JPH05309753A - Fiber-reinforced plastic molded body with disposed fiber-reinforced plastics as filler and manufacture thereof - Google Patents

Abstract

PURPOSE:To newly lighten weight of FRP, improve uniformity, chemical resistance, vibration proof, damping performance, and function for utilizing resources effective by mixing powders of fine dust or fine particle consisting of disposed fiber-reinforced plastics as a filler. CONSTITUTION:Disposed fiber-reinforced plastics is crushed to powders of fine dust or fine particle which are mixed as a filler for manufacturing a fiber- reinforced plastic molded body. That is, the powdered FRP are mixed in liquefied, pelletized, or grained thermoplastic resin or thermosetting resin so as to disperse in the resin uniformly. Particle diameter is 1mum-1mm. As a mixing quantity in this case, 1wt.%-300wt.% is possible with respect to the quantity of resin. At mixing, liquid matrix resin and the FRP powders are mixed fully by using a stirrer. For using as a filler, the FRP powers and other matrix resin may be used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a part or whole of an inorganic filler such as calcium carbonate used in the production of fiber reinforced plastic, which is made of fine powdery or granular waste fiber reinforced plastic. The present invention relates to a fiber-reinforced plastic molded body produced by mixing a fine powder or fine particles of a molecular substance into each resin.

[0002]

2. Description of the Related Art What is fiber reinforced plastic (FRP)?
As a reinforcing material, a resin containing glass fiber (GFRP), a resin containing carbon fiber (CFRP), or a resin containing other reinforcing fibers is all included. Examples of the resin as the constituent base material include a thermoplastic resin and a thermosetting resin. For example, GFRP is widely used in various fields. Large items are used for space and aerospace equipment such as space shuttles and large jets, structural materials for ships and railway vehicles, and small items are used for bathtubs, automobiles and other consumer products, golf clubs, and sports equipment such as fishing rods. .. It is also used in small precision machine parts. Such FRP products are manufactured by hand lay-up method, spray-up method. Press molding method, injection molding method, preform method, S
It is made by various methods such as the MC method, the BMC method, and the cold press method. Which method is used for manufacturing depends on the shape and properties of the product. FRP with these methods
In the case of molding and producing, not only the resin component and the reinforcing fiber but also various raw materials are added. For example, a filler as an extender, a curing agent that accelerates mold curing, a mold release agent that improves mold release after molding, a colorant such as a pigment, a thickener that adjusts viscosity during molding, and shrinkage control. There are low shrinkage agents. The blending thereof is determined by the properties of the molded product, workability, and the like. An example of the raw material mixture in the case of producing GFRP by the SMC method is as follows. Unsaturated polyester resin 25 wt%, low shrinkage material 6 wt%, curing agent 0.5 wt%, internal release agent 1.5 wt%, filler 40w
t%, colorant (pigment) 1.5 wt%, thickener 0.5 wt
%, Reinforcing material (glass fiber) 25% by weight. or,
As an example of a general raw material mixture in the BMC method, a resin (including a low-shrinking agent) 20 to 30 wt% and a filler 40 to 7 are used.
0 wt% Reinforcing agent 10 to 30 wt%, curing agent (including thickener, release agent, colorant) 1 to 5 wt%. As described above, FRP is made by mixing various raw materials, but the main components are resin, reinforcing fiber and filler. The main purpose of compounding the filler is to reduce the amount of resin used, but there are various other effects. For example, the purpose of compounding a filler when molding a polyester resin is to (1) reduce the price of the product, (2) clean the surface finish, (3) reduce the adsorption amount, (4). Product hardness,
Bending strength and compressive strength are improved, (5) Thermal expansion coefficient of resin and shrinkage rate at the time of molding are reduced, cracks are prevented, (6) Thermal conductivity of the product is improved, and at the time of molding Decrease the amount of heat generation and prevent the temperature rise of thick products, (7) make the product opaque and help the effect of pigments, (8) increase the viscosity of the resin and prevent it from flowing down from the wall surface, (9 ) Dimensional accuracy is improved, (10) Surface smoothness is improved, (1
1) To make the fluidity during molding uniform. As described above, the filler has various functions as an important factor for optimizing the FRP composition.

As the filler, calcium carbonate, magnesium carbonate, aluminum hydroxide, clay, clay, talc, gypsum, barium sulfate, silica, diatomaceous earth, mica powder,
Asbestos powder is used. Of these, the commonly used filler is heavy calcium carbonate obtained by mechanically crushing and classifying limestone because of its low cost. Usually, those having an average particle size of about 2 to 8 μm are used. Fine particles have excellent molding fluidity and a beautiful surface can be obtained. However, since the amount of adsorbed resin is large, the mixed viscosity of the resin and the filler is high, and defective impregnation of the resin into the glass fiber is likely to occur. Since calcium carbonate dissolves in acid, it is not suitable for applications exposed to acids. For this reason, aluminum hydroxide, clay, barium sulfate, etc. are used in the case of a molded article requiring chemical resistance. Aluminum hydroxide is used to improve heat resistance and flame retardancy. For example, a molded article made by the SMC method by adding aluminum hydroxide is made flame-retardant. In addition, by adding approximately the same amount of aluminum hydroxide as the resin, it becomes possible to have self-extinguishing property. Further, in order to increase the compounding amount of the filler in the molded product, it is preferable to use those having different particle sizes together. The surface of the filler may be treated with a chemical and a thinning agent or the like may be added.

The present invention has developed a completely new filler, which is different from the conventional one, for the plastic filler used in large quantities. It uses fine powder or fine particles obtained by crushing discarded FRP products as a filler, and can bring high functionality to the FRP molded body produced by it. Since the method of disposing of FRP waste has not been established yet, there are many things to be landfilled, which results in illegal dumping and the like, which is a serious social problem. It can play a role in the solution.

[0005]

Since the FRP product is reinforced with a reinforcing material such as glass fiber, it has excellent properties as a composite material and is used in many fields.
The usage amount and production amount tend to increase more and more in the future.
For example, since GFRP has high strength and high durability, it has the difficulty of crushing and the difficulty of decomposition due to it. Therefore, the disposal of GFRP has become a social problem. For example, when discarding large molded articles such as boats, boats, yachts, automobiles, consumer molded articles, or trimming scraps or defective products generated at the manufacturing stage, it is difficult because of the excellent properties of GFRP. The actual situation is that I am having trouble with this process. Especially, large-scale fishery wastes such as fishing boats and boats cause environmental damage because they are left untreated, and it is difficult to dispose of them. Further, in the automobile industry, with the progress of energy saving, the weight reduction of constituent materials is being promoted at a rapid pace. The mere factor is to use GFRP reinforced with glass fiber as a vehicle body material. The ratio is from 10% to 40% of the total body weight. They are trimming scraps or defective products that are generated at the stage of manufacturing an automobile. There is a problem that such a thing does not have a concrete method as well as a method of disposing of an abandoned automobile. Thus GF
Although RP is widely used both for industrial use and for consumer use, it is a reality that the technology and method for disposal of these wastes have not been established, and measures must be taken immediately for it. There is a social background of not becoming.

In view of the above situation, the present invention reuses the waste of the fiber reinforced plastic as a resource and reduces the weight of a new FRP from the viewpoint of preventing pollution and effectively utilizing the resource. The purpose is to improve the physical properties such as homogeneity, chemical resistance, anti-vibration / vibration performance, etc. inside the molded product and to enhance its functionality.

[0007]

DISCLOSURE OF THE INVENTION The present invention is a fiber-reinforced plastic molded body and a method for producing the same for solving the above-mentioned problems. First, the fiber-reinforced plastic molded body is made of discarded fiber-reinforced plastic. It is a product made by mixing powdery or fine powder as a filler,
Further, the method for producing a fiber-reinforced plastic molded article is to pulverize the discarded fiber-reinforced plastic into a fine powdery or fine-grained powder and compound the powder as a filler to produce a fiber-reinforced plastic molded article. is there. By the way, FR
In order to effectively use P waste as a resource, cutting,
It is to make it granular or powder by pulverization or the like. Since fiber-reinforced plastic is itself a highly durable substance, it is extremely difficult to make it into a fine powder. Nevertheless, one of the inventors of the present application focused on this problem and worked on the crushing process of FRP products. As a result of diligent efforts over the years, we succeeded in making fine powder with an average particle size of 44 to 74 μm. This was filed as Japanese Patent Application No. 61-181238. Further, the finely powdered FRP was investigated for use in cement and mortar products, and the application was filed as Japanese Patent Application No. 2-61080.

In order to recycle a large amount of discarded FRP, it is effective to mix it with the above-mentioned cement or mortar product, but apart from this, it is mixed again in a plastic product and reused. Thought. This improves the adhesion between FRP and resin, and is expected to improve mechanical properties. For that purpose, the FRP waste is made into a fine powder and used again as a filler for the FRP product. That is, the finely powdered FRP powder is mixed with a liquid or pellet-like or granular thermoplastic resin or thermosetting resin, and uniformly dispersed in the resin. The particle size of the FRP powder used for that purpose is 1 μm to 1 mm, and the compounding amount in that case can be 1 wt% to 300 wt% with respect to the resin amount. Resins that can be mixed are not only polyester resins, epoxy resins, phenol resins, etc., but also other general-purpose resins (polyethylene resin, polypropylene resin, vinyl chloride resin, diallyl phthalate resin, polyurethane resin, etc.) and engineering plastics (polyamide, polycarbonate). , Polyacetal, modified polyphenylene ether, polybutylene terephthalate, etc.). When mixing, it is important to thoroughly mix the liquid matrix resin and the FRP fine powder with a stirrer. Also, FR
What affects the properties of the resin molded product filled with P fine powder is the problem of adhesion between the matrix resin constituting them and the FRP fine powdered filler. This adhesion problem has a significant effect not only on the mechanical properties of the molding, but also on other properties. Therefore, if this point is good, it is clear that the whole molding gives favorable results. When FRP fine powder is recycled as a filler, it is basically FR.
It is best to mix in the same matrix resin as the resin used for the P fine powder, but even if it is a different matrix resin, the ease of making during molding, the mechanical properties of the molded product, etc. are not always impaired. Absent. The particle size of the manufactured FRP fine powder is adjusted by the degree of pulverization, and the particle size is several meters.
It can be made from m to several μm or less. When used as a filler, it may be used in a state in which particles having different particle sizes are mixed, or may be used after being sorted into particle sizes with a sieve or the like.

[0009]

[Operation] The present invention replaces the finely pulverized FRP powder with the conventional inorganic filler, and mixes it with the matrix resin as a part or all of the filler to recycle the FRP waste and to provide a new function. To produce a molded product having The FRP waste will be evenly distributed in the formed product, but this does not impair the previously mentioned properties as a filler. Also,
The bulk densities of the moldings were compared with the case of using calcium carbonate, which is generally used as a filler. The bulk density of the resin in which the fine powder of FRP is blended is larger than that in the case of blending calcium carbonate as a filler even if the blending amount is the same.
About 60% lighter. Further, the specific strength (flexural strength / density) of the FRP fine powder was 1.7 times higher than that of the calcium carbonate. For example, finely powdered GFRP was blended in an unsaturated polyester resin and used as a filler. The filling amount at that time was 10 to 200 parts with respect to 100 parts of the resin.
This was poured into a mold and heated to room temperature or about 50 ° C. to manufacture an unsaturated polyester resin mixed with GFRP fine powder. The bulk density of this was about 1.1 to 1.3 g / cm ^{3 and} did not change so much even if the filling amount of the GFRP powder was increased. On the other hand, when 10 to 200 parts of calcium carbonate is blended, the bulk density is 1.15 g /
It increased from cm ³ to about 1.9g / cm ^3. The bending strength of the unsaturated polyester resin plate containing 100 parts of GFRP powder was 390 kg / cm ² . This was about the same as the bending strength of 378 kg / cm ² when 100 parts of calcium carbonate was blended. When the specific strength is calculated from these results, it is 2.4 × 10 ⁵ cm in the case of the calcium carbonate blending, while it becomes 3.1 × 10 ⁵ cm in the case of the GFRP blending, and the latter is 1. It increased about three times. Next, when the amount of GFRP is changed,
The influence of the bending strength of the resin plate was examined. The bending strength when 100 parts of GFRP powder was mixed was 390 kg / cm ² , and calcium carbonate was 2
It was almost the same as when 100 parts were blended. Therefore, it can be said that up to this level of blending, the bending strength is about the same as that of the molded product made of calcium carbonate which is actually used as a filler. The surface of the sample prepared by blending the GFRP fine powder was smooth and beautiful, and it was difficult to compare this surface condition with that of calcium carbonate. Further, calcium carbonate as a filler has a drawback that it easily dissolves in acids, and is not suitable for uses exposed to acid rain or the like. On the other hand, GF
Since the RP fine powder has excellent chemical resistance equivalent to that of the resin used as the base material, it can be used in those fields and exhibits an excellent action. Furthermore, the blending of the FRP fine powder, which is a viscoelastic body, improves the loss elastic modulus of the molded product, and thus has the effect of suppressing vibration. Further, since the difference in density between FRP fine powder and resin is extremely smaller than that of calcium carbonate, it is difficult for interlayer separation to occur even during molding.
It is possible to make products with homogeneous properties. From the above facts, by mixing the FRP fine powder as the filler, the functionality of the molded product to be produced can be highly exhibited.

[0010]

The details of the present invention will be described in the following examples. Example 1. The discarded polybas was crushed with a diamond cutter to produce GFRP fine powder. The resin forming this polybas was an unsaturated polyester resin. When making fine powder, GFRP fine powder (fine powder A) that also contains fibrous glass fibers in a crushed state, and only GFRP fine powder obtained by removing fibrous glass fibers with a sieve (fine powder B ) Was produced. Of the two types of GFRP fine powder, the particle size distribution of fine powder A was measured,
It is shown in Table 1. The average particle shape of the fine powder A is 44 to 74 μ.
Mainly m, accounting for about 74%. The particle size distribution of the fine powder B is a distribution obtained by removing the powder and glass fiber of 100 μm or more from the results of Table 1. The difference between the fine powder A and the fine powder B was whether or not they contained some fibrous glass fibers.

[0011]

[Table 1]

To 100 parts of liquid unsaturated polyester resin, 10 parts, 25 parts and 50 parts of GFRP fine powder A are respectively added.
Parts, 75 parts, 100 parts, 150 parts, and 200 parts were added and mixed well in a mortar, which was 15 mm wide and 4 mm thick.
It was poured into a mold having a length of 220 mm and a length of 220 mm, and heated at room temperature or about 50 ° C. to prepare a polyester resin plate filled with GFRP fine powder A. The weight and size of the obtained resin plate were determined, and the bulk density was calculated. The bending strength was determined by the three-point bending test method with the distance between fulcrums set to 60 mm. GFRP
The appearance of the fine powder-filled resin plate became opaque by filling with the GFRP fine powder A. Table 2 shows the bulk density, bending test, specific strength, and relative density and relative strength of the resin plate without compounding.

[0013]

[Table 2]

For comparison, a sample was prepared under the same conditions for an unsaturated polyester resin plate containing a predetermined amount of calcium carbonate (150 mesh or less) powder, and the results are shown in Table 3.

[0015]

[Table 3]

The bulk density of the polyester resin plate prepared by blending the GFRP fine powder A was about 1.1 to 1.3 g / cm ³ . Further, even if the blending amount of the GFRP fine powder was increased, no significant difference was found in the bulk density. On the other hand, in the case of calcium carbonate, its bulk density is 1.2 g / c.
It increased from m ³ to 1.9 g / cm ³ . Also, G
In the case of both FRP fine powder and calcium carbonate, when these are added, the bending strength is half that of the non-added product.
It became about. However, comparing the specific strengths, the GFRP fine powder has 4.1 × 10 ⁵ cm even in the case of 50 parts of the compound, but 2.4 × 10 in the case of the calcium carbonate compound.
^It was only ^{5 cm} . Therefore, the specific strength of the produced resin plate was 1.7 times as large as that in the case where 50 parts of GFRP powder was mixed, as compared with the case where the same amount of calcium carbonate was mixed.

Example 2. 10 parts of GFRP fine powder B and 2 parts of 100 parts of liquid unsaturated polyester resin, respectively
5, 50, 75, 100, 150 and 20 parts
Add 0 parts and mix well in a mortar.
It was poured into a mold having a thickness of 4 mm and a length of 220 mm and heated at room temperature or about 50 ° C. to make a polyester resin plate filled with FRP fine powder B. The weight and size of the obtained resin plate were determined, and the bulk density was calculated. Also, the distance between fulcrums is 60
mm, and the bending strength was determined by the three-point bending test method. G
The appearance of the resin plate filled with FRP fine powder B is GFRP fine powder B
It became opaque by blending. Table 4 shows the bulk density, bending strength, specific strength, and relative density and relative strength of the unblended materials.

[0018]

[Table 4]

Even if the amount of GFRP fine powder B increased, the bulk density of the resin plate produced did not change much.
Bending strength tended to decrease. In this case, GF
Up to a sample plate containing 100 parts of RP differential powder B showed a bending strength similar to that of calcium carbonate. Also,
Regarding the specific strength of the resin plate, the one in which 50 parts of GFRP fine powder was blended was about 3 in comparison with the one in which the same amount of calcium carbonate was blended.
Increased by 0%.

Example 3. A phenol resin was used as the matrix of the GFRP fine powder. Phenol resin (resol type) / methanol solution (resin 60 wt
%, Methanol 40 wt%), the predetermined amount of the fine powder A shown in Example 1 (10 wt% to 70 wt% in the sample weight).
%). For example, in the case of a sample having a fine powder content of 50 wt%, the above phenol resin / methanol solution 8
50 g of GFRP fine powder A was added to 3 g (each containing 50 g of resin and 33 g of methanol). Both were placed in a mortar, thoroughly mixed, and then poured into a mold (width 40 mm, thickness 10 mm, length 60 mm). When the amount of GFRP fine powder blended was 50 wt% or more, it became difficult to mix the GFRP fine powder into the phenol resin when the sample was manufactured. I tried to be. Then, the GFRP fine powder and the resin component were sufficiently kneaded and then deaerated with a vacuum pump. Next, the mold was placed in a dryer and heated to 50 ° C.
Further heating was continued and the temperature was kept at 80 ° C. for 10 hours to prepare a phenol resin plate filled with GFRP fine powder A. Also, GFR
An attempt was made also for a case where the amount of P fine powder blended was 80 wt%, but sufficient mixing could not be obtained by the hand kneading method using a mortar. However, this point can be solved by using a kneading machine such as a mixer. Each of the obtained samples was pale yellow, and the whiteness increased as the amount of GFRP fine powder increased. Further, it was found that GFRP fine powder and glass fibers were distributed in the produced resin plate. Bulk density and bending strength for each sample (3-point bending, distance between fulcrums 5
cm) was obtained and the results are shown in Table 5. In Examples 1, 2 and 3 described above, the conventional inorganic filler was entirely replaced with fine FRP powder, but the conventional inorganic filler was not all, but only a part thereof was FR.
It does not matter if it is replaced with P fine powder. By doing so, the weight reduction and the high functionality of the manufactured FRP product are slightly sacrificed, but they are useful in terms of reducing the price of the product.

[0021]

[Table 5]

[0022]

INDUSTRIAL APPLICABILITY In the above embodiment, the case where FRP fine powder was blended as a filler for the unsaturated polyester resin molded product or the phenol resin molded product was exemplified.
The resin molded body made by mixing FRP fine powder as a filler can be made lighter than calcium carbonate generally used as a filler. Further, the mechanical strength represented by the bending strength shows a bending strength equal to or higher than that in the case where calcium carbonate is added as a filler even when the resin and the FRP fine powder are added in substantially the same amount. The specific strength is much higher when the FRP fine powder is mixed in the same proportion than when calcium carbonate is used. Also, FRP
The molded product containing the powder has a homogenous structure in its internal structure, is improved in chemical resistance, and is imparted with high functionality such as vibration-damping and vibration-damping properties. Therefore,
FRP products that have been discarded or have already been discarded, such as industrial waste, trimming waste, or defective products at the time of molding, can be recycled as a filler for resin molded products by pulverizing them. Furthermore, in the current plastic molding industry, plastic is
Although an inorganic substance (calcium carbonate, etc.) having completely different properties was used as a filler in the resin, in the present invention, the filler is adhered to the matrix by substituting an organic substance of the same quality (FRP fine powder). Will be improved.
The use of such a lightweight, inexpensive, and highly functional filler has an immeasurable effect on the plastic-related industry, and brings extremely great benefits to the field. From these results, the present invention provides 2
It can contribute to clean the global environment, which is an important issue for human survival in the first century, and to make more effective use of limited global resources, and its social ripple effect is extremely large. Can be said.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI technical display location B29C 67/16 7188-4F // B29K 105: 26 (72) Inventor Michiko Yoshikawa Nishimachi, Kokubunji, Tokyo 1-chome 24-26

Claims (2)

[Claims] 1. A fiber-reinforced plastic molding produced by mixing fine powdery or fine-grained powder of discarded fiber-reinforced plastic as a filler. 2. A fiber-reinforced plastic molded product, which is produced by pulverizing a fine powdery or fine-grained powder of discarded fiber-reinforced plastic and blending the powder as a filler to produce a fiber-reinforced plastic molded product. Method