JPH10245439A - Photooxidation-reactive fiber-reinforced plastic molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an FRP molded product that can remove hazardous substances and bad smell in the surroundings and can be readily disposed. SOLUTION: This FRP molded product is prepared by molding a mixture of 100 pts.wt. of the FRP feedstock with 5-10 pts.wt. of a semiconductor having photocatalytic action to decompose organic substances under irradiation with light. The semiconductor is preferably an activated multiple oxide that is prepared by supporting 1/10,000-5/10,000, based on the semiconductor, of platinum on an oxide mixture of 3-20wt.% of titanium oxide and 97-80wt.% of silicon oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fiber-reinforced plastic molded article having photooxidation reactivity.

[0002]

[Prior Art] Fiber Reinforc
ed Plastics (hereinafter abbreviated as FRP) combines the mechanical properties of fibers with the chemical properties of synthetic resins and replaces high-grade metal materials with aircraft, automobiles, railway vehicles, ships, building materials, and liquids. Widely used for containers and the like.

[0003] However, FRP generates harmful substances, even in a very small amount, for a considerable period of time after being molded, and produces odor. Further, the FRP molded article becomes unnecessary, and when it is discarded, it becomes a difficult-to-treat waste and pollutes the environment.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an FRP molded article which can remove harmful substances and odors and can be easily disposed of.

[0005]

According to the present invention, a semiconductor having a photocatalytic action for decomposing an organic substance under light irradiation is used in an amount of 3 to 10 parts by weight per 100 parts by weight of a fiber-reinforced plastic raw material.
It is a fiber-oxidized plastic molded article having photo-oxidation reactivity characterized by mixing parts by weight and molding. According to the present invention, TiO ₂ , SiO ₂ , ZnO, SrTi
O ₃ , CdS, GaP, InP, GaAs, BaTi
O ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₅ , WO ₃ , SnO
_{2, Bi 2 O 3, NiO} , Cu 2 O, SiC, MOS 2, I
At least one of the group consisting of nPb, RuO ₂ and CeO ₂ contains trace amounts of Pt, Rh, Nb, Cu and Sn
Is formed by mixing a known semiconductor having a photocatalytic action to which at least one kind of
RP molded products release oxidizing substances by the action of light,
It oxidizes and decomposes harmful substances and odorous components generated from FRP molded products. Further, since the FRP molded article of the present invention releases an oxidizing substance, it can be easily disposed of and has little effect on the environment. The mixing amount of the semiconductor having a photocatalytic action into the FRP raw material varies depending on the use of the FRP molded product.
If more than 10 parts by weight are mixed, the properties as FRP may be deteriorated.

Further, according to the present invention, the semiconductor is preferably titanium oxide 3
An active composite oxide comprising a composite oxide containing ２０20% by weight and 97-80% by weight of silicon oxide loaded with platinum in an amount of 1 / 10,000 to 5 / 10,000 of the composite oxide. I do. According to the present invention, an active composite oxide in which a trace amount of platinum is supported on a composite oxide containing titanium oxide and silicon oxide has particularly good reactivity to light in the semiconductor, and FR
The effect when used for P is remarkable. This is considered to be because electrons in the titanium oxide are transferred to platinum by light irradiation, a reduction reaction occurs on the platinum, and an oxidation reaction occurs in holes remaining in the titanium oxide. Not only harmful substances and foul odor components generated from the FRP molded product by this redox reaction, but also FR
Harmful substances near P are decomposed, and further exhibit antibacterial properties. Therefore, the space surrounded by the FRP molded product of the present invention,
For example, air in aircraft, automobiles, railway vehicles, and ships is purified, the liquid container of the FRP molded article of the present invention, for example, the inside of a water purification tank is kept in an aseptic state, and the waste liquid in the septic tank is treated. The mixing ratio of titanium oxide and silicon oxide in the composite oxide was determined by the present inventors through experiments. A single oxide of 100% titanium oxide may be used, but this is difficult to obtain, and its effect is reduced by even a small amount of impurities (silicon oxide). When, the effect increases. The amount of platinum supported on the composite oxide may be very small, but if it is less than 1/10000, the electron transfer does not occur. In addition, since platinum is expensive, supporting more than 5 / 10,000 is not economical.

The present invention is also characterized in that the active composite oxide has a particle size of 500 to 20 μm. According to the present invention, the particle size of the active composite oxide mixed with the FRP raw material is 500Å to 20μ, preferably 500Å to 1μ.
m. The smaller the particle size of the active composite oxide, the better, but it is not preferable to reduce the particle size to less than 500 ° C., since much power is required for pulverization. The upper limit of the particle size is determined in consideration of uniform mixing with the FRP raw material.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to embodiments.

(1) Preparation of Composite Oxide As a raw material, commercially available titanium chloride TiCl ₄ and ethoxyl silicon (C ₂ H ₅ O) ₄ Si are mixed so as to have a predetermined composition ratio, and hydrolysis is performed with dilute aqueous ammonia. Do. The resulting precipitate (hydroxide of titanium and silicon) was filtered, washed with water, dried, and calcined at about 1000 ° C. in air to obtain a titanium-silicon composite oxide powder shown in Table 1. This was immersed in a chloroplatinic-hydrochloric acid solution to cause platinum to be supported on the composite oxide to obtain an active composite oxide powder. A certain amount of the active complex oxide is filled in a glass tube having a fixed diameter, and a gas obtained by mixing propylene and water vapor at a molar ratio of 1: 1 is passed through the glass tube, and the mixture is supplied per 1 mole of titanium atom of the active complex oxide. Is obtained from the ratio of propylene and propane after the reaction, and is compared with pure titanium oxide.

[0010]

[Table 1]

It should be noted that, due to the reducing property of the active composite oxide,
Part of propylene is reduced to propane, and part of propylene becomes carbon dioxide and water due to its oxidizing property.

As is clear from Table 1, the titanium oxide supported on platinum alone has a high activity, but when a small amount of silicon oxide is mixed with the platinum, the activity is significantly reduced. It can be seen that the activity decreases most when the ratio of titanium oxide to silicon oxide is around 1: 1, and the activity increases again when the ratio of silicon oxide increases. Further, when the proportion of silicon oxide exceeds 97%, the activity sharply decreases, and the activity of silicon oxide alone becomes zero.

[0013] The activity of platinum-supported composite oxides or those having a supported amount of less than 1 / 10,000 is almost the same as in Table 1, but the degree of oxidation is incomplete and oxidized to CO ₂ and aldehydes and ketones are not obtained. Is generated. When harmful substances in the environment are decomposed and removed, it is not preferable to generate aldehydes and ketones.

From the above results, the ratio of titanium oxide to silicon oxide in the composite oxide is from 3:97 to 20:80,
Platinum supported on composite oxide in a ratio of 1 / 10,000 to 5 is used as the active composite oxide of the present invention.

As a method for producing a composite oxide, there are a chemical mixing method, a kneading method and the like in addition to the above-mentioned coprecipitation method, which may be adjusted by these methods. Further, instead of the active composite oxide, the above-mentioned semiconductor which performs a photocatalytic action of decomposing an organic substance under irradiation of light may be used.

(2) Preparation of FRP raw material FRP is obtained by dispersing fibers such as glass fiber, carbon fiber and organic fiber in a thermosetting synthetic resin such as polyester resin, epoxy resin and phenol resin, and laminating them in a plate shape. It is molded. Secondary materials such as a curing agent, a stabilizer, and a coloring agent are added to the thermosetting synthetic resin, and the thermosetting synthetic resin is cured by heating. For hollow tanks, a molded product is provided with a flange, and two or more molded products are combined with the flange and fixed with an adhesive, a bolt, or the like.

The active complex oxide prepared in (1) is added to the FRP raw material of the present invention as a part of the auxiliary material. That is, a thermosetting synthetic resin prepared by adding ethylene monomer as a curing agent (crosslinking agent) to a polyester resin powder was prepared.
According to the method of (1), titanium oxide 5% and silicon oxide 95
% Of the composite oxide was supported on the composite oxide and pulverized to obtain an active composite oxide having a particle size in the range of 500 to 10 μm. 100 parts by weight of the thermosetting synthetic resin was mixed with 7 parts by weight of the active composite oxide to impregnate the thermosetting synthetic resin raw material into glass fibers to obtain an FRP raw material.

[0018] (3) molding the FRP material obtained in septic tank fabrication (2), to obtain a septic tank upper 1 and septic tank bottom 2 shown in FIG. 1, the septic tank 3 the assembly in a volume of about 2m ³ this with bolts Made. A septic tank having a similar shape was manufactured from a conventional FRP raw material not mixed with an active complex oxide. Table 2 shows the analysis results of the water when the raw water to be purified was put into these septic tanks and left overnight.

[0019]

[Table 2]

From Table 2, it can be seen that the septic tank of the present invention has a smaller number of BOD, suspended solids, and coliform bacteria than the conventional septic tank. In particular, the BOD can be reduced to 10 mg / l or less, and this amount has little effect even if discharged directly into a river.

(4) Production of Purification Space The FRP raw material obtained in (2) was molded to produce a space A of about 1 m ³ supposed in an automobile. Further, a space B having the same shape as that of the conventional FRP raw material not mixed with the active complex oxide was produced.
There was no odor peculiar to FRP in the space A, and smoke for one cigarette was generated in the space, but this tobacco odor became almost insignificant after one hour. On the other hand, in the space B, the odor peculiar to FRP was present for about one week, and the odor due to the smoke of tobacco generated in the space was maintained for several hours.

(5) Others In the drinking water tank manufactured by the FRP of the present invention, a trace amount of organics in the drinking water stored in the tank is decomposed, so that chlorine and organic substances for disinfection are formed. There is no harmful trihalomethane and water without chlorine odor.

Titanium oxide is approved as a pharmaceutical, cosmetic, or food additive, and there is no problem in using it in a water tank. Silicon oxide has been used for a long time as ceramics and has no particular problem.

[0024]

As described above, according to the present invention, a FRP raw material is mixed with a photocatalytic semiconductor, particularly an active complex oxide, to produce an FRP molded product.
In addition to eliminating a peculiar odor, it can remove malodorous substances and bacteria near the FRP molded product.

[Brief description of the drawings]

FIG. 1 is a sectional view of a septic tank 3 made of FRP having photooxidation reactivity.

[Explanation of symbols]

 1 Septic tank upper part 2 Septic tank lower part 3 Septic tank

Claims (3)

[Claims] 1. A fiber-reinforced plastic raw material 1 comprising a semiconductor having a photocatalytic action for decomposing an organic substance under light irradiation.
A fiber-reinforced plastic molded article having photo-oxidation reactivity, wherein 3 to 10 parts by weight are mixed with respect to 00 parts by weight and molded. 2. The method according to claim 1, wherein the semiconductor is 3 to 20% by weight of titanium oxide.
And a composite oxide containing 97 to 80% by weight of silicon oxide,
2. A photo-oxidatively reactive fiber-reinforced plastic molded article according to claim 1, wherein said active oxide is an active composite oxide carrying platinum in an amount of 1 / 10,000 to 5 / 10,000 of said composite oxide. 3. The active composite oxide has a particle size of 500 ° -500 ° C.
The photo-oxidation-reactive fiber-reinforced plastic molded product according to claim 1, wherein the molded product has a thickness of 20 µm.