JP2016074843A - Composite resin material and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite resin material capable of accelerating effective utilization of coal ash, and obtaining sufficient material strength, and having a simple production process; and to provide a production method thereof.SOLUTION: Coal ash 16 and liquid paraffin 18 are mixed together, and a kneaded product thereof and a synthetic resin raw material 14 are kneaded together, to thereby obtain a composite resin material. A moisture content resulting from moisture absorption by the coal ash 16 is less than 5 mass%. The content of saturated carboxylic acid in the liquid paraffin 18 is less than 0.01 mass%. The liquid paraffin 18 is mixed at the ratio of 0.1-3 mass% to the coal ash 16. The coal ash 16 is mixed at the ratio of 10-90 mass% of the whole.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composite resin material obtained by mixing a synthetic resin and coal ash and a method for producing the same.

  Conventionally, a composite resin material in which synthetic resin and coal ash are mixed has been proposed as a technique for effectively using coal ash such as fly ash discharged from a coal-fired power plant. For example, Patent Document 1 discloses a coal ash-mixed thermoplastic resin material obtained by mixing a predetermined amount of a thermoplastic resin and coal ash which are at least partially modified by adding an unsaturated carboxylic acid. ing. This coal ash-mixed thermoplastic resin material includes, for example, coal ash, a thermoplastic resin raw material, and an unsaturated carboxylic acid introduced into a pelletizing process together with a radical initiator, and in the melt kneading process, It is manufactured by simultaneously proceeding acid modification with carboxylic acid (FIG. 2 of Patent Document 1), and improves the strength of a molded product made of a material obtained by mixing coal ash with a thermoplastic resin.

  In addition, there are composite resin materials in which various resin materials made of synthetic polymers and biomass (biological resources) are mixed. For example, Patent Document 2 discloses a composite produced by adding a synthetic polymer main ingredient and an excess water-containing biomass-derived component to a kneading means, kneading the mixture under a predetermined temperature and pressure, and dehydrating the mixture. A resin material is disclosed. According to the composite resin material and the manufacturing method, by performing kneading of the synthetic polymer resin material and the biomass-derived component under high-pressure steam, the biomass-derived component is refined and uniformly dispersed in the synthetic polymer resin material. In addition to facilitating the conversion, the pressure in the dehydration step can be gradually reduced to suppress reaggregation of the dispersed biomass-derived components. Furthermore, by adding a solid wax at room temperature, the wax melts ahead of the main component of the synthetic polymer in the kneading process, forming a mixed liquid phase with water to reduce the viscosity of the kneaded product, It is disclosed that kneadability is improved and the burden of kneading means can be reduced.

Japanese Patent Laid-Open No. 2000-136311 JP 2008-296569 A

  In general, it is not easy to mix coal ash with a pellet-like or powder-like resin raw material and uniformly disperse the coal ash particles in the resin raw material. In the method described in the method for producing a coal ash-mixed thermoplastic resin material of Patent Document 1, the coal ash particles cannot be dispersed sufficiently uniformly in the resin raw material, and the strength of the composite resin material can be improved. There was a limit on the proportion of coal ash that could be mixed. In particular, the unsaturated carboxylic acid contained in the coal ash-mixed thermoplastic resin material of Patent Document 1 reacts with moisture in the coal ash, enters the surface and pores of the porous coal ash, and melts the resin raw material. Hindered the penetration of coal ash into the pores of the coal ash, hindering the improvement of the strength of the composite resin material. Furthermore, the moisture in the coal ash causes hydrolysis of the resin raw material to reduce the strength, and causes silver streaks on the surface of the resin product manufactured by the composite resin material.

  In addition, the composite resin material of Patent Document 2 and the method for producing the same are those in which biomass-derived components that originally have a high proportion of water content are dispersed in a synthetic polymer material, and biomass that is an organic matter is to be kneaded. More moisture remains in the resin material, and there is a problem that the strength of the composite resin material is reduced due to hydrolysis and silver streaks are likely to occur on the surface of the resin product to be produced, as compared with the case of Patent Document 1 described above. It was. In addition, the dehydration process in the kneading process requires a lot of energy to evaporate a large amount of water, and the temperature and pressure must be precisely controlled, making the manufacturing process complicated and managing the conditions. It is troublesome. Therefore, such a method for producing a composite resin material using a biomass-derived component as a kneading target cannot be applied to the production of a composite resin material in which an inorganic material and a synthetic resin material are kneaded as disclosed in Patent Document 1.

  The present invention has been made in view of the above-mentioned background art, and provides a composite resin material that can promote effective utilization of coal ash, obtain sufficient material strength, and has a simple manufacturing process, and a method for manufacturing the same. With the goal.

  The present invention is formed by kneading coal ash, mineral oil, and a synthetic resin raw material, the mineral oil penetrates into the particle surface of the coal ash, and the coal ash particles pass through the mineral oil to the synthetic resin raw material. It is a composite resin material that is uniformly dispersed therein.

  The mineral oil has a fatty acid content of less than 0.01% by mass. Furthermore, the mineral oil preferably has an unsaturated carboxylic acid content of less than 0.01% by mass. The mineral oil is mainly composed of paraffin, and liquid paraffin is particularly preferable.

  The vaporization temperature of the mineral oil is higher than the melting temperature of the synthetic resin raw material. The mineral oil is mixed at a ratio of 0.1 to 3% by mass with respect to the coal ash, and more preferably mixed at a ratio of 0.5 to 1% by mass with respect to the coal ash. .

  The coal ash is a mixture of 10 to 90% by mass of the entire composite resin material.

  The present invention also includes kneading coal ash and mineral oil, mixing a synthetic resin raw material into the kneaded product of the coal ash and mineral oil, kneading under pressure and heating, and melting the synthetic resin raw material. The method for producing a composite resin material, wherein the coal ash is uniformly dispersed in the synthetic resin material to form a composite resin material. The coal ash used here has a moisture content by moisture absorption of less than 5% by mass. The mineral oil mixed with the coal ash has an unsaturated carboxylic acid content of less than 0.01% by mass.

  The mineral oil mixed with the coal ash is liquid paraffin. The said mineral oil mixed with the said coal ash mixes in the ratio of 0.1-3 mass% with respect to the said coal ash.

  It is preferable that at least a part of the mineral oil is volatilized during mixing with the synthetic resin raw material and heating and kneading.

  The coal ash is mixed at a ratio of 10 to 90% by mass of the whole, and the coal ash is uniformly dispersed in the synthetic resin weight loss by kneading and extruded to form a pellet.

  In the composite resin material of the present invention, the synthetic resin material surely enters the pores of the porous coal ash particles, promotes consumption of the coal ash, and forms a composite resin material having high molding strength. Furthermore, since it does not contain fatty acids or moisture, or is suppressed to a very small amount, it is possible to produce a resin molded article made of a composite resin material having high molding strength and good appearance.

  Furthermore, according to the method for producing a composite resin material of the present invention, after kneading coal ash and mineral oil, the synthetic resin raw material is mixed and kneaded, so that the coal ash particles are uniformly dispersed in the synthetic resin raw material by kneading. As a result, the synthetic resin material surely enters the pores of the porous coal ash particles, and a composite resin material with higher molding strength can be formed. Furthermore, since it does not contain fatty acids or moisture, or is suppressed to a very small amount, it is possible to produce a resin molded product made of a composite resin material having high molding strength and good appearance. Moreover, this manufacturing method can shorten a process, can simplify a manufacturing apparatus, can also suppress the thermal denaturation of a synthetic resin raw material, and can further improve the quality and product strength of a composite resin material.

It is a figure which shows the formation process of the composite resin material of one Embodiment of this invention.

  Hereinafter, an embodiment of the composite resin material of the present invention will be described. The composite resin material 10 of this embodiment is obtained by kneading coal ash 16, liquid paraffin 18 that is mineral oil, and an appropriate synthetic resin raw material 14. As will be described later, the liquid paraffin 18 is added in advance to the coal ash 16 and kneaded, and penetrates into the particle surface and pores of the porous coal ash 16. The coal ash 16 is configured such that the liquid paraffin 18 functions as a surfactant and is uniformly dispersed in the synthetic resin raw material 14.

  The composite resin material 10 is manufactured in the composite resin manufacturing process 12 shown in FIG. First, the coal ash 16 and the liquid paraffin 18 are kneaded in the kneading step K1, and the liquid paraffin 18 is uniformly permeated into the particle surfaces and pores of the porous coal ash 16. Thereafter, in the kneading step K2, the synthetic resin raw material 14 is mixed with the kneaded product of the coal ash 16 and the liquid paraffin 18 and kneaded under pressure and heating to melt the synthetic resin raw material 14, and in the synthetic resin raw material 14 The composite resin material 10 is formed by uniformly dispersing the coal ash 16. The kneaded composite resin material 10 is extruded from a nozzle of a kneading apparatus (not shown), formed into a pellet in the pelletizing step P, and shipped.

  As the synthetic resin raw material 14 that can be used in the present invention, either a thermoplastic resin or a thermosetting resin can be employed.

  Examples of the thermoplastic resin that can be used as the synthetic resin raw material 14 include low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), and ethylene-acrylic acid. Polyolefin resins such as ethyl copolymer (EEA) are preferred. In addition, without limitation, polycarbonate resin (PC), polyethylene terephthalate resin (PET), acrylic / butylene / styrene (ABS), polylactic acid (PLA), polybutylene succinate (PBS), polycaprolactone ( PCL), Tegranobon (trademark), ECM Masterbatch (trade name) from Macrotech Research (USA), etc., as long as they have the property of being heat-flowable by heating and can be extruded, use without particular limitation. Can do. Furthermore, these thermoplastic resins may be used as a mixture of two or more.

  Examples of the thermosetting resin that can be employed as the synthetic resin raw material 14 include epoxy resins, phenol resins, unsaturated polyester resins, urea resins, melamine resins, polyimides, diallyl phthalates, and alkyds. These thermosetting resins can be formed into molded articles by adding a known curing agent to the main agent, maintaining a predetermined shape, and setting the curing temperature to a polymerization reaction. The main component of these thermosetting resins can be liquid, solid, or semi-solid because the monomer before the polymerization reaction is a low molecular weight compound, but it exhibits a fluid state at least when the temperature is raised. It is. Therefore, the main component of the thermosetting resin and the coal ash 16 are kneaded at a kneading temperature set to a temperature lower than the curing temperature.

The coal ash 16 is, for example, fly ash or clinker ash discharged from a coal-fired power plant, and the components include iron oxide (Fe ₂ O ₃ ), silica (SiO ₂ ), alumina (Al ₂ O ₃ ), and others. Oxides such as CaO, MgO, and Na ₂ O are included. Fly ash is a fine powdery ash collected by an electrostatic precipitator among coal ash generated when coal is burned. The particle size is about 0.01 mm to 0.1 mm, and the average particle size is Since it is as small as about 25 μm, it can be put into the kneading step K1 without any particular processing. Clinker ash is a massive ash that has fallen to the bottom of the boiler, and its particle size is slightly large, about 0.1 mm to 10 mm, so it must be crushed as finely as fly ash before being put into the kneading process K1. Is preferred.

  The coal ash 16 preferably has a low water content, and no water is added in the kneading steps K1 and K2. Therefore, in the storage state of the coal ash 16, the moisture content contained in the coal ash 16 due to moisture absorption is less than 5% by mass, preferably less than 2% by mass.

  The mineral oil is an oil refined from crude oil, and the liquid paraffin 18 that is the mineral oil of this embodiment is rich in olefinic hydrocarbons among paraffins that are alkanes having 20 or more carbon atoms, and is liquid at room temperature. Of oil. The mineral oil that can be used in addition to the liquid paraffin 18 may be an oil used as a lubricating oil, a hydraulic oil, or the like, and is a mineral oil that does not contain an animal or vegetable oil containing an unsaturated carboxylic acid or other fatty acid, or at least an unsaturated carboxylic acid. Alternatively, it is a mineral oil having a fatty acid content of less than 0.01% by mass.

Furthermore, mineral oils such as liquid paraffin 18, 10 mm in kinematic viscosity ^{40 ℃ 2 / s~100mm 2 / s} , preferably 20mm ² / s~40mm 2.5mm ² / s~11 at ² / s, 100 ° C. .5mm ² / s, preferably 4.0mm ² /s~7.0mm ² / s.

  The liquid paraffin 18 mixed in the kneading step K1 is a ratio of 0.1 to 3% by mass with respect to the coal ash 16, and preferably mixed at a ratio of 0.5 to 1% by mass with respect to the coal ash 16. . The mixing ratio is appropriately determined in consideration of the state of the coal ash 16 such as the particle size and surface properties, the use and required strength of the composite resin material 10, kneading properties and the like. For example, in order to improve kneadability, it is better to have more liquid paraffin 18, but if it is more, the viscosity at the time of extrusion in the subsequent kneading step K2 will decrease, and cooling in the pelletizing step P will be necessary, The amount of the liquid paraffin 18 is determined in consideration of these factors because it also causes a decrease in the strength of the composite resin material 10 to be formed.

  The coal ash 16 kneaded with the liquid paraffin 18 is put into a kneading apparatus in the kneading step K2, and melted and kneaded at a predetermined high temperature. The temperature here is slightly higher than the melting temperature of the synthetic resin raw material 14 and is set according to the type of the synthetic resin raw material 14.

  At this time, the liquid paraffin 18 functions to increase the fluidity of the kneaded product and adheres to the particle surface of the coal ash 16, so that the surface activity of the surface of the coal ash 16 is increased, and the synthetic resin raw material 14. Promotes uniform dispersion of coal ash 16 therein. Therefore, the kneadability is remarkably improved, and the molten synthetic resin raw material 14 can be uniformly dispersed and blended without forming colonies of particles of the coal ash 16, and the kneading resistance is low and the burden of the kneading apparatus is reduced. It is reduced.

  In addition, since this composite resin material 10 is kneaded by adding liquid paraffin 18, which is a mineral oil having high temperature stability, there is an advantage that the kneading conditions can be easily set. As the characteristics of the liquid paraffin 18, the kneading temperature can be easily increased by using a material having a vaporization temperature higher than the melting temperature of the synthetic resin raw material 14, and the kneading temperature and pressure are in a minimum necessary state. Can be processed. Thereby, the heat history to the synthetic resin raw material 14 can be reduced, deterioration such as discoloration and decomposition hardly occurs, and the quality of the composite resin material 10 can be improved.

  Moreover, the liquid paraffin 18 penetrates well into the particle surface and pores of the porous coal ash 16, disperses the coal ash 16 uniformly in the synthetic resin raw material 14, and synthesizes it into the surface and pores of the coal ash 16. The resin raw material 14 adheres reliably and the composite resin material 10 with high intensity | strength can be formed. In addition, since the liquid paraffin 18 reduces static electricity generated in the raw material of the coal ash 16, the operation of mixing the raw materials can be performed efficiently.

  The kneading apparatus used in the kneading steps K1 and K2 can be a known appropriate kneading apparatus, and is appropriately selected depending on the material, amount, use, and the like of the composite resin material 10 to be manufactured.

  In the next pelletizing step P, the kneaded product made in the kneading step K2 and extruded from the nozzle of the extrusion device is cut into a pellet and cured. A commercially available general pelletizing apparatus can be used as the equipment for pelletizing.

  The composite resin material 10 formed into a pellet shape in the pelletizing step P is used as a molding resin material composed of coal ash 16 and a raw material resin 14. The composite resin material 10 can be re-melted and molded into various shapes, and sufficient molding strength can be obtained. Therefore, the composite resin material 10 can be used for various items such as daily necessities, building materials, and the like.

  Here, when the composite resin material 10 is melted and molded, if the composite resin material 10 absorbs water above a certain level, defective molding is likely to occur. However, the composite resin material 10 is hydrolyzed in the manufacturing process. However, it is difficult to absorb moisture by mixing the liquid paraffin 18, so that it is very advantageous as a resin material for molding a resin product.

  For example, 1% by mass of liquid paraffin 18 is mixed, the synthetic resin raw material 14 and the coal ash 16 are mixed at a ratio of 3: 7, and the prototyped pellet-shaped composite resin material 10 is sufficiently dried, and then the temperature is 30 ° C. When the test was allowed to stand in an environment with a humidity of 80%, the water absorption was 5% by mass in 2 hours and 8% by mass in 4 hours. On the other hand, in the case of a composite resin material in which about 1% by mass of an unsaturated carboxylic acid is mixed instead of the liquid paraffin 18 and is formed under the same conditions, 7% by mass in 2 hours and 11.7 in 4 hours. There was a mass% water absorption.

  Therefore, according to this composite resin material 10, even when this composite resin material 10 is stored as a resin material for molding in a resin molding factory or the like, management of storage conditions (temperature, humidity, period, etc.) becomes easy. High quality molding can be performed.

  As described above, the composite resin material 10 is obtained by mixing the liquid paraffin 18 with the coal ash 16 and kneading, and mixing and kneading the synthetic resin raw material 14 with the kneaded product. The particles can be uniformly and densely dispersed in the synthetic resin raw material 14, and high molding strength can be obtained. Moreover, the fluidity | liquidity of the compound resin material 10 which knead | mixed the synthetic resin raw material 14 and the coal ash 16 can be adjusted with the addition ratio of the liquid paraffin 18, and the extrusion state in the pelletization process P can be set to an apparatus, an environment, other It can be adjusted arbitrarily according to the situation. Furthermore, the process can be simplified, and the manufacturing cost can be reduced by simplifying the apparatus and reducing kneading energy.

A composite resin material of polypropylene resin was prototyped by the composite resin production process 12, and the physical properties and ease of production of the composite resin material were evaluated. As described above, good results were obtained.
(1) Raw material
Synthetic resin raw material = polypropylene resin (PP): 30% by mass
Coal ash = fly ash: 70% by mass (after liquid paraffin kneading)
Mineral oil = Liquid paraffin: 0.5% by mass with respect to fly ash
(2) Manufacturing conditions Kneading step K1 Kneading temperature: Room temperature
Kneading pressure: Under atmospheric pressure
Kneading time: 2 minutes Kneading step K2 Kneading temperature: 180 ° C
Extrusion pressure during kneading: about 5 MPa
Kneading time: 4 minutes

A composite resin material of polyethylene resin was prototyped by the composite resin production step 12, and the physical properties and ease of production of the composite resin material were evaluated. As described above, good results were obtained.
(1) Raw material Synthetic resin raw material = polyethylene resin (PE): 20% by mass
Coal ash = fly ash: 80% by mass (after liquid paraffin kneading)
Mineral oil = Liquid paraffin: 1% by mass with respect to fly ash
(2) Manufacturing conditions Kneading step K1 Kneading temperature: Room temperature
Kneading pressure: Under atmospheric pressure
Kneading time: 3 minutes Kneading step K2 Kneading temperature: 200 ° C
Extrusion pressure during kneading: about 5 MPa
Kneading time: 5 minutes

A composite resin material of an unsaturated polyester resin as a thermosetting resin was prototyped by the composite resin production process 12, and the physical properties and ease of production of the composite resin material were evaluated. As described above, good results were obtained. It was.
(1) Raw material
Synthetic resin raw material = unsaturated polyester resin: 25% by mass
Coal ash = fly ash: 75% by mass (after liquid paraffin kneading)
Mineral oil = Liquid paraffin: 1% by mass
(2) Manufacturing conditions Kneading step K1 Kneading temperature: Room temperature
Kneading pressure: Under atmospheric pressure
Kneading time: 3 minutes Kneading step K2 Kneading temperature: 300-320 ° C
Extrusion pressure during kneading: about 5 MPa
Kneading time: 5 minutes

DESCRIPTION OF SYMBOLS 10 Composite resin material 12 Composite resin manufacturing process 14 Synthetic resin raw material 16 Coal ash 18 Liquid paraffin K1, K2 Kneading process P Pelletization process

Claims (16)

  Coal ash, mineral oil and synthetic resin raw material are kneaded, and the mineral oil penetrates into the particle surface of the coal ash, and the coal ash particles are uniformly in the synthetic resin raw material through the mineral oil. A composite resin material characterized by being dispersed.   The composite resin material according to claim 1, wherein the mineral oil has a fatty acid content of less than 0.01 mass%.   The composite resin material according to claim 1, wherein the mineral oil has an unsaturated carboxylic acid content of less than 0.01% by mass.   The composite resin material according to claim 1, wherein the mineral oil is mainly composed of paraffin.   The composite resin material according to claim 4, wherein the paraffin is liquid paraffin.   The composite resin material according to claim 1, wherein a vaporization temperature of the mineral oil is higher than a melting temperature of the synthetic resin raw material.   The composite resin material according to any one of claims 1 to 5, wherein the mineral oil is mixed at a ratio of 0.1 to 3% by mass with respect to the coal ash.   The composite resin material according to claim 7, wherein the mineral oil is mixed at a ratio of 0.5 to 1 mass% with respect to the coal ash.   The composite resin material according to any one of claims 1 to 8, wherein the coal ash is mixed at a ratio of 10 to 90 mass% of the entire material.   Kneading coal ash and mineral oil, mixing a synthetic resin raw material into a kneaded product of the coal ash and mineral oil, kneading under pressure and heating, melting the synthetic resin raw material, and the synthetic resin raw material A method for producing a composite resin material, wherein the coal ash is uniformly dispersed therein to form a composite resin material.   The said coal ash is a manufacturing method of the composite resin material of Claim 10 whose moisture content by moisture absorption is less than 5 mass%.   The said mineral oil mixed with the said coal ash is a manufacturing method of the composite resin material of Claim 10 whose content of unsaturated carboxylic acid is less than 0.01 mass%.   The method for producing a composite resin material according to claim 10, wherein the mineral oil mixed with the coal ash is liquid paraffin.   The said mineral oil mixed with the said coal ash is a manufacturing method of the composite resin material in any one of Claims 10 thru | or 13 mixed with the ratio of 0.1-3 mass% with respect to the said coal ash.   The said mineral oil is a manufacturing method of the composite resin material of Claim 14 which volatilizes at least one part during mixing the said synthetic resin raw material and heat-kneading.   The coal ash is mixed at a ratio of 10 to 90% by mass of the whole, and the coal ash is uniformly dispersed in the synthetic resin weight loss by kneading and extruded to form pellets. The manufacturing method of the composite resin material of description.

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