JPH04339841A - Filler for resin, and resin composition - Google Patents

Abstract

PURPOSE:To provide a filler which, when compounded into a resin, gives a compsn. moldable into an article excellent in impact strength, heat resistance, etc., by selecting a specific combustion ash as the filler. CONSTITUTION:A combustion ash which is discharged, e.g. during combustion of a combustible material contg. lime (e.g. a combustible waste) in a fluidized- bed boiler at a relatively low temp., mainly comprises SiO2 and Al2O3, and has a wt. average particle size of 1-20mum and a specific surface area of 9X10<3>cm<2>/g or higher is selected.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to fillers for resins useful as extenders for resins and resin compositions containing the fillers.

0002

[Prior Art] Conventionally, by filling resin with various inorganic fine particles having a high elastic modulus, the elastic modulus, creep resistance,
It is known that mechanical properties such as compressive strength and heat distortion temperature can be significantly improved. For example, low-cost fillers such as calcium carbonate, calcium sulfate, talc, and clay are added to resins because they can improve rigidity and heat resistance. However, although the addition of these fillers can increase the heat deformation temperature, hardness, and economic efficiency of the resin, it tends to reduce elongation at break, impact strength, and the like.

[0003] Furthermore, as an effective use of waste, there is a proposal to mix fly ash, which is the high-temperature combustion ash of coal produced by pulverized coal sintering, into thermoplastic resin as a filler (Japanese Patent Laid-Open No. 61-72059; Showa 47-34635
(Japanese Patent Application Laid-Open No. 48-29848). This fly ash is mainly composed of silicon oxide and alumina and has a 1600%
Because it is emitted through high-temperature combustion at temperatures around ℃, there is very little unburned material, which is melted, dispersed, and solidified during high-temperature firing to form small-sized spheres with smooth glassy surfaces, and the slippage between each substance is extremely high. get well. Therefore, this fly ash can be kneaded and blended into a resin very easily. Furthermore, the resin filled with this resin does not lose its fluidity, so its processability does not deteriorate. Furthermore, since this fly ash is spherical, it can be packed densely into the resin, and it is said that the processability of the resin will not deteriorate even if the amount blended is increased.

0004

[Problems to be Solved by the Invention] By the way, in order to improve the economic efficiency and heat resistance of resins using inexpensive inorganic fillers,
It is necessary to increase the amount of filler added. however,
When the amount of filler increases, the bond between the polymers of the resin is weakened, and the physical properties generally deteriorate. In addition, the degree of deterioration in physical properties varies depending on the particle size of the filler, with larger particles having a greater reduction in physical properties than smaller particles, and the physical properties also changing depending on the type of filler. In particular, if the tear strength, hardness, and elongation are significantly reduced, problems such as underfilling and reduced dimensional accuracy of the molded product occur during molding of the resin composition.

[0005] In conventional resin compositions containing inorganic fillers,
To increase mechanical strength, a dispersant is added to prevent agglomeration in the resin, and the surface of the filler is coated to increase its affinity with the resin. It is also known that it is possible to classify the filler and use one with a small particle size to increase the amount of dispersant and suppress the deterioration of physical properties. However, none of these methods sufficiently improves the physical properties of the molded product considering the increase in the cost of the filler.

Furthermore, when a rubber component is mixed or copolymerized with the resin as a method of increasing the impact resistance of the resin, there is a problem in that the resin layer becomes soft, hardness does not increase, and heat resistance does not improve. An object of the present invention is to provide a filler and a resin composition thereof that cause less problems during molding and less deterioration of the physical properties of the molded product even if a large amount is blended into the resin.

[0007]

[Means for Solving the Problems] The present inventors have discovered that the combustion ash generated when combustible materials including coal are burned in a fluidized bed boiler, etc., differs from known fly ash and contains a large amount of unburned matter. It was discovered that ash particles have irregular shapes, porous surfaces, and relatively large particle sizes. As a result of considering applications that take advantage of this feature,
This combustion ash was obtained after discovering that it has excellent advantages as a filler for molding resins.

[0008] The resin filler of the present invention is a filler that is mixed into a resin and used for molding, and is composed of combustion ash having a weight average particle size of 1 to 20 μm and a specific surface area of 9 x 10 cm2 /g or more. It is characterized by The resin composition of the present invention contains, as a filler, combustion ash having a weight average particle diameter of 1 to 20 μm and a specific surface area of 9×10 cm2 /g or more, and a thermoplastic resin such as a vinyl chloride resin or a polypropylene resin or Made of thermosetting resin.

[0009] This combustion ash has a weight average particle size of 1 to 20 μm.
Shapes in the range of m can be applied. If the particle size exceeds 20 μm, the dispersibility in the resin will deteriorate, which is not preferable. Therefore, when the particle size is within this range, it is possible to uniformly disperse in the resin and suppress deterioration of physical properties. Further, it is necessary that the specific surface area of this combustion ash is 9×10 3 cm 2 /g or more. The specific surface area of this combustion ash is 9×10
If it is less than 3 cm2/g, the adhesion with the resin will decrease and the physical properties of the molded article cannot be improved, which is not preferable.

In order to obtain the above-mentioned filling effect, it is preferable that the combustion ash is blended as a filler in an amount of 5% by weight or more based on the resin. Furthermore, since this filler can suppress deterioration of the physical properties of the resin, it can be added in a larger amount than conventional fillers to improve economic efficiency. This combustion ash acts to increase the volume in the resin, and unlike conventional fillers, it can suppress the deterioration of the mechanical properties of the resin. That is, since this combustion ash has a porous structure, it can be entangled with each other at the interface with the resin to form a close contact surface. Therefore, it is thought that when stress is applied to the resin, separation at the interface is prevented, and cracks are prevented from occurring in the molded product, thereby suppressing deterioration of mechanical properties. Therefore, unlike conventional fillers, reduction in mechanical strength can be reduced.

[0011] In order to blend this combustion ash into the resin, a V-type mixer, a W-type mixer, a cylindrical mixer or a Henschel mixer is used.
It is possible to apply a method in which the resin is mixed for a predetermined period of time using a mixer such as the above, and then kneaded and extruded using an extruder or the like, or a filler or the like is supplied from a vent while the resin is kneaded using an extruder or the like. At this time, additives such as plasticizers, stabilizers, lubricants, and colorants can also be added and blended at the same time.

[0012] This combustion ash is combusted and discharged at around 800°C, and has a different shape from fly ash that is combusted and calcined at around 1600°C, like the fly ash discharged from conventional pulverized coal combustion boilers. have In other words, as shown in Table 1, the main components of both are silicon oxide and alumina, but in the case of high-temperature combustion, the ash content is melted and calcined to form spherical particles, and the particle size is relatively small (Figure 1 shows the particle structure). On the other hand, in the case of combustion in a fluidized bed combustion boiler, there is a large amount of unsintered content, and the ash content is rarely melted and burned, so the shape is not constant and irregularly shaped, as shown in Figure 11 (
As shown in the photograph of the particle structure, it is porous and has a relatively large particle size. Note that since this combustion ash is not exposed to high temperatures, the particle size distribution will not become wide due to melting, agglomeration, etc. As a result, particles within a predetermined size range can be obtained without performing operations such as classification.

[0013] The average particle size is calculated based on weight distribution. This combustion ash is emitted, for example, when combustible materials (such as waste) containing coal are incinerated at a relatively low temperature in a fluidized bed boiler. Note that this combustible material may be coal alone. Moreover, since this combustion ash mainly contains hard ceramic materials such as silicon oxide and alumina, when it is blended into a resin, it can increase the hardness and heat resistance of the resin.

[0014] This combustion ash is preferably blended with the resin as a filler in a range of 5% to 60% by weight in order to obtain a sufficient filling effect. Examples of resins that can be blended with this filler include thermoplastic resins such as polyethylene, polypropylene, vinyl acetate resin, polystyrene, acrylic resin,
ABS resin, vinyl chloride resin, nylon, polyester, thermosetting resin such as polyester resin, polyurethane resin, phenol resin, melamine resin, etc. can be applied.
Particularly preferred are polypropylene resins and vinyl chloride resins.

Homopolymers, copolymers, and block polymers commonly used as polypropylene resins
Polypropylene resins such as can be used. Ethylene propylene copolymers having an ethylene component content of 30% or less can also be used. As the vinyl chloride resin, commonly used hard, soft, and copolymerized vinyl chloride resins can be used, and there is no particular limitation.

In a molded article in which the combustion ash is blended with a resin, the porous structure on the surface of the combustion ash is entangled with the resin to form a close contact surface. Therefore, when stress is applied to the molded product, separation of the resin and filler at the interface can be suppressed, and cracks can be prevented from occurring in the resin. As a result, reductions in impact resistance, tensile strength, tear strength, etc. of the molded product can be suppressed. Therefore, there is no need to modify the resin component by adding rubber or the like. Furthermore, this filler can be blended into the resin in large amounts because it has a low degree of deterioration of physical properties. By adding this filler, the molded article can increase its hardness and heat distortion temperature and improve its heat resistance.

[0017] In addition, in the case of vinyl chloride resin, chlorine gas is generated when it is burned and disposed of, but if this combustion ash is contained in the resin, it can absorb this chlorine gas and reduce the amount generated. can. That is, this combustion ash contains unburned carbon with polarity in its porous pores. Therefore, gases such as chlorine gas are trapped within the porous pores due to physical suction and van der Waals forces. As a result, it is possible to suppress harmful chlorine gas from being released into the surroundings as a gas during combustion.

Calcium carbonate has conventionally been used in vinyl chloride resins for reasons such as improving heat resistance and reducing costs. This calcium carbonate turns into calcium oxide due to heat, and it is possible that this reacts with chlorine to generate calcium chloride, but this is inefficient. Gas adsorption using zeolite, silica gel, activated carbon, etc. is also considered, but it is too expensive to use as a filler, so it cannot be applied. However, this combustion ash is cheap and can be effectively used as a filler.

[0019]

[Function] The resin filler of the present invention has a weight average particle diameter of 1 to 1.
It is low-temperature combustion ash with a specific surface area of 20 μm and 9×10 3 cm 2 /g or more. Since this combustion ash has a porous structure, it is entangled with the resin at the contact interface with the resin, and is uniformly dispersed in the resin in a close contact state.

Since this filler has a particle size within a specific range, it has good dispersibility in the resin, and even when added in a large amount, moldability does not deteriorate. Furthermore, since this filler has a porous structure, it has good adhesion to the resin and can suppress deterioration of the mechanical properties of the resin composition compared to conventional fillers. Furthermore, since this filler has a porous structure and has a high affinity with the resin at the interface, there is no need to perform a treatment such as coating on the surface to increase the affinity. Therefore, it can be provided as an inexpensive filler.

[0021] Furthermore, since this filler contains a ceramic substance having high hardness, it is possible to increase the hardness of the resin and improve the heat resistance.

[0022]

[Examples] Hereinafter, the present invention will be explained in detail using examples. (Example 1) As the filler for this resin, 700% of coal was used.
Ash combusted in a fluidized bed boiler at ~800°C was used. The composition of this combustion ash is as shown in Table 1, SiO2, Al2
It is a fine powder with a porous structure containing O3 as a main component, a weight average particle size of 3 to 20 μm, and a specific surface area of 7×10 3 cm 2 /g or more. Figure 1 shows the particle structure of this combustion ash. As an analysis example is shown in Table 1, the combustion ash of the present invention has a large amount of unburned matter compared to the fly ash obtained by the pulverized coal combustion method, and the combustion ash particles have an irregular shape, a porous structure on the surface, and a small particle size. Relatively large. The combustion ash was classified and the relationship between average particle size and specific surface area was measured based on JISR5201. The results are shown in Figure 2. When the average particle size is 20 μm or less, the specific surface area is 9×10 3 cm 2 /g or more.

For comparison, a fly ash formed by pulverized coal sintering method at high temperature was similarly investigated and the results are shown in FIG. In the case of fly ash, the specific surface area is 7×10 3 cm 2 /g or less regardless of the particle size, and it hardly shows a porous structure. The combustion ash of the example had a weight average particle size of 3 to 20 μm and a specific surface area of 7×10 cm2 /
It is a filler with a porous structure when it is more than 100 g.

[0024] The following examples show that this filler is blended with resin and has excellent effects. (Example 2) Test pieces were prepared in which the blended amounts of the combustion ash filler, soft calcium carbonate, and heavy calcium carbonate (both manufactured by Shiraishi Calcium Co., Ltd.) were mixed into soft vinyl chloride resin. Regarding this test piece, tensile strength, elongation, hardness,
Tear strength was measured and compared.

The blending composition is vinyl chloride resin (ρ=1.0
5) 100 parts by weight, 50 parts by weight of plasticizer (D.O.P),
3 parts by weight of white lead, 1 part by weight of stearic acid, 0 to 20 parts by weight of filler
It is 0 parts by weight.

[0026]

[Table 1] The results are shown in Figures 3-6. In the figure, the white circle is the filler of combustion ash.
The black circles represent soft calcium carbonate, and the x marks represent heavy calcium carbonate.

In this measurement range, the combustion ash filler is
Compared to calcium carbonate, it exhibits higher values at all blending amounts, with little deterioration in physical properties. Particularly when adding a large amount, there is little decrease. Therefore, it is an excellent filler that can be added in larger amounts than the commonly used calcium carbonate. (Example 3) Next, vinyl chloride resin paste was used as the applied resin. The filler added to the paste has a low melt viscosity and is most desired to have improved impact resistance.

The vinyl chloride resin paste (Geo
n 121 Geon Co., Ltd.) 100 parts by weight, plasticizer (D.O.P) 60 parts by weight, lead stearate 1 part by weight,
The filler is 0 to 40 parts by weight. The melt viscosity of this resin composition was measured, and a sheet-like test piece was prepared and subjected to an impact test. The results are shown in Figures 7-8.

Within this measurement range, the combustion ash filler has a lower melt viscosity than when the same amount of calcium carbonate is added;
The impact resistance is higher than when the same amount of calcium carbonate is added and is also improved compared to when no filler is added. (Example 4) Here, the same filler as in Example 2 was used in polypropylene resin to conduct a comparative study of the filler.

[0030] The blending amount of the filler is 10% of the polypropylene resin.
A test piece was prepared by adding each filler in a range of 0 to 60% by weight relative to 0 part by weight. Then, the tensile strength and elongation were measured. The results are shown in Figures 9-10. Within this measurement range, the tensile strength of this combustion ash filler is higher than that of calcium carbonate, and even when added in a large amount, it exhibits a high tensile strength. Furthermore, the elongation value is also higher than that of calcium carbonate. This indicates that this combustion ash has excellent properties as a filler. (Example 5) Polypropylene resin is manufactured by Sumitomo Chemical Co., Ltd.
20% by weight (No. 6-1) and 40% by weight (No. 6-2) of the combustion ash obtained in Example 1 were added using AW-564 produced by the company, and blended in a cylindrical mixer. The mixture was kneaded using a twin-screw extruder to obtain a molding material. This molding material was injection molded to produce test pieces for impact tests and heat distortion temperature measurements. (Reference Example) As a reference example, a test piece was molded from polypropylene resin (AW-564) to which no filler was added. (Comparative Example) In a comparative example, a test piece was prepared in the same manner as in the example except that the filler in Example 6 was changed to one shown below. As shown in Table 2, No. No. 1 and No. 2 contain 20% by weight and 40% by weight of calcium carbonate (KS-500 manufactured by Dowa Calfine) with a weight average particle diameter of 5 μm. No. 3
, No. 4 was prepared by adding 20% by weight and 40% by weight of JIS standard fly ash discharged from a pulverized coal boiler (the particle structure is shown in FIG. 11) with a weight average particle diameter of 5 μm. No. 5 is talc (manufactured by Hayashi Kasei Co., Ltd.: JR
-2), No. No. 6 was wollastonite (manufactured by Hayashi Kasei Co., Ltd.: VM-4N). No. 7 contains clay (manufactured by Shiraishi Calcium Co., Ltd.: Burgess KE50). 8 is mica (
200HK (manufactured by Kuraray Co., Ltd.) was blended in an amount of 40% by weight.

The Izod impact value and heat distortion temperature were measured for each test piece obtained. The results are shown in Table 2. The Izod impact value was measured using an Izod impact tester based on ASTM D256 using a test piece with a thickness of 1/8 inch and no notch. The heat distortion temperature was determined based on ASTM D648 under a load of 18.5 kg/cm2.

As shown in Table 2, when comparing cases where the same amount of filler is added, Example No. In No. 6-1 and No. 6-2, the heat distortion temperature is higher than that of the known filler of Comparative Example, and the impact strength is also significantly improved. Therefore, it has sufficient physical properties to be used as an industrial material without adding a rubber component to the resin to improve the impact strength of the molded product.

[0033]

[Table 2] Comparative example No. 1 of fly ash discharged from a pulverized coal combustion boiler. 3, 4 and Example No. Figures 12 and 13 are line graphs comparing the Izod impact values and heat distortion temperatures of fillers No. 6-1 and No. 6-2. The impact strength of the example when the filling amount is 20% by weight is significantly higher than that of the comparative example, and even when the filling amount is 40% by weight, it shows a higher value than that of fly ash. Furthermore, the heat distortion temperature exceeds 80° C. at 40% by weight, which is superior to the case where fly ash is blended. (Example 6) The combustion ash of Example 1 was classified using a classifier (MS-1H manufactured by Hosokawa Micron Co., Ltd.) into five types of particle sizes (1, 2, 3, 4, and 5 in Figure 16). Used separately. The particle size distribution is shown in the graph of FIG. 50% by weight of each filler classified to this particle size was added to vinyl chloride resin (manufactured by Mitsubishi Kasei), a test sheet was prepared by a conventional method, and the tensile strength and tear strength were evaluated based on JIS-6301 9. . The results are shown in Figures 15-16.

For comparison, calcium carbonate of a specific particle size (manufactured by Nitto Funka Co., Ltd.: A; NS300) was used instead of combustion ash.
0, B; NS800, C; CSS80, D; SS30,
E; NN200) was used. The particle size distribution of this calcium carbonate is shown in FIG. A test sheet containing the same amounts of these five types of calcium carbonate as in the case of combustion ash was prepared and evaluated.

The results are shown in Figures 15 and 16. In the figure, the ● mark indicates an example of combustion ash, and the ○ mark indicates a calcium carbonate filler. The strength of the filler in the example increases as the particle size decreases, as in the case of calcium carbonate, but the physical properties are higher than that of calcium carbonate even in the region of relatively large particle sizes. In other words, even if the average particle size is larger than 15 μm, the particle size is 1.5 μm.
It maintains the same strength as calcium carbonate. When the average particle diameter is the same, the filler of this example maintains higher strength. Therefore, even with a coarse particle filler that is not classified, the same effect as when using calcium carbonate with small particle size and good dispersibility can be obtained. Therefore, this filler does not require classification, and costs can be reduced.

In addition, the fly ash obtained by the pulverized coal combustion method, whose particle structure is shown in FIG. 11, was classified and the relationship between the average particle size and strength was investigated in the same manner as in the example. The results are shown by △ marks in FIGS. Shown below. This fly ash shows almost the same tendency as the case of calcium carbonate, and the strength decreases when the particle size is large. That is, in this case, the deterioration of physical properties cannot be suppressed unless the particles are classified to only have small particle sizes.

Since this combustion ash has a porous structure, it is in close contact with the resin through interaction at the interface, so that the strength of the resin is higher than in the case of calcium carbonate, which does not have a porous structure. (Example 7) 100 parts by weight of vinyl chloride resin was mixed with calcium carbonate (Whiten, manufactured by Shiraishi Calcium Co., Ltd.), combustion ash, and DOP of a plasticizer in the proportions shown in Table 3, and its physical properties were investigated. . No. 1 as a filler. No. 10 contains 14 parts by weight of combustion ash and 129 parts by weight of calcium carbonate.
No. 11 contains 36 parts by weight of combustion ash and 107 parts by weight of calcium carbonate. No. 12 contains 71 parts by weight of combustion ash and 71 parts by weight of calcium carbonate. 13 contains 143 parts by weight of combustion ash only,
No. For comparison, No. 14 contains 143 parts by weight of calcium carbonate.

[0038]

[Table 3] When the amount of combustion ash increases, physical properties other than elongation decrease, which are equivalent to or higher than those using only calcium carbonate.

Furthermore, the amount of chlorine gas generated by combustion was investigated for each of the above blended resins. Here, the combustion involves burning the above-mentioned blended resin in an electric furnace at 1000°C, and checking the generated gas for the presence or absence of chlorine gas using a gas chromatograph.
and its amount was quantified. The quantitative results are shown in FIG. 17. As the amount of combustion ash increases, the generation of chlorine gas is suppressed and the amount of chlorine in the combustion gas decreases.

[0040] Therefore, a vinyl chloride resin composition that generates less harmful chlorine gas when incinerated can be obtained.

[0041]

[Effect] The resin filler of the present invention has a specific surface area of 9×10
It is a fine powder with a specific particle size range of 3 cm2/g or more, and has an irregular shape rather than a spherical shape. Therefore, when the filler is blended with the resin and kneaded, the filler and the resin intertwine and can be dispersed and present in a tightly adhered state at the interface.

[0042] Therefore, a molded article made of a resin composition containing this filler can be prevented from deteriorating physical properties such as impact strength, which is the case when conventional fillers are added. In addition, there is no lack of thickness or reduction in dimensional accuracy during molding of the resin composition due to insufficient mechanical strength of the resin. Therefore, there is no need to treat or classify the surface of the filler. Furthermore, even if a large amount of filler is added to the resin, there is little deterioration in the physical properties of the molded product, so adding a large amount can reduce costs. Since this filler contains a highly hard ceramic material as a main component, it can increase the hardness and heat resistance of the resin and provide excellent physical properties. Furthermore, since it is combustion ash, it can be blended in large quantities as a cheap and economical filler. Furthermore, since it is an effective use of what would otherwise have been discarded, it can also address environmental issues.

Furthermore, when blended with vinyl chloride resin, the porous combustion ash absorbs and retains chlorine gas during incineration, so the amount of chlorine in the combustion gas can be reduced. Therefore, corrosion due to chlorine gas is prevented, and special treatment facilities can be made unnecessary.

[Brief explanation of the drawing]

[Figure 1] Enlarged photographic diagram of the particle structure of the filler in combustion ash.

FIG. 2 is a line graph showing the relationship between the average particle diameter and specific surface area of combustion ash and fly ash.

FIG. 3 is a tensile strength line graph showing the relationship between the amount of filler added to a soft vinyl chloride resin and physical properties.

FIG. 4 is a line graph of elongation showing the relationship between the amount of filler added to a soft vinyl chloride resin and physical properties.

FIG. 5 is a hardness line graph showing the relationship between the amount of filler added to a soft vinyl chloride resin and physical properties.

FIG. 6 is a line graph of tear strength showing the relationship between the amount of filler added to soft vinyl chloride resin and physical properties.

FIG. 7 is a melt viscosity line graph showing the relationship between filler content, melt viscosity, and impact strength of vinyl chloride resin paste.

FIG. 8 is a line graph of filler content, melt viscosity, and impact strength of vinyl chloride resin paste.

FIG. 9 is a tensile strength line graph showing the relationship between the amount of filler added, tensile strength, and elongation of polypropylene resin.

FIG. 10 is an elongation line graph showing the relationship between the amount of filler added, tensile strength, and elongation of polypropylene resin.

FIG. 11 is an enlarged photograph of the particle structure of fly ash.

FIG. 12 is a line graph showing the relationship between impact strength and filling amount when the combustion ash and fly ash of the present invention are added.

FIG. 13 is a line graph showing the relationship between heat distortion temperature and filling amount.

FIG. 14 is a graph showing particle size distribution.

FIG. 15 is a graph showing the relationship between the tensile strength and particle size of a resin blended with classified particles.

FIG. 16 is a graph showing the results of a tear strength test of the sample of FIG. 15.

FIG. 17 is a graph showing the measurement results of the amount of chlorine gas generated in the combustion test.

Claims (2)

[Claims] Claim 1: A filler mixed into a resin and used for molding, characterized by being combustion ash having a weight average particle size of 1 to 20 μm and a specific surface area of 9×10 cm2 /g or more. Filler for resin. [Claim 2] A molding resin as a matrix and a filler having a weight average particle diameter of 1 to 20 μm and a specific surface area of 9×
A resin composition consisting of 103 cm2/g of combustion ash.