JP6782927B2 - Manufacturing method of composite resin material - Google Patents

Description

The present invention relates to a method of producing a composite resin material comprising a mixture of synthetic resin and coal ash.

Conventionally, as a technique for effectively utilizing coal ash such as fly ash discharged from a coal-fired power plant, a composite resin material in which a synthetic resin and coal ash are mixed has been proposed. For example, Patent Document 1 discloses a coal ash-mixed thermoplastic resin material obtained by mixing at least a part of a thermoplastic resin acid-modified by adding an unsaturated carboxylic acid and coal ash in a predetermined ratio. ing. In this thermoplastic resin material mixed with coal ash, coal ash, a thermoplastic resin raw material and an unsaturated carboxylic acid are introduced into a pelletization step together with a radical initiator, and in the melt-kneading process, the unsaturated carboxylic acid of the thermoplastic resin raw material is used. Manufactured by simultaneous acid denaturation. According to this coal ash mixed thermoplastic resin material and the method for producing the same, the strength of a molded product made of a material obtained by mixing coal ash with a thermoplastic resin is improved.

Further, Patent Document 2 discloses an apparatus for producing a polymer composite material in which fly ash is kneaded with a synthetic resin, and a method for producing the same. This manufacturing device has a cylinder in which a hopper for charging raw materials is provided on the upstream side and a die portion for extruding kneaded material is provided on the downstream side, and while the raw materials are pushed out from upstream to downstream by rotating the shaft inside this cylinder. A screw that is heated to make a kneaded product and a vent portion that discharges a gas component separated from the kneaded product from a cylinder are provided. Then, a container that separately stores the fly ash, the synthetic polymer, and the liquid medium and supplies a predetermined amount thereof, and the liquid medium as the dispersant of the supplied fly ash, the synthetic polymer, and these powders are mixed together. However, it is equipped with a mixing section that is charged into the hopper of the cylinder as a raw material. According to this polymer composite material manufacturing apparatus and its manufacturing method, fly ash, synthetic polymer material and water as a liquid medium are mixed and then supplied to the hopper of the cylinder, so that fly ash can be mixed even at a high content. It is possible to make a uniformly dispersed polymer composite material, it is not necessary to add excess water to uniformly disperse fly ash, and a large amount of heat of vaporization is not taken away when water is discharged. It is a thing.

Japanese Unexamined Patent Publication No. 2000-136311 Japanese Patent No. 5584807

In general, it is not easy to mix coal ash with a pellet-shaped or powder-shaped resin raw material and uniformly disperse coal ash particles in the resin raw material. With the method described in the method for producing a thermoplastic resin material mixed with coal ash in Patent Document 1, the coal ash particles cannot be sufficiently and evenly dispersed in the resin raw material, and the strength of the composite resin material can be improved. There was a limit to the proportion of coal ash that could be mixed. Further, a large number of fine bubbles are formed inside the produced thermoplastic resin material mixed with coal ash due to the gas generated in the kneading step, and the appearance is not good and the strength is lowered.

Further, as disclosed in the polymer composite material manufacturing apparatus and the manufacturing method thereof in Patent Document 2, even if a predetermined amount of water suitable as a dispersant is mixed, the resin is similar to the case of Patent Document 1. It was not possible to disperse the particles of coal ash sufficiently uniformly in the raw material, and the water as the liquid medium produced a large number of fine bubbles inside and the strength was low.

The present invention has been made in view of the above-mentioned problems of the background technology, promotes effective utilization of coal ash, has few bubbles generated inside, has a good appearance, can obtain sufficient material strength, and is manufactured. An object of the present invention is to provide a method for producing a composite resin material having a simple process.

In the present invention, coal ash, mineral oil, synthetic resin raw material, and acid modifier are mixed at once and kneaded under pressure and heating to melt the synthetic resin raw material and acid-modify it with the acid modifier. , A method for producing a composite resin material in which the coal ash is uniformly dispersed in the synthetic resin raw material with the mineral oil to form a composite resin material.

The synthetic resin raw material is acid-modified with an acid modifier of an unsaturated carboxylic acid. The acid modifier is a maleic anhydride grafted polyolefin resin, and the amount of the acid modifier added is 1 to 6% by mass with respect to the synthetic resin raw material. The mineral oil to be mixed with the coal ash is preferably liquid paraffin.

The temperature at the time of kneading is higher than the melting temperature of the synthetic resin raw material and lower than the vaporization temperature of the mineral oil. The coal ash is mixed at a ratio of 20 to 80% by mass of the whole, and the coal ash is uniformly dispersed in the composite resin raw material by kneading and extruded to be formed.

The mineral oil adheres to and permeates the surface of the coal ash particles, and the coal ash particles are uniformly dispersed in the synthetic resin raw material via the mineral oil.

At least a part of the mineral oil remains on the surface of the coal ash and in the raw material resin.

The mineral oil is mixed in a proportion of 0.2 to 0.7% by mass with respect to the coal ash. The liquid paraffin is mixed with the coal ash at a ratio of 0.4 to 0.5% by mass.

According to the method for producing a composite resin material of the present invention, coal ash and mineral oil, and a synthetic resin raw material and an acid modifier are mixed and kneaded at once, so that the coal ash particles are uniformly dispersed in the synthetic resin raw material by kneading. Mix with each other. The synthetic resin raw material is acid-modified with an acid modifier such as maleic anhydride grafted polyolefin resin, and both mineral oil can surely enter into coal ash particles to form a stronger composite resin material. it can. Moreover, this manufacturing method has a short process, can simplify the manufacturing equipment, can suppress thermal denaturation of the synthetic resin raw material, has little deterioration in the quality and product strength of the composite resin material, and is weather resistant. It is possible to provide a high-quality resin material.

Further, in the composite resin material according to the present invention, the synthetic resin material can surely enter into the pores of the porous coal ash particles, the amount of coal ash used can be increased, the molding strength is high, the deterioration to ultraviolet rays is small, and the weather resistance is low. Highly sexual. Therefore, it is possible to manufacture a resin molded product made of a composite resin material which is durable and has a good appearance.

It is a figure which shows the molding process of the composite resin material of one Embodiment of this invention. It is a schematic view which shows the manufacturing apparatus of the composite resin material of this embodiment, the schematic vertical sectional view (a), and the schematic horizontal sectional view (b). It is a graph which shows the measurement result of the bending maximum stress of the composite resin material of the Example of this invention. It is a graph which shows the measurement result of the maximum tensile stress of the composite resin material of the Example of this invention. It is a graph which shows the measurement result of the impact value of the composite resin material of the Example of this invention. It is a graph which shows the measurement result of the elastic modulus of the composite resin material of the Example of this invention. It is a graph which shows the measurement result of the tensile elastic modulus of the composite resin material of the Example of this invention. It is an electron micrograph of the cross section of the composite resin material of the Example of this invention. It is each electron micrograph of the composite resin material (a) and the synthetic resin raw material (b) of the Example of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 shows an embodiment of the present invention, in which the composite resin material 10 of this embodiment is made by kneading coal ash 12, liquid paraffin 14 which is a mineral oil, and an appropriate synthetic resin raw material 16. The liquid paraffin 14 is mixed with the coal ash 12 as described later and permeates into the particle surface and the pores of the porous coal ash 12. The coal ash 12 is formed by the liquid paraffin 14 functioning as a surfactant and uniformly dispersed in the synthetic resin raw material 16. The synthetic resin raw material 16 is acid-denatured by adding an acid denaturing agent 18 of a maleic anhydride grafted polyolefin resin, which is an unsaturated carboxylic acid, to improve the surface activity and the strength.

The coal ash 12 is, for example, fly ash or cleaner ash discharged from a coal-fired power plant, and has iron oxide (Fe ₂ O ₃ ), silica (SiO ₂ ), and alumina (Al ₂ O ₃ ) as components. other CaO, MgO, contains oxides of Na ₂ O or the like. Fly ash is a fine powdered ash collected by an electrostatic collector among the coal ash generated when coal is burned, and has a particle size of about 0.01 mm to 0.1 mm and an average particle size. Since it is as small as about 25 μm, it can be put into the kneading step 1 without any special processing. Clinker ash is a lumpy ash that has fallen to the bottom of the boiler and has a slightly large particle size of about 0.1 mm to 10 mm. Therefore, it should be crushed as finely as fly ash before being put into the first mixing step. Is preferable. The coal ash 12 preferably has a low water content, and the water content contained in the coal ash 12 due to moisture absorption during storage is preferably less than 5% by mass, preferably less than 2% by mass.

The liquid paraffin 14 is a mineral oil refined from crude oil, which is an alkane having 20 or more carbon atoms, and is rich in olefin hydrocarbons and liquid at room temperature. In addition to the liquid paraffin 14, the mineral oil that can be used may be an oil used as a lubricating oil, a hydraulic oil, or the like. Liquid paraffin 14, when the kinematic viscosity is ^{40 ℃, 10mm 2 / s~100mm 2} / s, preferably when the ^{20mm 2 / s~40mm 2 / s,} 100 ℃, 2.5mm 2 /s~11.5mm ² / s, preferably 4.0mm ² /s~7.0mm ² / s. The vaporization temperature of the mineral oil used here, such as liquid paraffin 14, is higher than the melting temperature of the synthetic resin raw material 16, and does not easily vaporize when the synthetic resin raw material 16 is melted, and the coal ash 12 and the synthetic resin raw material are not easily vaporized. It contributes to uniform mixing and kneading of 16.

As the synthetic resin raw material 16, a thermoplastic resin is preferably used. The thermoplastic resin that can be used as the synthetic resin raw material 16 is low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethyl ethylene-ethyl acetate. Polypropylene-based resins such as copolymer (EEA) are suitable. In addition, without being limited to these, polycarbonate resin (PC), polyethylene terephthalate resin (PET), polystyrene (PS), acrylic butylene styrene (ABS), polylactic acid (PLA), polybutylene succinate (PBS). ), Polycaprolactone (PCL), Tegranobon ™, ECM Masterbatch (trade name) of Macrotech Research (USA), etc., as long as they have the property of heat-flowing by heating and can be extruded. It can be used without particular limitation. Further, these thermoplastic resins may be used by mixing two or more kinds.

The acid modifier 18 is a functional resin used for assisting the bonding of dissimilar resins in a molten state, improving processability, and uniformly dispersing glass fibers, elastomers, and flame retardants. For example, maleic anhydride is used, and specifically, FUSABOND (registered trademark) P613RESIN manufactured by DuPont Co., Ltd., which is a maleic anhydride grafted polyolefin resin, can be used as an example. The amount added is 1 to 6% by mass with respect to the synthetic resin raw material 16.

Next, the method for producing the composite resin material 10 of this embodiment will be described with reference to FIGS. 1 and 2. First, the granular synthetic resin raw material 16 is put in the hopper 20, the coal ash 12 is put in the hopper 22, and the acid modifier 18 is put in the adjacent hopper 24. The synthetic resin raw material 16 is polypropylene, for example, trade name Novatec PPMA3 (manufactured by Japan Polypropylene Corporation). The coal ash 12 is fly ash, and the above-mentioned FUSABOND is added as the acid modifier 18.

In the mixing step, coal ash 12, liquid paraffin 14, synthetic resin raw material 16, and acid modifier 18 are put into the mixer 26 provided below the hoppers 20, 22, and 24 from the hoppers 20, 22, and 24, respectively. The liquid paraffin 14 is, for example, trade name HYCOAL K-230 (manufactured by Kaneda Co., Ltd.). The amount of the liquid paraffin 14 added is 0.2 to 0.7% by mass, preferably 0.4 to 0.5% by mass with respect to the coal ash 12, and the temperature, humidity, and other additions are high. It depends on the amount of the agent. As a result, the liquid paraffin 14 adheres to the surfaces of the coal ash 12 and the granular synthetic resin raw material 16, and the coal ash 12 and the granular synthetic resin raw material 16 are smoothly and uniformly mixed.

The amount of the acid modifier 18 added is about 1 to 6% by mass, preferably 3 to 5% by mass, based on the synthetic resin raw material 16, the state of the synthetic resin raw material 16 and the liquid paraffin 14 kneaded with the coal ash 12. It depends on the amount of. The mixed mass ratio of the synthetic resin raw material 16 and the coal ash 12 can be appropriately changed, such as 8: 2 to 2: 8, for example, 1: 1 or 3: 7.

The mixture 9 produced by the mixing step is charged into a metering stirrer 28 located on a twin-screw extruder 32 described later for kneading the composite resin material 10. A metering and stirring device 30 is provided below the metering and stirring machine 28, and the mixture 9 is charged into the twin-screw extruder 32 by the metering and stirring device 30 from the metering and stirring machine 28, and kneading is performed under pressure heating. Make the composite resin material 10.

Here, a general twin-screw extruder 32 will be described. The twin-screw extruder 32 is provided with an inlet 34 for charging the mixture 9 on the upstream side, and an extrusion port 36 on the downstream end for extruding the composite resin material 10 made by kneading. The cylinder 38 has a screw 39 that rotates around the inside of the cylinder 38 to heat the mixture 9 while pushing it from the upstream to the downstream and kneads the mixture, and a vent portion 40 that discharges the gas component separated from the mixture 9 from the cylinder 38. Is provided. The screw 39 is a screw in which two screws are provided in parallel with each other and have the same spiral direction and rotate in the same direction.

A heater 42 is provided on the outer peripheral surface of the cylinder 38 to control each zone of C1 to C3 partitioned along the longitudinal direction of the cylinder 38 to an appropriate temperature. The zone C1 located at the upstream end has a feed zone into which the mixture 9 is charged and fed downstream. A charging port 34 for charging the mixture 9 is provided in the zone C1, and a portion located on the downstream side of the zone C1 melts the synthetic resin raw material 16 contained in the mixture 9.

Zone C2 on the downstream side of zone C1 is a dispersion / kneading region in which coal ash 12 is uniformly dispersed and kneaded in the molten synthetic resin raw material 16, and a feed region in which the mixture 9 is moved. Zone C2 is provided with a vent portion 40 that discharges the gas component separated from the mixture 9 into the atmosphere. The vent portion 40 is released under atmospheric pressure.

On the downstream side of the zone C2, a zone C3 which is a compression region in which the mixture 9 is pressed by the screw 39 is provided. An extrusion port 36 for discharging the composite resin material 10 in which the mixture 9 is kneaded under pressure and heating is provided on the downstream side portion of the zone C3. A general pelletizing system (not shown) is provided at the extrusion port 36 of the twin-screw extruder 32. The pelletizing system performs a pelletizing step of cutting the composite resin material 10 extruded into a strand shape from the extrusion port 36 into a pellet shape.

Next, the kneading step of the composite resin material 10 by the twin-screw extruder 32 will be described. The metering / stirring device 30 provided below the metering / stirring machine 28 is moved, and the mixture 9 contained in the metering / stirring machine 28 is dropped into the inlet 34 of the twin-screw extruder 32 via the metering / stirring device 30. The charged mixture 9 is kneaded with the coal ash 12 by melting the synthetic resin raw material 16 while passing through the cylinder 38 under pressurized heating. The synthetic resin raw material 16 is melted and acid-modified by the acid denaturing agent 18, and the interfacial adhesiveness is improved. The temperature at the time of kneading is higher than the melting temperature of the synthetic resin raw material 16 and lower than the vaporization temperature of the liquid paraffin 14. The liquid paraffin 14 functions to increase the fluidity of the mixture 9, and also enhances the surface activity of the surface of the coal ash 12 in a state of being attached to the particle surface of the coal ash 12, and the coal ash in the molten synthetic resin raw material 16 Promotes uniform dispersion of twelve. As a result, the acid-modified molten synthetic resin raw material 16 enters between the particles of the coal ash 12 to which the liquid paraffin 14 is attached and is kneaded, and the coal ash 12 is uniformly melted in the molten synthetic resin raw material 16. The composite resin material 10 is produced in a dispersed manner.

The kneaded composite resin material 10 is extruded in a strand shape from the extrusion port 36. The extruded composite resin material 10 is pelletized by a pelletizing system (not shown) attached to the extrusion port 36.

The thermoplastic composite resin material 10 formed in the form of pellets is used as a resin raw material for molding various products such as daily necessities, building materials, etc., and has high molding strength and high weather resistance against ultraviolet rays. It is remelted and molded into products for various purposes.

According to the composite resin material 10 of this embodiment, the particles of the coal ash 12 are uniformly and densely dispersed in the synthetic resin raw material 16, and the synthetic resin raw material 16 is surely dispersed in the pores of the particles of the porous coal ash 12. It is possible to produce a resin molded product made of the composite resin material 10 which penetrates and has high molding strength. Even if a large amount of coal ash 12 is contained, there are very few bubbles inside and high strength can be obtained. Therefore, the ratio of coal ash 12 is increased to promote the consumption of coal ash 12, and the coal ash 12 is effectively used as a resource. can do. In particular, since the coal ash 12 shields and absorbs ultraviolet rays and is less deteriorated by ultraviolet irradiation, it has high resistance to ultraviolet rays and high durability.

Further, according to the method for producing the composite resin material 10 of this embodiment, the liquid paraffin 14 has satisfactorily penetrated into the particle surface and the pores of the porous coal ash 12, so that the interface of the surface of the coal ash 12 By increasing the activity, the coal ash 12 is uniformly dispersed in the synthetic resin raw material 16, and the synthetic resin raw material 16 is surely adhered to the surface and holes of the coal ash 12 to form a high-strength composite resin material 10. be able to. Since the liquid paraffin 14 functions to increase the fluidity of the mixture 9, the kneadability is remarkably improved, and the liquid paraffin 14 can be uniformly dispersed and blended in the molten synthetic resin raw material 16 without forming a mass of particles of the coal ash 12. it can. Moreover, the resistance in the kneading process can be reduced, and the load on the twin-screw extruder 32 is also reduced. Further, the fluidity of the synthetic resin material 10 can be adjusted by the addition ratio of the liquid paraffin 14, and the extrusion state in the pelletization step can be arbitrarily adjusted according to the apparatus, environment and other conditions. Since the liquid paraffin 14 has high high temperature stability, it is easy to set kneading conditions, and by using a liquid paraffin 14 having a vaporization temperature higher than the melting temperature of the synthetic resin raw material 16, the kneading temperature is adjusted to match the synthetic resin raw material 16. It can be set, and the kneading temperature and pressure can be set to the minimum necessary. As a result, the heat history of the synthetic resin raw material 16 can be reduced, deterioration such as discoloration and decomposition is unlikely to occur, and the quality of the composite resin material 10 can be improved. Further, the liquid paraffin 14 can reduce the static electricity generated in the coal ash 12 and efficiently perform each mixing operation of mixing the raw materials.

The synthetic resin raw material 16 is acid-modified with an acid modifier 18 of a maleic anhydride-grafted polyolefin resin, and since the interfacial adhesiveness between the synthetic resin raw material 16 and the coal ash 12 is improved, the synthetic resin raw material 16 is acid-modified with maleic anhydride alone. Compared with the one using the synthetic resin raw material 16, the mechanical strength of the molded product can be greatly improved, and the high performance can be maintained even if the amount of the coal ash 12 mixed in is increased. Since the synthetic resin raw material 16 has strong molecular bonds due to the acid modifier 18 and does not generate gas, the number of bubbles mixed in the composite resin material 10 in the kneading step is reduced and the density is increased, and high strength is also obtained from this point. You can also do it. Further, since there are few bubbles, the unevenness on the surface of the molded product is reduced, and the appearance is improved. The acid modifier 18 which is a maleic anhydride grafted polyolefin resin can be well compatible with the liquid paraffin 14 containing a large amount of olefin hydrocarbons and can increase the strength.

Further, the thermoplastic composite resin material 10 formed in the form of pellets has sufficient strength as a resin raw material for molding and high molding strength can be obtained, and also has high resistance to ultraviolet rays and high weather resistance. Further, it has few bubbles and a beautiful appearance, and can be remelted into various shapes. In particular, since it has sufficient molding strength and high weather resistance, it can be used for various purposes such as daily necessities, building materials and the like.

When the composite resin material 10 is melted and molded, if the composite resin material 10 absorbs water more than a certain level, molding defects are likely to occur. However, in this composite resin material 10, the liquid paraffin 14 is mixed with the liquid paraffin 14. It remains in the composite resin material 10, and the composite resin material 10 is less likely to absorb moisture, which is very advantageous for storage as a resin material for molding a resin product. For example, when the composite resin material 10 is stored as a resin material for molding in a resin molding factory or the like, the storage conditions (temperature, humidity, period, etc.) can be easily managed, and high-quality molding can be performed. ..

Further, in the composite resin material 10, since the coal ash 12 is uniformly dispersed, the surface resistivity, which is the electrical resistance, is low. Since the composite resin material 10 is less deteriorated by ultraviolet rays, it can also be used for molded products used outdoors.

Further, in the method for producing the composite resin material 10, since the coal ash 12, the liquid paraffin 14, the acid modifier 18, and the synthetic resin raw material 16 are mixed at once in the mixing step, the particles of the coal ash 12 are mixed with the synthetic resin raw material 16. Is easily and uniformly dispersed and mixed, and the synthetic resin raw material 16 surely enters into the uneven pores on the particle surface of the porous coal ash 12. Further, this manufacturing method has a short process, can simplify the manufacturing apparatus, can suppress heat denaturation of the synthetic resin raw material 16, has high manufacturing efficiency, and improves the quality and product strength of the composite resin material 10. be able to. Further, by simplifying the process, it is possible to simplify the apparatus and reduce the kneading energy, which also contributes to the reduction of the manufacturing cost.

The composite resin material of the present invention and the method for producing the same are not limited to the above-described embodiment, and the kneading device used in the kneading step may be other than the above-mentioned twin-screw extruder, and the composite resin material to be produced may be used. It is appropriately selected depending on the material, amount, application, etc. A hopper, a mixer, a metering stirrer, a quantitative feeding device, a pelletizing device, etc. can be freely selected as appropriate. The coal ash, liquid paraffin, synthetic resin raw material, and acid modifier acid may be other than the above, and can be appropriately changed as long as they have the same function.

The results of various performance tests on the composite resin material of the present invention are shown below. The sample is shown in the above embodiment by the fly ash coal ash 12, liquid paraffin 14, polypropylene (PP) synthetic resin raw material 16, and maleic anhydride grafted polyolefin resin acid modifier 18. Two types were produced by the production method and had different amounts of coal ash 12. The sample name FPC70 is 70% by mass of coal ash 12 and 50% by mass of the sample name FPC50 with respect to the total amount of the composite resin material 10. For comparison, the same performance test was performed on the sample name MA3 (PP) in which the coal ash 12 was 0% by mass. The polypropylene MA3 has a melt mass flow rate (MFR) of 5 g / 10 min and a density of 1.3 g / cm ² . For each of these three types of samples, 10 samples were tested and average values were obtained. The variation in the performance of each sample was small, and it was confirmed that the composite resin material can be stably and uniformly produced by the production method of the present application.

First, the result of measuring the maximum bending stress is shown in FIG. The maximum bending stress is 59 MPa for FPC70, 57 MPa for FPC50, and 35 MPa for MA3, and the higher the content of coal ash 12, the larger the maximum bending stress. That is, it was found that it is less likely to be deformed than the synthetic resin raw material 16 alone and has high strength.

The result of measuring the maximum tensile stress is shown in FIG. The maximum tensile stress is 25 MPa for FPC70, 29 MPa for FPC50, and 43 MPa for MA3, and the lower the content of coal ash 12, the larger the maximum tensile stress. That is, the addition of coal ash 12 reduced the maximum tensile stress, albeit slightly.

Next, the result of measuring the impact value is shown in FIG. Impact value, FPC 70 is 3.1kj ^/ m 2, FPC50 is 4.0 kJ ^/ m 2, MA3 is 3.5kj / ^{m 2,} related to the content of the coal ash 12 is not observed, coal ash It was confirmed that the impact value, which is the resistance to impact, does not decrease so much even if 12 is added.

The results of measuring the elastic modulus are shown in FIG. The elastic modulus is 4928 MPa for FPC70, 2516 MPa for FPC50, and 1500 MPa for MA3, and the higher the content of coal ash 12, the higher the elastic modulus. That is, it was found that it is less likely to be deformed than the synthetic resin raw material 16 alone and has high strength.

The result of measuring the tensile elastic modulus is shown in FIG. The tensile elastic modulus is 2700 MPa for FPC70, 1800 MPa for FPC50, and 1600 MPa for MA3, and the higher the content of coal ash 12, the higher the tensile elastic modulus. That is, it was found that it is less likely to be deformed than the synthetic resin raw material 16 alone and has high strength.

From the results of each of the above performance tests, the composite resin material of the present invention does not have a decrease in strength as compared with the case of 100% synthetic resin raw material even if the amount of coal ash 12 added is large, but rather has high strength. I understood.

Next, an electron micrograph of a cross section of the composite resin material of FPC50 is shown in FIG. As a result, it was confirmed that the composite resin material has an extremely small number of bubbles as shown by the arrow in FIG.

Next, Table 1 shows the results of measuring the change in intensity before and after irradiation with ultraviolet rays. The materials used in this example are also the same as those in the above embodiment, and are fly ash coal ash 12, liquid paraffin 14, polypropylene (PP) synthetic resin raw material 16, and maleic anhydride-grafted polyolefin resin acid modifier. 18 is made by the production method shown in the above embodiment. In the composite resin material of this example, the lower column labeled PP in Table 1 is the measurement result in the case of 100% polypropylene, and the lower column labeled FPC 50% is 1: 1 for polypropylene and fly ash. It is the result of the mass ratio of. Ultraviolet irradiation was performed under the following conditions: Equipment used: UV fluorescent lamp type accelerated weather resistance tester Measurement conditions: UV fluorescent lamp: UVA-340
Illuminance: 0.76 W / m ² / nm (340 nm)
Black panel temperature: 60 ° C
Time: 600 hours (UV continuous irradiation only)

As can be seen from Table 1, the composite resin material of this example has less deterioration before and after irradiation with ultraviolet rays as compared with the original synthetic resin raw material (PP) resin, and is almost physical except for the Charpy impact value. It was confirmed that there was no change in the target performance.

FIG. 9 shows a micrograph of the composite resin material and the synthetic resin raw material (PP) irradiated with ultraviolet rays in Example 2. As shown in FIG. 9A, the cracks of the arrows shown in the electron micrograph of the composite resin material of the example are extremely small and few in number, but are shown in the electron micrograph of the synthetic resin raw material resin of FIG. 9B. The cracks at the points indicated by the arrows were relatively large, and the number of similar cracks was large.

Next, a composite resin material in which fly ash coal ash 12 and HDPE (high density polyethylene) are kneaded as a resin for extrusion molding is produced in addition to polypropylene (PP) as a kneaded product of fly ash coal ash 12. did. It is important to maintain the fluidity of the resin even in extrusion molding, and in order to maintain the MFR of the basic compounded resin of the synthetic resin raw material when making this composite resin material, the compounding of polyethylene resin is made of HDPE (high density polyethylene). The basic composition was 10% (density polyethylene) and 90% LLDPE (linear low-density polyethylene). When the fly ash coal ash 12 was kneaded, the amount of LLDPE in the synthetic resin raw material having the above basic composition was replaced with the coal ash 12 to produce a composite resin material.

The twin-screw extruder and fly ash coal ash used in this production are the same as those used in the production of the above PP. In this example, HDPE 10% and low-density polyethylene (LLDPE) are used in the table. The proportion (mass%) of coal ash in the composite resin material was increased in three steps of 30%, 40%, and 50% and kneaded to produce a fly ash kneaded polyethylene resin for extrusion shaping. The results are shown in Tables 2 and 3. Table 2 shows the relationship between the amount of fly ash kneaded and the strength when the amount of fly ash is 0%, 30%, and 40%. Table 3 shows the relationship between the resin grade and the strength, where the amount of fly ash is 50%.

As a result, in the polyethylene resin, the MFR tended to decrease as the amount of fly ash added increased, as compared with the resin material to which fly ash was not added. In addition, the bending strength and the flexural modulus tended to increase. Furthermore, it was confirmed that polyethylene did not break even after an impact resistance test, and that a resin having sufficient characteristics of polyethylene could be produced. It was also found that the fly ash kneaded composite resin material has a strength higher than the initial strength even when compared with the PE resin without fly ash. Further, even when 50% of fly ash is added, by adding 10% of high density polyethylene (HDPE) rather than only low density polyethylene (LLDPE), MFR is slightly lowered, but other physical properties are improved. I found out.

From the above, it was found that by properly adjusting the MFR of the composite resin material, it is possible to mold the resin product using the composite resin material even if the molding method is different. Therefore, it can be said that the composite resin material produced by the method for producing a composite resin material of the present invention can be molded into three types: injection molding, extrusion molding, and compression molding.

10 Composite resin material 12 Coal ash 14 Liquid paraffin 16 Synthetic resin raw material 18 Acid modifier 26 Mixer 28 Weighing stirrer 32 Twin-screw extruder

Claims (9)

Coal ash, mineral oil, synthetic resin raw material, and acid modifier are mixed at once and kneaded under pressure and heating to melt the synthetic resin raw material and acid-modify it with the acid modifier, and the synthetic resin. A method for producing a composite resin material, which comprises forming a composite resin material by uniformly dispersing the coal ash in a raw material. The method for producing a composite resin material according to claim 1, wherein the acid modifier is an unsaturated carboxylic acid. The method for producing a composite resin material according to claim 1, wherein the acid modifier is a maleic anhydride grafted polyolefin resin, and the amount added is 1 to 6% by mass with respect to the synthetic resin raw material. The method for producing a composite resin material according to claim 1, wherein the mineral oil to be mixed with the coal ash is liquid paraffin. The method for producing a composite resin material according to claim 1 or 4, wherein the temperature at the time of kneading is higher than the melting temperature of the synthetic resin raw material and lower than the vaporization temperature of the mineral oil. The composite according to any one of claims 1 to 5, wherein the coal ash is mixed at a ratio of 20 to 80% by mass of the whole, and the coal ash is uniformly dispersed in the composite resin raw material by kneading and extruded to be molded. Method of manufacturing resin material. The production of the composite resin material according to claim 5, wherein the vaporization temperature of the mineral oil is higher than the melting temperature of the synthetic resin raw material, and at least a part of the mineral oil remains on the surface of the coal ash and in the raw material resin. Method . The method for producing a composite resin material according to claim 1 or 4, wherein the mineral oil is mixed with the coal ash at a ratio of 0.2 to 0.7% by mass. The method for producing a composite resin material according to claim 4, wherein the liquid paraffin is mixed with the coal ash at a ratio of 0.4 to 0.5% by mass.