, and an extra compatibilizer and the like. Since it is not necessary to add any additives, an optimal method can be provided for optical materials and electronic / electrical materials that require a continuous and pure microstructure.

  In Example 1 or 2, an industrial polymer was used as a material, but it can be said that the role played as a solid dispersion of a poorly soluble drug or generally as a research use for a dispersion is extremely large.

The shear forming machine used for carrying out the present invention is composed of apparatuses assembled according to the design drawings shown in FIGS. That is, a cylinder 2 provided with a sample input part 12 as a material input part for supplying a polymer material, a kneading part heater 13 attached to the cylinder 2, and a hollow part provided in the cylinder 2; It includes at least an internal feedback screw 1 for generating a shear flow field by rotation, and a film discharge port 10 as a discharge port for taking out a polymer blend material obtained by kneading the polymer material. Preferably, the distance (gap 22) between the most distal portion 20 and the screw front stage 21 is set to 2 mm, and the screw cavity inner diameter 23 is set to 2.5φ. If the gap 22 is set to 2 mm or more and the screw cavity inner diameter 23 is set to 2.5φ or more, the effect of kneading is reduced, and an expected result cannot be obtained.

  In order to mix the mixture of polyvinylidene fluoride and nylon 11, a dry blending method in which the mixture is mixed in a granular state can be used. Dry blending was performed after the sample was dried in vacuum at 100 ° C. for 12 hours. In addition, in order to verify how much the molecular weight of the homopolymer decreases after high shear molding, the dependence on screw rotation speed and kneading time was examined using polystyrene with a narrow molecular weight distribution. The polystyrene was pre-dried at 90 ° C. for 12 hours.

  As described above, after dry blending, it is melt-kneaded for a predetermined time at 205-215 ° C. at a predetermined rotation speed, extruded from the T-die 9, and passed through a cooling water tank 24 to be passed through a cooling water tank 24 to be polyvinylidene fluoride and nylon. An 11 blend extrudate is obtained. The size of the obtained extrudate is a sheet-like extrudate having a thickness of 0.5 mm and a width of 30 mm. Similarly, polystyrene was melt-kneaded for a predetermined time at 215 to 225 ° C. at a predetermined rotation number, extruded from the T-die 9, and subjected to a cooling process by passing through a cooling water tank 24 to obtain a sheet-like extrudate of polystyrene.

  When the melt kneader is used, the degree of shearing or kneading can be changed by adjusting the gap 22 between the most advanced portion 20 and the screw front stage 21 and the internal feedback screw inner diameter 23. Normally, the gap 22 can be set to any value between 0 mm and 5 mm at 0.5 mm intervals, and the screw inner diameter 23 can be set to any value between 1 φ and 5 φ at 0.5 φ intervals. Although possible, optimum results could be obtained by setting the gap 22 and the internal feedback screw inner diameter 23 to 2 mm and 2.5φ, respectively.

  The present invention is characterized in that high shear mixing is carried out with the gap 22 between the foremost portion 20 and the screw front stage 21 and the internal feedback type screw inner diameter 23 set to optimum values under the specific temperature. Thus, good results can be obtained only by combining specific conditions. Even if one of the setting conditions such as the temperature setting or the gap is not satisfied, a satisfactory result cannot be obtained.

Next, the present invention will be described in more detail with reference to examples.
The microscopic dispersion structure and weight average molecular weight (Mw) described in the present specification were measured as follows.
(Microscopic dispersion structure)
1) Scanning electron microscope (SEM) observation: When observing the structure, the blended sample was double-stained with osmium tetroxide (OsO ₄ ) and ruthenium tetroxide (RuO ₄ ), then cut with a diamond knife and ion-etched. After coating with platinum, it was subjected to measurement. The structure was observed using a field emission scanning electron microscope S800 manufactured by Hitachi, Ltd. at an acceleration voltage of 10 KV and magnifications of 1000 and 5000.
2) Observation with a transmission electron microscope (TEM): For structural observation, after blending a blend sample with osmium tetroxide (OsO ₄ ) and ruthenium tetroxide (RuO ₄ ), an ultramicrotome (Ultracut UCT manufactured by Leica) Thus, an ultrathin section (120 nm) was prepared and developed on a collodion-attached mesh. As a measuring apparatus, JEM1230 manufactured by JEOL Ltd. was used and the acceleration voltage was 120 kV.
(Weight average molecular weight: Mw)
The measurement was performed with a UV detector (254 nm) using a Shodex K-804L column using a JASCO GULLIVER system. The mobile phase was measured using chloroform at 35 ° C. with a flow rate of 1 ml / min.

<Example 1-1>
Polyvinylidene fluoride (PVDF) as a raw material was manufactured by Scientific Polymer Products, and nylon 11 (PA11) manufactured by Aldrich was used as nylon. Both were dried under vacuum at 100 ° C. for 12 hours, and then dry blended at room temperature with 80% by weight of PVDF and 20% by weight of PA11. Furthermore, about 3 g of this dry blend was put into a micro-type high shear molding machine which is a shear molding machine used for carrying out the present invention , and the gap 22 and the internal feedback type screw inner diameter 23 were each 2 mm, Set to 2.5φ, heated and melted at 205 to 215 ° C., kneaded (screw rotation speed: 2000 rpm, kneading time: 1 minute), extruded from T-die 9 and cooled and solidified by passing through cooling water tank 24 An extrudate having a good surface condition could be obtained.

<Example 1-2>
Polystyrene with a narrow molecular weight distribution (weight average molecular weight Mw: 106000, molecular weight distribution Mw / Mn = 1.06) in order to verify how much the molecular weight of the homopolymer is reduced by high shear molding using this apparatus. Was used and heated and melted at 215 to 225 ° C., and the screw rotation speed and kneading time dependence were examined. The screw rotation speed was changed from 500 rpm to 3000 rpm, and the kneading time was changed from 0.5 minutes to 8 minutes.

<Example 1-3>
The measurement results by the scanning electron microscope of PVDF / PA11 = 80/20 blend samples prepared in Example 1 -1 shown in Fig. As shown in the figure, in a PVDF rich system, PVDF and PA11 form a microscopic co-continuous structure (a structure in which both polymer components are microscopically continuously connected to each other). I understood that. In the figure, the black portion is the PA11 domain, and the portion that appears whitish is that in which the nano-level PA11 domain has entered the PVDF domain.

<Example 1-4>
Further increasing the magnification of the prepared in Example 1 -1 PVDF / PA11 = 80/ 20 blend sample is in Figure 7 for the structure PA11 domain of nano level is just enters into the PVDF domain was observed by a transmission electron microscope . In the photograph on the right side of FIG. 7 , the white part is the PVDF domain, and the black part (small circles) dispersed therein is the PA11 domain. Here, it was found that there are PA11 domains at a level of 100 nm and a smaller level of 10 to several tens of nm.

<Example 1-5>
The relationship between the weight average molecular weight of polystyrene (PS) extrudate prepared in Example 1 2 (Mw) to the screw rotational speed shown in FIG. In this figure, the kneading time was 1 minute. As shown in the figure, it was found that the molecular weight gradually decreased as the screw rotation speed increased, but the decrease rate was about 85%.

<Example 1-6>
The weight average molecular weight of polystyrene (PS) extrudate prepared in Example 1 2 (Mw) to the relation between kneading time shown in FIG. In the figure, two screw rotation speeds of 500 rpm and 1000 rpm were selected. As can be seen from the figure, the molecular weight gradually decreased as the kneading time increased, but the decrease rate was found to be about 85%.

  In order to knead the mixture of polyvinylidene fluoride (PVDF) and polyamide 11 (PA11) used in the present invention, a method by dry blending in which the mixture is mixed in the form of granules can be used. Dry blending was performed after the sample was dried in vacuum at 100 ° C. for 12 hours.

  PVDF and PA11 are incompatible, and in order to obtain a blend thereof, they are usually mixed using a biaxial melt kneader or the like at 200 to 240 ° C. near the melting point. When one component is a matrix, the internal structure of the product becomes a so-called phase-separated structure in which the dispersed phase size of the other component is coarsened to a level of several microns to several tens of micrometers.

  According to the researches of the present inventors, a blend consisting of PVDF and PA11 was mixed with a micro-high shear molding machine equipped with an internal feedback screw instead of a normal biaxial screw kneader, and both of them were in the vicinity of the melting point. It has been found that a blended extrudate having a nano-dispersed structure in which a PA11 dispersed phase of 10 to several tens of nanometers is uniformly and densely dispersed in a PVDF matrix phase can be obtained by melt-kneading at 200 to 240 ° C. .

  When using the above-mentioned trace amount type high shear molding machine equipped with an internal feedback screw, not only the setting of the above specific temperature but also the setting of the screw speed and kneading time in the molding machine are important as the molding process conditions. . In the present invention, the screw rotation speed can be set to 500 to 3000 rpm, and the kneading time can be set to 0.5 to 60 minutes, but the rotation speed and kneading time are set to 1000 to 2000 rpm and 1 to 4 minutes, respectively. As a result, optimum results were obtained.

  The present invention is characterized in that high shear molding is carried out with the screw rotation speed and kneading time set to optimum values under the specific temperature. Thus, good results can be obtained only by combining specific conditions. Even if one of the setting conditions such as the temperature setting or the screw rotation speed is not satisfied, a satisfactory result cannot be obtained.

  When using the above-mentioned trace type high shear molding machine equipped with an internal feedback type screw, shearing is performed by adjusting the gap between the tip of the cylinder filled with the blend and the tip of the screw, or the inner diameter of the internal feedback type screw. The strength of the flow field or the degree of kneading can be changed. In general, the gap can be set to any value between 0.5mm and 1mm between 1mm and 5mm, and the screw inner diameter can be set to 0.5mm interval between 1φ and 5φ as well. However, the optimum results could be obtained by setting the gap and the internal feedback screw inner diameter to 2 mm and 2.5φ, respectively.

  The present invention is characterized in that high shear molding is carried out with the gap between the most advanced portion and the screw tip and the internal diameter of the internal feedback screw at optimum values under the specific temperature. Thus, good results can be obtained only by combining specific conditions. Even if one of the setting conditions such as the temperature setting or the gap is not satisfied, a satisfactory result cannot be obtained.

Next, the kneading according to the present invention will be described in more detail.
Here, the microscopic dispersion structure and the stress-strain curve described in the present specification were measured as follows.
(Microscopic dispersion structure)
Transmission electron microscope (TEM) observation: For structural observation, after double-staining the blend sample with osmium tetroxide (OsO ₄ ) and ruthenium tetroxide (RuO ₄ ), ultramicrotome (Ultracut UCT manufactured by Leica) Ultrathin sections (120 nm) were prepared and developed on collodion-laminated mesh. As a measuring apparatus, JEM1230 manufactured by JEOL Ltd. was used and the acceleration voltage was 120 kV.
(Stress-strain curve)
The stress-strain curve was measured with a dumbbell sample using Tensilon UMT-300 manufactured by Orientec Co., Ltd. This measurement is performed at a speed of 5 mm / min. At a temperature of 20 ° C. and a relative humidity of 50%.

<Example 2-1>
The raw material polyvinylidene fluoride (PVDF) used was KF850 manufactured by Kureha Chemical Industry Co., Ltd., and Rilsan BMN-O manufactured by Atfina was used as polyamide 11 (PA11). Both were dried at 100 ° C. for 12 hours under vacuum, and then dry blended at a ratio of 90 to 20% by weight of PVDF and 10 to 80% by weight of PA11 at room temperature. Furthermore, the 2~5g of the dry blend, the present invention was placed in micro-volume high-shear processing machine is a shear processing machine used to implement, the gap and internal feedback screw inner diameter, respectively 2 mm Set to 2.5φ, heated and melted at 200 to 240 ° C., kneaded (screw rotation speed: 1000 rpm, kneading time: 1 minute), extruded from a T-die, and cooled and solidified by passing through a cooling water bath. An extrudate having a good state could be obtained.

<Example 2-2>
In the PVDF / PA11 = 90/10 blend sample prepared in Example 2-1, the structure in which the nano-level PA11 domain has entered the PVDF matrix is observed with a transmission electron microscope (TEM) in FIG. In the photograph of FIG. 10, the white part is the PVDF matrix phase, and the black-stained part (small circles) dispersed therein is the PA11 domain. Here, it has been found that PA11 domains of ten to several tens of nanometer level exist uniformly and densely in the PVDF matrix phase. Such a nano-dispersed structure could be observed in a wide range of blend compositions of PVDF / PA11 = 90 / 10-20 / 80 blend.

<Example 2-3>
FIG. 11 shows the stress-strain curve measured for the PVDF / PA11 = 80/20 blend sample prepared in Example 2-1. In FIG. 11, curve b is the result of the blend extrudate produced by a normal molding machine. It was found that the results with extrudates made according to the invention (curve c) not only show 5-6 times the elongation of b, but also show properties comparable to almost pure PA11.

  In the above, the sample amount is 2 g to 5 g in the embodiment, but the sample amount can be increased by scaling up. Further, kneading at a high temperature up to 500 ° C. can be performed by attaching a high-temperature seal. Although not shown in the figure, a structure that maintains the set temperature may be added by cooling the cylinder due to the temperature rise caused by shear heating during kneading.

It is explanatory drawing of the theoretical limit of the minimum dispersion particle diameter (D) of the disperse phase in an incompatible blend. It is explanatory drawing which shows each part name of a kneading part. It is a principle diagram of a kneading part. It is an adjustment figure of a gap. It is a whole explanatory drawing of a trace amount type high shear molding processing machine. It is a SEM photograph of PVDF / PA11 = 80/20 blend system. It is a TEM photograph of PVDF / PA11 = 80/20 blend system. It is a graph which shows the relationship between the weight average molecular weight (Mw) of polystyrene (PS), and a screw rotational speed. It is a graph which shows the relationship between the weight average molecular weight (Mw) of polystyrene (PS), and kneading | mixing time. In the PVDF / PA11 = 90/10 blend sample of Example 2-1, it is the figure which observed the structure where the nano level PA11 domain has penetrated in the PVDF matrix with the transmission electron microscope (TEM). It is a measurement graph of the stress-strain curve in the PVDF / PA11 = 80/20 blend sample of Example 2-1.

Explanation of symbols

1 Screw for kneading polymer material 2 Cylinder for making kneading part by combining with screw 3 Gap adjustment cylinder that can set gap adjustment by moving this cylinder 4 Polymer material kneaded from inside cylinder Seal for preventing leakage to prevent leakage to the outside 5 Extrusion tip for mainly flowing from the kneading section to the T die 6 T Open / close valve to open when pouring into the die 7 Thermocouple to measure the temperature of the kneading part 8 Kneading part to knead the polymer material 9 Film making T to make the kneaded polymer material into a film Die 10 Film outlet 11 for discharging the kneaded polymer material in a film state Thermocouple 12 for measuring temperature of T die part Feeding section 13 Kneading section heater 14 for heating the kneading section Extrusion tip section heater 15 for heating the extrusion tip section Sample loading section heater 16 for heating the sample loading section T T die front section heating T-die front heater 17 T-die rear heater 18 for heating the rear part of the T die 19 Bearing 19 for stabilizing the screw during rotation 19 Shaft 20 for transmitting power from the motor to the screw This is a place that needs to be read when adjusting the gap The most advanced part 21 The front stage of the screw, which is a place that needs to be read at the time of gap adjustment 22 The gap adjustment range 23 The screw inner diameter adjustment range 24 The cooling water tank 25 into which water is put to rapidly cool the film-like sample discharged from the T-die A motor to rotate the screw at times 26 Cylinder lock to fix the cylinder 7 Cylinder lock and cooling plate 28 outage motor for releasing the heat to the cylinder rear, control switches required to work such as control of the heating has not been assigned BOX

Claims (2)

A method for producing a polymer blend material, in which a polymer material is kneaded in a molten state in a cylinder and a polymer blend material is produced by a shear molding process,
An incompatible polymer blend-based polymer material is placed in the latter stage of the internal feedback screw that is disposed in the cylinder and has an inner diameter of 1 to 5 mm without adding a compatibilizer. And a process of
The internal feedback screw is rotated at 500 rpm to 3000 rpm to increase the shear flow field, and the charged polymer material is kneaded while being fed to the previous stage by the internal feedback screw and the most advanced part of the cylinder And the gap between the leading edge and the tip of the internal feedback screw is filled, and the polymer material filled in the gap is returned to the subsequent stage through the cavity of the internal feedback screw. By repeating this in the cylinder, the step of circulating and kneading the polymer material repeatedly,
Discharging the polymer blend material obtained by the kneading step from the cylinder;
With
In the polymer blend material, one polymer component is a matrix, and the other polymer component is a dispersed phase having a size of several tens of nanometers.
A method for producing a polymer blend material. Including a step of maintaining the set temperature by cooling the cylinder, the temperature increase due to shear heating generated in the step of repeatedly kneading,
The manufacturing method of the polymer blend material of Claim 1 characterized by the above-mentioned.

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