JP4122299B2 - A method for heating fiber-reinforced thermosetting resin. - Google Patents

Description

The present invention is a technique related to heating and heating treatment of a cured fiber reinforced thermosetting resin (hereinafter abbreviated as FRP), and can be used particularly in the technical field of volume reduction and reuse of waste FRP.

Conventional heating and heating treatments for FRP are often used as a means for reaction-curing resin (see, for example, Patent Document 1 and Patent Document 2).
Some are used for the treatment of the interlayer resin by FRP heat treatment (see, for example, Patent Document 3).
FRP warming treatment is not found in cutting, breaking, peeling, shaping, compression and volume reduction.
Currently, most of the waste FRP is disposed of in landfills by cutting or breaking, and part of it is crushed and reused as fillers for various resins. At present, reuse is studied as a raw material and fuel in pyrolysis and cement manufacturing processes.

JP 2002-307465 A (summary) JP-A-8-112860 (summary) Patent No. 2679477 (action)

However, even if FRP becomes a waste material, it has excellent durability and toughness, and the high rigidity and high strength of FRP require a large amount of power for cutting and breaking, etc. The heat from the blade of the machine is not released and it is damaged by heat. In addition, there are problems such as generation of dust due to large noise during processing such as cutting and breaking. Furthermore, when this waste FRP is disposed of by landfill by cutting or breaking, it is prescribed that the maximum diameter is not more than 15 cm, not a hollow state, which requires a great deal of power and labor.

In such waste FRP treatment, the thermosetting resin is not deteriorated and deteriorated without being dissolved or dissolved in chemicals or by overheating, and softened in a high temperature range (shown in and after Example 3). In this state, the waste FRP is cut or ruptured or peeled off the reinforcing fiber bundle or pressed and ruptured (abbreviated as rupture treatment) with a small amount of power while suppressing noise and dust. The purpose was to reduce the amount of landfill disposal as much as possible by reusing or reducing the volume of durable and tough waste FRP while maintaining the properties of thermosetting resin. . Another object of the present invention is to provide a method for heating FRP, which is used for manufacturing molded products and structures by heating and shaping FRP.

In order to achieve the above object, the FRP heating method according to claim 1 reduces the hardness and rigidity of the FRP in a state where the cured FRP is heated to a predetermined temperature at which the thermosetting resin does not deteriorate. By utilizing the phenomenon of cutting, rupture treatment such as cutting or rupture or pressure rupture, or by means of pressurizing and compressing, returning to room temperature, curing and volume-reducing solidification.

In addition, the FRP heat treatment method according to claim 2 utilizes the tensile strength of the reinforcing fiber in a softened state in which the cured FRP is heated to an appropriate high temperature range without losing the properties of the thermosetting resin. By rupturing the resin between the reinforcing fiber bundles and between the bundles, peeling the reinforcing fiber bundles and rupturing such as cutting, or compressing the ruptured product to normal temperature and curing it to reduce the volume and solidify.

Further, the FRP heating method according to claim 3 covers the whole or part of a long structure such as a waste ship and construction waste made of FRP with an airtight material such as a heat insulation sheet, and shields it from the outside air. Is heated to an appropriate temperature that does not cause deterioration and deterioration of the resin, and the rough rupture treatment such as dismantling or this rough rupture treatment piece is applied by remote control of a cutting machine or construction machine in a state where the thermosetting resin loses rigidity. By means of re-breaking treatment in a warm state or compression and returning to room temperature to cure and volume-reducing and solidifying.

In addition, the FRP warming method according to claim 4 uses a phenomenon in which the reduced volume and solidified FRP is warmed to a predetermined temperature to restore the pre-compression state. By changing and compressing, returning to normal temperature and curing, re-volume reduction solidification or by means of manufacturing a processed product.

Further, the FRP warming method according to claim 5 is based on the above-mentioned warming treatment under an inert gas and resin component atmosphere.

Further, in the FRP warming method according to claim 6, the water is sprayed in an appropriate amount to the combustion gas having a pressure higher than the atmospheric pressure, and the temperature is adjusted by using the latent heat of evaporation, and the warming is performed by the generally inert warming gas. By means.

Further, the FRP warming method according to claim 7 is based on a means for warming the cured FRP by sucking a heated gas whose temperature is lowered by a blower or the like, reheating it, and circulatingly blowing it.

  Further, the FRP warming method according to claim 8 is based on a means for heating and softening the cured FRP to break it in the presence of a high temperature liquid or a saturated liquid.

Further, the FRP heating method according to claim 9 is a method in which a hardened FRP or a cured thermosetting resin is heated to a predetermined temperature and pressure-bonded to a hard mold, and then shaped or pressure-bonded. By means of surface treatment of a pattern or the like, or processing such as embedding of an object by applying pressure, and returning to room temperature to cure and solidify.

Further, in the FRP heating method according to claim 10, a liquid resin or the like is infiltrated into the gap between the shaped article or the surface treatment or solid embedding according to claim 9 or a cured and solidified shaped article. By means of curing and producing a solid shaped product.

Further, the FRP heating method according to claim 11 is such that the hardened FRP plate and the FRP hardened to a set shape are heated and softened to a predetermined temperature, and the shape is changed by the stress within the fracture limit of the resin. This is based on the production of a molded product that is cured and solidified by returning to a predetermined temperature, and a means for producing a structure that can be joined and disassembled by assembling the molded product and heating it to a predetermined temperature to restore the shape before shaping.

That is, in the present invention, the thermosetting resin, which is considered to have no thermoplasticity, also has a softening phenomenon (referred to as a phenomenon shown in the examples) as the temperature rises, and as the temperature rises, the hardness and rigidity of the FRP decrease. In the case of a general-purpose unsaturated polyester resin, a decrease appears remarkably after approximately 70 ° C. to 100 ° C. (Experimental data indicating that the bending strength decreases to 1/10 or less depending on the characteristics of the resin and the composition of the reinforcing fiber, (It can also be found in the FRP Design Handbook issued by the Japan Association for Reinforced Plastics.) If the temperature is too high (in the case of the above-mentioned general-purpose resin, the heat-resistant temperature is about 150 ° C.), the bonding of the composition components breaks and the resin itself When the temperature is too low, the softening phenomenon cannot be sufficiently obtained.

Depending on the type of thermosetting resin that constitutes this FRP, waste FRP is ruptured or pressurized using the state that loses the hardness and high rigidity of FRP by heating to a predetermined temperature in a high temperature range that does not deteriorate and deteriorate. When the volume is reduced and the temperature is returned to room temperature with a compressive stress applied at this temperature, the material hardens (the hardness returns to room temperature, strictly speaking, the uncured part is cross-linked by heating and the hardness tends to increase). The volume is reduced and fixed (abbreviated as volume reduction and solidification) using the phenomenon of solidifying in a compressed state.

When the FRP reinforcing fiber bundle is peeled off at room temperature, it requires high power due to its high hardness and rigidity, and the reinforcing fiber bundle itself is easily broken with the resin, so an appropriate high temperature range that does not lose the properties of the thermosetting resin. Resin layer between the reinforcing fiber layers and between the bundles by applying stress in the direction in which the reinforcing fiber bundle is difficult to break (stretching direction of the reinforcing fiber) using the tensile strength of the reinforcing fiber in the softened state heated to The reinforced fiber bundle is peeled off and subjected to a rupture treatment such as cutting, and the reinforced fiber bundle and the like whose volume (apparent volume) has been increased by the rupture treatment is warmed and compressed in a softened state and subjected to stress to apply Return to volume and solidify.
The softening and melting temperature of the reinforcing fiber (glass fiber or the like) is in a higher temperature range than the general-purpose resin, and the difference from the softening temperature is large. Further, the softened state of the resin varies depending on the heating temperature, and the peeled state of the reinforcing fiber bundle changes, so that the peeled state can be adjusted according to the reuse application.

Also, when dismantling such as dismantling a large structure such as an FRP abandoned ship, transportation costs and large power are required, causing dust scattering and noise generation. Appropriate temperature of 60 ° C to 150 ° C that prevents the deterioration of this resin by heating means that covers the whole or part of the structure with a material, covers and shields the outside air, and adjusts the pressure and temperature. In a state in which the thermosetting resin (general-purpose unsaturated polyester resin) loses its rigidity after being heated to a predetermined temperature (economically, about 100 ° C., the condensation temperature of water vapor under atmospheric pressure). Disruption and other dismantling processing is performed by remote control of construction machinery. At the same time, because the heat conduction of FRP is poor, it is economical that the waste FRP pieces selected after rough rupture treatment are finely re-ruptured or compressed in the warmed state before returning to room temperature to return to room temperature and solidify. Is.

In addition, when the fractured piece of FRP with reduced volume and solidification is heated to a predetermined temperature (around 100 ° C for the above-mentioned general-purpose resin), the volume is reduced and solidified by utilizing the phenomenon that it is almost restored to the state before compression. It can be solved by re-breaking or changing the size, compressing, applying stress, returning to normal temperature and solidifying again. In addition, the FRP can be reduced in volume by heating treatment, or by utilizing this restoration phenomenon, it is possible to create various processed products by bonding and curing with a new resin or the like.

Heating and heating FRP in the presence of oxygen, such as air, may cause oxidation and ignition combustion, so the atmosphere of an inert gas (water vapor, combustion gas, etc.) or resin component is suppressed by suppressing evaporation and oxidation of the resin component. In order to prevent deterioration, heat treatment is performed in a situation where oxygen and other reaction components such as a resin component liquid and a resin component gas are as little as possible.

Moreover, temperature adjustment (especially at about 100 ° C. under atmospheric pressure) by spraying an appropriate amount of water (room temperature water to high temperature water) to combustion gas higher than atmospheric pressure, such as a burner with a blower, and utilizing the latent heat of evaporation. It is easy to stabilize the temperature), and the FRP is warmed by a generally inert warming gas (water vapor, combustion gas, a small amount of residual air, excess air, etc.).

Furthermore, the heat efficiency of FRP heating can be increased by sucking the heated gas with a reduced temperature by sucking it with a blower, etc., reheating it with combustion gas, etc., and circulating it. The heat transfer rate to the FRP can be increased.

In addition, when continuously breaking the waste FRP piece, even if the FRP is heated and loses rigidity, the heat conduction is poor and the cutting edge of the breaking device is easily damaged by heat. In the case of saturating water or high-temperature water, etc.), it is possible to remove the heat of the blade edge by using the latent heat of evaporation of the saturated liquid or high-temperature liquid to suppress damage to the blade edge. it can.

Molded by pressing and pressing a hardened FRP or thermosetting resin (breaking FRP piece, etc.) to a hard mold in a softened state heated to a predetermined temperature, or pressing and pressing to a mold pattern Surface treatment, pressurization and solid (metal, plastic, cement, wood, mineral, ceramics, etc. pressure-resistant solids) embedding and wrapping, etc. to return to room temperature and solidify to produce various shaped products To do. Furthermore, when strength is required for this shaped article, a liquid binder such as a thermosetting resin or a thermoplastic resin before curing is permeated into the gap at the time of warm shaping or the solidified shaped article is hardened (adhered). It can also be made.

In the softened state where the hardened FRP plate and the FRP hardened to the set shape according to the application are heated, the stress is changed within the rupture limit of the thermosetting resin, and the shape is changed to normal temperature to be cured and fixed (solidified. ) To produce a molded product. It is also possible to produce an assembly structure that can be joined and disassembled using the restoration phenomenon caused by heating the molded product.

Temporary softening phenomenon by heating the type of reinforcing fiber (metal, inorganic, organic, etc.) and composition (combination of fibers) or thermosetting resin (unsaturated polyester resin, epoxy resin, polyurethane resin, etc.) The cross-linked resin that is hard at room temperature is selected according to the heating temperature, and the above-mentioned molded product is produced with flexibility against the stress during molding. The above-mentioned assembled structure is manufactured by taking a large amount of deformation and deformation in the warming and softening state by forming and curing the curved play portion or notch portion.

1) Heat treatment of the waste FRP reduces the high rigidity and strength of the FRP, so the power required for the breaking process can be reduced, noise and dust generation can be suppressed, and the cutting edge of the cutting machine or breaking machine Can also reduce damage.
2) At the disposal of FRP, compress the FRP piece that has been ruptured by heating to increase the apparent specific gravity and reduce it to any size (block shape with a maximum diameter of 15 cm or less, etc.) It can solidify.
3) By heating waste FRP, it becomes possible to peel a bundle of reinforcing fibers longer than room temperature, making it easy to reuse the high strength of the reinforcing fibers.
4) The waste FRP pieces that have been ruptured can be pulverized with less power at room temperature.
5) Volume reduction and solidification can be achieved by heating the crushed FRP pieces.
6) By heating the waste FRP, the force required for bending and twisting can be reduced, and the molded product can be made and reused by shaping and the reuse rate can be increased.
7) The waste FRP piece that has been heat-treated and reduced in volume and solidified can be restored to its original state by re-heating, and it can be re-ruptured or changed in size and compressed and re-reduced and solidified.
8) Various shapes of processed products, molded products, assembled structures, etc. can be produced by using the phenomenon of shaping or restoring by heating processing of FRP.
9) Since there is no deterioration and deterioration of the waste FRP piece material, it can be reheated by molding using a new similar resin, and can be reused after being remolded.
10) The molding process can be freely performed any number of times by press-molding the reinforced fiber bundle and the like that have been subjected to the fracture treatment and the thermoplastic resin, and heating the material resin to a temperature at which the material resin does not deteriorate.
11) Heating at about 60 ° C. to 150 ° C. is sufficient, and energy cost is lower than that of thermal decomposition. Heating and breaking treatment can be carried out, and volume reduction solidification and efficient series treatment can be performed.
12) A large structure such as a waste FRP ship is shielded from the outside air with a heat insulation sheet, etc., and heated to about 100 ° C to dismantle and break with less power at the site and near the site while suppressing dust and noise. .
13) A suitable amount of hot water can be sprayed on the combustion gas such as a burner, and the temperature of the fuel can be adjusted and heated using the latent heat of evaporation. The danger of fire etc. can be avoided by processing.
14) Waste FRP with poor heat conduction can be efficiently heated by sucking, reheating and circulating the heated gas with a blower or the like.

FRP of abandoned ships, etc. is softened by heating to a predetermined temperature with a heating gas such as water vapor (refers to the phenomenon shown in the third and subsequent examples), suppresses the generation of noise and dust, and breaks with less power In addition, it is shaped and compressed in a warmed state, and it is molded and volume-reduced and solidified by returning to room temperature by applying stress, and the structure is restored to the state before applying stress by further reheating. Manufacturing and re-breaking or re-volume solidification of objects and shaped articles.

In FIG. 1, an appropriate amount of waste FRP material is put into a filling chamber 2 of a heating container 1, steam is supplied from a steam supply port 4, heated to a predetermined temperature, and slid in the direction indicated by an arrow in the figure. Waste FRP partially compressed and broken by the pressure feeding device 5 that is compressed in the pressure direction by the pressure device 3 and that is slid in the direction indicated by the arrow in the pressure feeding device 5 that rotates in the direction indicated by the arrow in the drawing. The material is ruptured to an appropriate size by a breaker 8 such as cutting rotating in the direction indicated by the arrow through the presser plate 7 and introduced into the pressure reducing chamber 10 by the guide plate 9 to be ruptured and apparent. An appropriate amount of FRP piece having an increased volume is compressed and compressed by a pressure device 11 that slides in the direction of the arrow in the figure, and then pressurized and compressed by a pressure extrusion device 12 that slides in the direction of the arrow in the figure. Then, it is returned to room temperature by the cooling means 13 and cured and fixed (volume reduction solidification), and the discharge port 14 is opened and pressed. The primary pressurizing device 3, the pressurizing feed device 5, the pressurizing device 11, the pressurizing extruding device 12, and the discharge port 14 are shown by arrows in the figure. Return to the solid line position in the direction and repeat the same process. Further, the heating and cooling chamber 10 is supplied with water vapor from the water vapor supply port 4A to adjust the heating temperature.
In addition, the FRP piece is more evenly stressed by pressurizing and compressing from the pressurizing device 11 and pressurizing and extruding device 12 of the pressurizing volume reducing chamber 10 and the other three-dimensional direction (not shown). It can be solidified.

In FIG. 2, the direction of the arrow in the figure indicates the flow of waste FRP treatment. The heating means 1a is filled with a waste FRP plate and the temperature of superheated steam is adjusted to a high temperature range that does not lose the properties of the thermosetting resin. Warming and softening, feeding and adjusting the thickness and amount by the feeding means 2a, and the abacus ball breaking means 3a composed of an abacus ball-shaped rotating roller capable of adjusting pressure and a gear-shaped rotating roller capable of adjusting pressure. A tensile treatment is applied to the longitudinal fibers and the transverse fibers of the waste FRP plate passing between the gear-shaped breaking means 4a constituted by the above, and the resin part between or between the reinforcing fiber bundles is broken and peeled to break the breaking treatment means 5a. In the same manner as in Example 1, the volume is compressed and reduced by the pressure compression means 6a, and returned to normal temperature by the cooling means 7a and cured to reduce the volume and solidified waste FRP pieces. In addition, the directions indicated by the arrows in the figure and the heating means 1a to the pressure compression means 6a are in a heated state.

A flat plate cut out from a waste FRP ship with a length of 220 mm, a width of 20 mm, and a thickness of about 5 mm is immersed in boiling water. Curing and solidifying (fixing) in this state, even if it is allowed to stand at room temperature for several days, no change in torsion is observed, and the rigidity and hardness in this state are not significantly changed from the original state. Further, the twisted FRP plate began to recover from about 60 ° C., and when it was immersed in boiling water, it recovered to a substantially flat plate shape in about 50 seconds. In addition, the thinly peeled glass fiber bundle is heated, coiled, cooled with water, solidified, and similarly restored in a short time when immersed in boiling water. Present. Further, when the waste FRP is heated to about 100 ° C., it can be cut with a cutter knife, and when about 140 ° C., a waste FRP plate having a width of 20 mm and a thickness of about 5 mm can be cut.

FRP pieces that have been fractured are packed into a metal pipe with an inner diameter of 32 mm, heated to about 100 ° C., applied to a metal shaft with a diameter of 30 mm with a weight of about 60 kg (588 N), pressurized and compressed to return to room temperature and solidified. When taken out and measured, the volume is reduced and solidified with an apparent specific gravity (weight of FRP piece / solidification volume) of about 0.9. Further, when this solidified state is heated to about 100 ° C., the FRP pieces are almost restored to the state before compression, the solidified state is dissolved, and the expanded state is dismantled and the original shape (volume-reduced solidified state) is not retained.

General-purpose marine unsaturated polyester resin (Hitachi Polyset NR2907PT-S production number B30073.) Curing agent (Nippon Yushi Permek N production number 2501) 1% (Nittobo Glass Fiber.) Matt M450, Cross R570, FRP ship The FRP (hereinafter abbreviated as 2907 · MR) flat plate, which has been defoamed with an iron roller to M + R + M + R + M, which is the main composition of glass fiber, and laminated and cured at a room temperature of about 3 mm at room temperature (23 ° C.) (hereinafter abbreviated as 2907 · MR. A pressure test piece trimmed to a length of 0.5 mm and a length of 100 mm is placed on a metal pipe with an inner diameter of 30 mm, and the upper and lower ends are inclined (inclination of about 13 degrees from the vertical). The maximum hydraulic pressure, which is obtained by subtracting the piston resistance until it is damaged by applying a hydraulic piston (diameter 35mm) in a vertical direction with a 2mm metal shaft, is 2.5MPa. When measured with a pressure gauge of the manufacturing number 3015203 of the megapascal range, the average pressure at room temperature (24 ° C.) is about 2.32 MPa, and breaks at about 1/3 of the test piece, 100 ° C. (about 10 minutes in boiling water) When heated to 0.35 MPa, it was whitened and bent from the center. As a result, the failure stress is reduced to 1/6 or less.

A 3.3 mm thick FRP (hereinafter abbreviated as 2907 · 5M) flat plate obtained by laminating and curing in the same manner as described above to M + M + M + M + M with the mat M450 in order to ensure isotropic glass fiber composition with the general-purpose unsaturated polyester resin. When the maximum hydraulic pressure was measured in the same way with the above-mentioned dimension pressurization test piece, it broke at about 1/3 of the average at 2.44 MPa at normal temperature (21 ° C.), 0.33 MPa at 100 ° C. did.

Since the fracture treatment by shearing is considered to be the mainstream, the 2907 · MR plate of Example 5 was cut to 115 mm length and 15.5 mm width and inclined, and the middle part was provided with medium details of 12.5 mm width and 50 mm length One end is fixed with a twisted torsion test piece, a torque wrench (T3FN6 manufactured by Maeda Metals Co., Ltd.) and a rotation angle meter are attached to the free end, and a 86 mm span (fixed end to free end of the test piece from the fixed end to the free end) When measuring the maximum torque (referred to as the moment of force) torsional breakage and breakage in space length), it emits a high tone at a position rotated by 180 degrees at room temperature 23 ° C, and is centered at 3.5 N · m (Newton meter). When heated to 100 ° C. (boiling water) where the part was diagonally broken, it showed 0.5 N · m at a position rotated by 180 ° to 190 °, and whitening broke with the center portion twisted. To confirm the sound at the time of breakage, when it is pulled up in the air and twisted to about 190 degrees, the torsional breakage maximum torque that is whitened and damaged by whitening is reduced to about 1/7 by heating to 100 ° C.
At 70 ° C in warm water, the center was twisted at 2.0 N · m at 80 ° C, 1.4 N · m at 90 ° C, 0.7 N · m at 90 ° C, and 0.3 N · m at 150 ° C (in vegetable oil). (The waste FRP ships etc. are considered to be safe and economical to heat at about 90-100 ° C).
Further, in the above-described dimensional torsion test of the 2907 / 5M plate of Example 5 , the average value of 4.05 N · m was shown at a position rotated by 50 ° to 60 ° at room temperature of 18 ° C., and the position gradually decreased and rotated by 90 °. The torsional breakage maximum torque that broke at 100 ° C (boiling water) at 150 ° C to 170 ° and showed an average maximum value of 0.53 N · m at the position rotated at 150 ° C to 170 ° C. Is also reduced to 1/7 or less.
When heated at 70 ° C in warm water, it is 2.1 N · m at a position rotated by 160 ° to 180 °, 1.3 N · m at 80 ° C, 0.8 N · m at 90 ° C, and whitening with the center part twisted. Damaged.

Furthermore, the above-mentioned 2907-5M (normal temperature curing) torsion test piece and the recured test piece obtained by re-curing the test piece in vegetable oil at about 130 ° C. for about 2 hours at 60 ° C., 70 ° C., 80 ° C. in warm water Table 1 shows a comparison of torque N · m (moment of force) corresponding to torsion angles up to 90 ° C and 100 ° C.
The upper part shows the torque at room temperature 20 ° C. and the maximum torque damaged at the tail of the room temperature cured test piece. However, one test piece was used for each temperature, and the heating time until breakage took about 10 minutes.

It can be inferred from Table 1 that the unsaturated polyester resin (thermosetting resin) is heated and uncured (unsaturated) sites are cured and cured, and the rigidity is chemically increased.
It can also be seen that the rigidity of the resin cured at room temperature and the resin cured by crosslinking and recuring are greatly reduced by raising the heating temperature.

Furthermore, both of the above (2907 · 5M and · MR) torsion test pieces were heated to 100 ° C. (boiling water), twisted by 120 degrees, returned to room temperature (cooled in water), and twisted by 115 degrees. When it was heated again to 100 ° C., it was restored to a twisted state of 2 to 4 degrees.

General-purpose marine unsaturated polyester resin (Hitachi Polyset 2915PT-L Production No. G30293) Curing agent (Nippon Yushi Permek N Production No. 2501) 1% is laminated and cured to 5M at room temperature (30 ° C) as in Example 6. 3.9 mm thick FRP (abbreviated as 2915 / 5M) after 4 months. The above-mentioned dimensional torsion test piece has an average maximum of 5.75 N · m at a position rotated about 50 degrees at room temperature (18 ° C). The value was shown and the center fractured at a position rotated about 80 degrees. At 100 ° C. (boiling water), the average rotated 0.95 Nm at a position rotated about 150 degrees to 170 degrees and whitened and damaged in a state where the center portion was twisted.
At 70 ° C in warm water, it was 3.2 N · m at 80 ° C, 2.4 N · m at 90 ° C, and 1.3 N · m at 90 ° C. When heated to about 150 ° C. (in vegetable oil), whitening breakage occurred at 0.4 N · m.
Also, when heated to 100 ° C. (boiling water) and returned to room temperature (twisted by water) after being twisted by 120 degrees, it solidifies (hardens) at a twist of about 112 degrees, and when heated to 100 ° C. again, it is 3 degrees. Restored to a twisted state of ~ 4 degrees.

Furthermore, in order to avoid the heat of curing at 2915.5M, the FRP (M.10) flat plate with a thickness of 7.3 mm, which was left for about 3 hours with the same resin and mat and further cured for 5 months with a thickness of 4 months, was 115 mm wide and 15 mm wide. A torsional test piece with a trimming slope of 0.5 mm and a center of 7.3 mm wide and 50 mm long details (7.3 x 7.3 mm) is 4.5 N · m at room temperature (18 ° C). The test piece was damaged at 2.2 N · m at 70 ° C, 1.5 N · m at 80 ° C, 1.0 N · m at 90 ° C, and 0.9 N · m at 100 ° C. There has occurred.

In addition, a three-component gel coat made by a fellow (64.5% unsaturated polyester resin, 12.3% titanium oxide, 13.6% styrene monomer, 7.9% extender pigment, other thickener), cobalt naphthenate 0 Cured at room temperature to a thickness of 3.3 mm (abbreviated as gel coat 5M) with the above 5M glass fiber composition with 1.2% of the curing agent and the maximum breaking torque of the torsion test piece having the above dimensions. On average, at normal temperature, the sound was emitted at a position rotated about 60 ° at 4.8 N · m, and the center was broken diagonally. When heated to 100 ° C (boiling water), the center was broken at a location rotated about 2.2 N · m 70 °. did.
Moreover, when it heated to about 150 degreeC in vegetable oil, it peeled and broke in the state twisted in the position rotated about 70 to 80 degree | times at 0.8 N * m.
Further, when heated to 100 ° C. (boiling water) and returned to room temperature after being twisted by 70 degrees (cooled with water), it is solidified while being twisted by about 60 degrees (solidifies). When heated to 100 ° C. again, it is 7 degrees. It was restored to a twisted state.

As described above, the rigidity of the general-purpose resin varies depending on the type and the curing conditions, and it can be seen that the rigidity is greatly varied depending on the heating temperature, and the rigidity is lowered when the temperature is increased.

A glass cloth 11-ply reinforced epoxy resin substrate with a thickness of 3.1 mm (abbreviated as G epoch) and a torsional test piece with the above dimensions shows a torque of 6.5 N · m when twisted 180 degrees at a room temperature of 27 ° C. When the angle was kept at about 180 °, it decreased to 5.0 N · m, indicating the behavior of a viscoelastic body, and even after releasing this torsional stress and leaving it for several days, it showed a residual strain of about 60 °. Also, when this test piece is heated to 100 ° C, the strain is restored to about 8 degrees, and when it is twisted to 180 degrees, the torque is 1.2 N · m, and when it is twisted 360 degrees, whitening peeling damage occurs with the center portion twisted. The maximum torque at this time was 1.8 N · m.
When another torsion test piece with the above dimensions is heated to about 150 ° C in vegetable oil and twisted 180 degrees, it shows 0.6 N · m, and when it is twisted 360 degrees, the center part is twisted and whitening peels and breaks. The maximum torque is 0.7 N · m was indicated.
In addition, when another dimensional torsion test piece is heated to about 150 ° C. in vegetable oil and returned to room temperature after being twisted by 120 degrees, it is solidified (set) by twisting by about 115 degrees. When this twisted state was heated again to 150 ° C., it was restored to a twisted state of about 4 degrees.

In the twisted test piece of the above dimensions with a single plate made of phenolic resin (thickness 3.1 mm power distribution board without reinforcing fiber), an average of 3.05 N · m at a position twisted at 70 ° C. to 75 ° C. at ambient temperature of 21 ° C. A high-pitched tone was emitted and the film was peeled diagonally from the center, and when heated to 100 ° C in vegetable oil, it showed an average of 1.30 N · m at a position twisted 70 degrees, and an average of 1.60 N · m at a position twisted 110 degrees At about 150 ° C, it was broken by 70 degrees and showed an average of 0.5 N · m. At 110 degrees, it showed 0.7 N · m, and at 200 degrees, it showed 1.0 N · m. .
When the torsion test piece is heated to 150 ° C. and twisted to 120 ° C. and returned to room temperature (water-cooled), it solidifies (sets) in a twisted state of about 110 °. When this twisted test piece was heated again to 150 ° C., it was restored to a twisted state of about 35 degrees.
In addition, the above-mentioned torsional test piece on another distribution board of the same shape and thickness is 2.9 N · m at room temperature of 20 ° C, 1.6 N · m at 100 ° C in vegetable oil, and 1.1 N · m at 150 ° C. All were damaged at a twisted position of 70 to 80 degrees. There is no big difference in breaking torque, but because of the use of no reinforcing fiber, a difference in curing conditions, or a big difference in breaking torsion angle. When this test piece is heated to 150 ° C. and returned to normal temperature by 70 degrees, it is about 62 degrees. When it was solidified and heated again to 150 ° C., it was restored to a twisted state of about 15 degrees.

As in Example 4 , when a FRP piece fractured into a metal pipe with an inner diameter of 30 mm was packed and heated to 100 ° C., a solid piston with a diameter of 28.2 mm was subjected to a load of about 3000 N with a hydraulic piston, returned to room temperature and solidified. The volume can be reduced to an apparent specific gravity of 1.2. Similarly, the volume could be reduced to a specific gravity of about 1.35 at a load of about 10,000 N. Further, the FRP powder collected by the dust collector is similarly solidified with an apparent specific gravity of about 1.23 when pressurized with 3000 N.
Also, urethane foam (FRP core material) diameter 30mm, height 80mm, weight 5g is packed into the above metal pipe and heated to about 100 ° C, and the metal shaft is driven to about 3000N by a hydraulic piston and returned to room temperature. (Thickness) 6.6 mm The volume can be reduced and solidified to an apparent specific gravity of about 1.07, and the volume is reduced and solidified to about 1/12.
In addition, when the temperature was reheated to 100 ° C., the volume-reduced solidified state was melted and expanded to restore the original state.

The FRP test piece and the thermosetting resin single piece (phenol substrate) were subjected to a constant load of about 187.23 kgf ( 1836.1 N. ) on a bearing steel ball of 7.9 mm with a hardness of 100 ° C. ( Brinell hardness P / D ² = 3.) The indentation diameter is shown in Table 2 in mm. However, the diameter was measured using a magnifying glass and a vernier caliper when a load was applied to the mirror surface at room temperature for about 5 minutes, and at 100 ° C. for about 10 minutes. . Re-curing is a test piece obtained by heating a room-temperature-curing test piece at 140 ° C. for about 2 hours and re-curing it. Further, 2915 · MR is a test piece in which the glass fiber constitution is M + R + M + R + M as in 2915 · 5M.

From Table 1 and Table 2, it can be seen that the thermosetting resin is also chemically cured by heating, and that the resin recured by increasing the heating temperature has greatly reduced hardness and rigidity. In the present invention, this phenomenon is expressed as softening.

1) coarse waste FRP caused by processing of waste FRP boats by increasing the capacity of such heating container 1 and the primary pressing device 3 and pressure圧送Ri device 5 also becomes possible to process heating.
2) It can be pressurized and compressed by the apparatus up to the heating container 1, the primary pressurizing device 3, and the pressurizing and feeding device 5 to return to room temperature and solidify.
3) By pressurizing and compressing from the primary pressurizing device 3, the pressurizing and feeding device 5 and the other three-dimensional direction, the waste FRP can be evenly stressed and volume-reduced and solidified.
4) The waste FRP which has been roughly ruptured and reduced in volume in Example 1, etc., can be stored, transported, etc., reheated and finely broken in Example 2, etc. to be reused.
5) A veneer cut from FRP ship or building FRP waste material is heated to about 100 ° C, and the stress within the fracture limit of the resin is applied to the entire veneer, shaped back to room temperature, solidified, and reused at room temperature. it can.
6) Cover general-purpose thermosetting resin products such as long waste FRP ships with heat-insulating sheets, etc., and heat them to about 100 ° C to reduce dust and noise with less than 1/6 power compared to room temperature fracture treatment. By dismantling and rupturing on-site, it is possible to reduce the cost of scrapping ships.
7) Workpieces and structures can be manufactured using the molding and restoration phenomenon caused by heating the FRP.

It is a cross-sectional explanatory drawing of a heating processing method. Example 1 It is flow explanatory drawing of a heating process method. (Example 2)

Explanation of symbols

1: Heating container 2: Filling chamber
3: Primary pressure device 4, 4A: Water vapor supply port 5: Pressure feed device 6: Pressure adjusting roller 7: Presser plate 8: Breaking device 9: Guide plate 10: Pressure reduction chamber 11: Pressure device 12: Pressurizing and extruding device 13: Cooling means 14: Discharge port 1a: Heating means 2a: Feeding means 3a: Abacus ball breaking means 4a: Gear-like breaking means 5a: Breaking treatment means 6a: Pressure compression means 7a: Cooling means

Claims (3)

Cover all or part of a long structure such as waste ship and construction waste made of fiber-reinforced thermosetting resin of general-purpose unsaturated polyester resin with an airtight material such as a heat insulating sheet, and shield this structure from the outside air. in a state where the binding composition component 60 ° C. ~ heat resistant temperature of 0.99 ° C. thermoset at a constant temperature of keeping the nature of the resin warmed thermosetting resin resin itself is not altered degrade off-deleted rigidity Roughly ruptured with a cutting machine or construction machine, or this ruptured piece is finely re-ruptured in the heated state of the above-mentioned temperature, compressed and reduced in volume, and cured by returning to room temperature while applying compression stress to reduce volume and solidify A method for heating a fiber-reinforced thermosetting resin, characterized by comprising:
The claim 1 volume reduction solidified fiber reinforced thermosetting resin while applying a compressive stress according storage or transportation to by restored to the state before heating compression to a predetermined temperature according to the first aspect volume reduction solve the solidified state, the re-breaking process or any size claim 1 Symbol placement of fiber reinforced thermosetting resin, characterized in that re-reduced in volume and solidified back to room temperature and compressed into block-like warming Processing method.
Claim, characterized in that more heating process to the pressurizing Yutakaga scan inert atmosphere to adjust the temperature by using the latent heat of appropriate amount sprayed water into high-pressure combustion gas from the atmospheric pressure evaporation 1 or claim 2 heating treatment method of the serial mounting of the fiber-reinforced thermosetting resin.

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