JP2010234658A - Method of manufacturing composite container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a composite container which has a desired shape and a desired strength, and to provide a manufacturing apparatus for the composite container. <P>SOLUTION: A resin of a tow prepreg 20 is heated by a heating apparatus 6 before the tow prepreg 20 is wound on a liner 5, and the viscosity of the resin is lowered in advance more than the viscosity before the heating. Then, the resin of the tow prepreg 20 is cooled while winding the tow prepreg 20 on the liner, and the viscosity of the resin which has been lowered is raised again. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method of manufacturing a composite container that stores high-pressure gas or liquid.

  Conventionally, composite materials using glass fibers, carbon fibers, aromatic polyamide fibers, etc. as reinforcements and epoxy resins, unsaturated polyester resins, vinyl ester resins, etc. as matrix resins have been widely used for sports equipment and automobile parts. Yes.

  As a method for producing a composite material, a method is widely adopted in which a fiber reinforced material is impregnated with an uncured matrix resin to form a prepreg, and the prepreg is molded and cured. On the other hand, a hollow material forming method using FW, a so-called FW method, is also widely used as a method for producing a composite material.

  In the FW (filament winding) method, a strand prepreg impregnated with a thermosetting resin matrix is prepared in advance, and this is wound around a mandrel (Dry FW method), while the strand is impregnated with a low-viscosity resin, It is widely known that there is a method (Wet FW method) in which a mandrel is wound around and formed. Furthermore, the Wet FW method is classified into a kiss touch method, a dipping method, and other methods depending on the type of method in which the strand is impregnated with the low viscosity resin.

  FIG. 1 shows a schematic conceptual diagram of an example of a manufacturing apparatus for a tank having a resin bath used in the Wet method.

  The manufacturing apparatus shown in FIG. 1 impregnates a supply roll 101 in which a tow of carbon fiber or the like is wound, a resin bath 103 in which a resin 102 is stored, a rotary roll 104 that is rotatably provided in the resin bath 103, and a resin. And a liner 105 for winding a tow and forming a tank.

  Tows supplied from a plurality of supply rolls 101 are guided into the resin bus 103. The carbon fibers in the resin bath 103 are impregnated with resin while being guided along the periphery of the rotary roll 104. Excess resin is squeezed out by the resin content adjusting roll 106, and the resin content is adjusted. The tow whose resin content has been adjusted is wound around the liner 105 while the tension at the time of winding is adjusted by the winding tension adjusting unit 107.

  However, in the resin bath method, after the tow is passed through the resin bath 103 and impregnated with resin, excess resin is squeezed out by the resin content adjusting roll 106 to adjust the resin content, and friction with the tow occurs. Damage to the tow accompanied by cutting and fluffing occurs. Moreover, since resin content is adjusted by squeezing out resin, it is difficult to adjust resin content with high precision.

  Moreover, since the resin bath method allows the tow to pass directly through the resin bath 103, there is a problem that the inside of the resin bath 103 is fouled by fuzz or the like.

  Furthermore, the resin accommodated in the resin bath 103 has a low viscosity of, for example, about 0.1 Pa · s at room temperature. If the rotating roll 104 is rotated at high speed in such a low-viscosity resin, the resin is scattered, and therefore the rotation speed of the rotating roll 104 is limited. In addition, since a low-viscosity resin is used, the tow wound around the liner 105 is in a slippery state. In particular, when the shape of the end portion of the liner 105 is a dome shape, the tow slips easily and it is difficult to obtain a desired thickness or shape. If it does so, since intensity | strength will run short in a liner edge part, in order to ensure intensity | strength, it was necessary to wind the tow | toe extra. Further, in the Wet method, it is necessary to repeat control such that the apparatus is temporarily stopped and the resin is hardened and the apparatus is driven again when solidified in order to obtain a desired shape of the molded product. For these reasons, it is difficult to improve the productivity of the Wet method.

  In the resin bath method, a highly reactive resin is often used, so that the curing reaction gradually proceeds at room temperature, and the resin viscosity tends to increase during winding. Such a change in viscosity affects the amount of resin pick-up, and as a result, the uniformity of the resin content is impaired.

  In this way, molded products manufactured by the resin bath method have low quality stability due to the difficulty of maintaining a constant weight ratio between fiber and resin, and to prevent damage caused by tow friction. There are problems such as high manufacturing costs due to low production speed.

  Therefore, a so-called Dry method in which FW is performed using a tow prepreg impregnated with a resin in advance may be used. FIG. 2 shows a schematic conceptual diagram of an example of a tank manufacturing apparatus using a tow prepreg. Here, the “tow prepreg” means a fiber bundle impregnated with a resin to be in a semi-cured state.

  The manufacturing apparatus shown in FIG. 2 includes a supply roll 201 around which a tow prepreg is wound, a winding tension adjusting unit 207, and a liner 205 that forms a tank.

  Since the tow prepreg supplied from the supply roll 201 is already impregnated with resin, the tow prepreg is wound around the liner 205 while adjusting the winding tension by the winding tension adjusting unit 207 without passing through the resin bath. At the time of winding the tow prepreg around the liner 205, the tow prepreg is cured by heating the tow prepreg from the outside of the liner 205. In addition, the viscosity of the resin impregnated in the tow prepreg is about 5 Pa · s to 100 Pa · s at the supply roll 201 portion, and is about 10 Pa · s at the time of winding around the liner 205, compared to the Wet method tow. High viscosity.

  According to the Dry method using a tow prepreg, the problems of the Wet method are solved. That is, according to this method, it is possible to increase the accuracy of the amount of resin contained, and tow damage that occurs when the resin is squeezed out, such as yarn breakage and fluffing, does not occur. In addition, since no resin bath is used, there is no limitation on productivity improvement due to the contamination of the resin bath and the viscosity of the resin.

  On the other hand, with respect to the problem of fiber slip, Patent Document 1 and Patent Document 2 provide a step-like or streak-like structure at the end (dome) of the liner to prevent fiber slip. Yes. Patent Document 3 discloses a method of solidifying a resin after fixing a filament using photopolymerization.

JP-A-8-219390 JP 2000-106142 A JP 2005-324456 A

  However, in the case of the invention disclosed in Patent Document 1 or Patent Document 2 in which a structure is provided at the end of the liner, the liner body must be processed.

  In addition, in the case of the invention disclosed in Patent Document 3, it is necessary to add a substance that generates radicals by light in the resin, and such a substance that reacts with light causes the deterioration of the resin during long-term use. It can be.

  In the case of the invention disclosed in Patent Document 4, the apparatus and the program become complicated.

  As described above, the inventions disclosed in each of the above-mentioned patent documents are considered to be highly effective in that they can suppress toe slip, but are still not sufficient in terms of simply manufacturing a composite container. I can't say that.

  The bundle of fibers in the tow prepreg has a substantially circular cross-sectional shape. In the conventional DRY method, even when such a tow prepreg is wound around the liner, the fiber bundle of the tow prepreg remains circular without spreading each fiber. This is because the fiber bundle was difficult to be deformed because the resin of the tow prepreg used in the conventional DRY method had a relatively high viscosity. When the fibers are wound around the liner without spreading, there is a problem that voids are easily generated in the fibers and the resin layer, and the strength as a composite container is difficult to be exhibited.

  Then, an object of this invention is to provide the manufacturing method of the composite container which can manufacture the composite container which has a desired shape and intensity | strength simply.

  In order to achieve the above object, the method for manufacturing a composite container according to the present invention is a method for manufacturing a composite container in which a fiber pre-impregnated with a thermosetting resin is wound around a liner to manufacture a composite container. A heating process in which the resin is heated before the fiber is wound around the liner and the viscosity of the resin is lowered below the viscosity before the heating, and after the heating process, while the fiber is wound around the liner A cooling step of cooling the resin and increasing the viscosity of the resin lowered in the heating step.

  In the production method of the present invention, the viscosity of the resin impregnated in the fiber is reduced by heating the fiber before winding it on the liner. For this reason, at the moment when the resin is wound around the liner, the viscosity of the resin is lowered, so that the fibers are easily spread. That is, air bubbles existing between the fibers and in the resin are removed by spreading the fibers and reducing the viscosity of the resin to increase the fluidity. As a result, it is possible to obtain a composite container having a sufficient strength without a void.

  Furthermore, the manufacturing method of this invention raises resin viscosity again by cooling resin, winding a fiber around a liner. This prevents the fiber from slipping and allows the composite container to be formed into a desired shape.

  According to the present invention, a composite container having a desired shape and strength can be easily produced.

It is a typical conceptual diagram of an example of the manufacturing apparatus of the tank which has a resin bath used for the Wet method. It is a schematic conceptual diagram of an example of the manufacturing apparatus of the tank using a tow prepreg. It is a typical conceptual diagram of the manufacturing apparatus of the composite container which concerns on one Embodiment of this invention. It is a figure which shows the manufacture flow of the manufacturing method of the composite container which concerns on one Embodiment of this invention.

  FIG. 3 is a schematic diagram for explaining a manufacturing apparatus used in the method for manufacturing a composite container according to the present embodiment.

  The manufacturing apparatus 10 of the present embodiment includes a supply unit 1, a winding tension adjustment unit 2, a speed sensor pulley 3, a delivery eye 4, a liner 5, a heating device 6, a cooling device 7, and a control unit 8. Have

  The supply unit 1 is a device that supplies the tow prepreg 20 and includes a plurality of supply rolls 11 around which the tow prepreg 20 is wound. The tow prepreg 20 wound around the supply roll 11 is held in a state of maintaining a viscosity of 5 Pa · s to 100 Pa · s, preferably 7 Pa · s to 50 Pa · s.

  The tow prepreg 20 laminated and wound around the supply roll 11 may be wound with a reduced amount of the thermosetting resin impregnated from the inner layer toward the outer layer. By doing in this way, the tow prepreg 20 laminated and wound on the liner 5 is wound in a state where the amount of impregnation of the thermosetting resin is increased from the inner layer to the outer layer.

  The supply speed of the tow prepreg 20 from the supply unit 1 is controlled by the control unit 8. In addition, although the supply part 1 in this embodiment demonstrates to an example the system by which the tow prepreg already manufactured is supplied in the state wound by the supply roll 11, this invention is not limited to this. For example, the supply unit 1 may employ a method in which a tow prepreg is manufactured by supplying resin to the tow and the manufactured tow prepreg is supplied.

  The winding tension adjusting unit 2 and the speed sensor pulley 3 are disposed between the supply unit 1 and the liner 5. The winding tension adjusting unit 2 is configured to apply a required winding tension to the tow prepreg 20 wound around the liner 5, and the winding tension applied by the control unit 8 is controlled. The speed sensor pulley 3 is a speed sensor that senses the linear speed of the tow prepreg 20. The linear velocity of the tow prepreg 20 detected by the velocity sensor pulley 3 is transmitted to the control unit 8 from a signal transmitter (not shown). The control unit 8 controls the supply speed of the tow prepreg 20 from the supply unit 1 based on the signal from the signal transmitter. That is, the linear velocity of the tow prepreg 20 is always measured by the velocity sensor pulley 3 and fed back to the control unit 8 from the signal transmitter in real time. For example, when the velocity drops when the delivery eye 4 is turned back, or Even when the diameter of the winding molded body changes from the start of winding to the end of winding, the amount of resin supply is controlled, and the amount of resin impregnation with respect to the tow is controlled to be constant throughout the FW molding.

  The delivery eye 4 is a device that focuses the tow prepreg 20 supplied from the supply unit 1 and winds the tow prepreg 20 around the liner 5 by FW, and is provided so as to be reciprocally movable in a direction parallel to the axial direction of the liner 5. The orientation angle of the tow prepreg 20 is determined by the ratio of the rotational speed of the liner 5 and the moving speed of the delivery eye 4. The moving speed of the delivery eye 4 is controlled by the control unit 8.

  The material of the liner 5 around which the tow prepreg 20 is wound is selected from resin and metal depending on the application. As a resin liner, a resin liner formed with a thermoplastic resin such as high-density polyethylene formed into a container shape by rotational molding or blow molding is generally used. A metal liner is generally provided with a die shape after being shaped into a container shape by spinning or the like from a pipe shape or plate shape made of aluminum alloy, steel, or the like.

  The liner 5 is rotationally driven by a driving device (not shown). The tow prepreg 20 that has passed through the delivery eye 4 is wound around the outer peripheral surface of the liner 5 by FW.

  The heating device 6 is a heater for heating the tow prepreg 20 immediately before being wound around the outer peripheral surface of the liner 5 to reduce the viscosity of the resin, and the temperature of the heating device 6 is controlled by the control unit 8. The The heating device 6 heats the resin of the tow prepreg 20 so that the temperature of the resin is 50 ° C to 100 ° C, more preferably 60 ° C to 90 ° C. That is, the heating device 6 heats the tow prepreg 20 at a temperature at which the resin of the tow prepreg 20 does not instantaneously cure, although the viscosity of the resin is reduced.

  The cooling device 7 is heated by the heating device 6 and cools the tow prepreg 20 by blowing cooling air onto the tow prepreg 20 immediately after being wound around the liner 5. The tow prepreg 20 is heated by the heating device 6 before being wound around the liner 5, so that the viscosity of the resin is lower than that before the heating. The cooling device 7 is used to increase the viscosity again by cooling the resin whose viscosity has decreased. The temperature control of the cooling device 7 and the control of the air volume are performed by the control unit 8, and the temperature of the cooling air is controlled to be 40 ° C. or lower, preferably 35 ° C. or lower.

  As described above, the control unit 8 drives and controls the supply unit 1, the winding tension adjusting unit 2, the delivery eye 4, the liner 5, the heating device 6, the cooling device 7, and the like.

  The thermal characteristics of the thermosetting resin used in the tow prepreg 20 of the present embodiment are such that the viscosity is 5 Pa · s to 100 Pa · s at 25 ° C., and the viscosity is 0.1 Pa · s to 1.2 Pa · s at 80 ° C. It is. In addition, when the viscosity of the thermosetting resin is less than 5 Pa · s at 25 ° C., the fibers cannot be bundled. When the viscosity exceeds 100 Pa · s, the thermosetting resin of the layer before being wound around the liner 5 Adhesion worsens and cannot be used for FW. Further, when the viscosity is less than 0.1 Pa · s at 80 ° C., there is a problem that the thermosetting resin flows, and when it exceeds 1.2 Pa · s, there is a disadvantage that the fibers are difficult to spread.

  Examples of the thermosetting resin of the tow prepreg 20 of this embodiment include phenol resin, urea resin, unsaturated polyester resin, vinyl ester resin, polyimide resin, bismaleimide resin, polyimide resin, polyurethane resin, diallyl phthalate resin, epoxy Examples of the resin include, but are not limited to, resin.

  As the molecular structure of the thermosetting resin, for example, in the case of epoxy resin, bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc. Can be mentioned.

  Examples of the curing agent to be added to the thermosetting resin include aliphatic amines such as ethylenediamine, aliphatic polyamines such as diethylenetriamine, aromatic amines such as metaphenylenediamine or diaminodiphenylsulfone, piperidine or diazapicycloundecene. And acid anhydride curing agents such as primary and tertiary amines and methyltetrahydrophthalic anhydride.

  Examples of the fiber used in the tow prepreg 20 of the present invention include carbon fiber, glass fiber, aramid fiber, boron fiber, polyethylene fiber, steel fiber, zylon fiber, vinylon fiber, etc., but particularly high strength, High elastic modulus and lightweight carbon fiber is preferable.

  The number of fibers (filaments) used in the tow prepreg 20 of the present invention is not particularly limited, but is in the range of 1000 filaments to 50000 filaments, preferably 3000 filaments to 30000 filaments. When the number of fibers is lower than 1000 filaments, the content of the thermosetting resin contained in the fibers may be reduced. When the number exceeds 50000 filaments, the fibers become thick and difficult to wind.

  Next, the manufacturing method of the composite container concerning this embodiment is demonstrated using FIG. FIG. 4 is a diagram showing a manufacturing flow of the manufacturing method of the present embodiment.

  First, the tow prepreg 20 of the supply unit 1 is supplied to the winding tension adjusting unit 2 (step S1).

  Subsequently, the tow prepreg 20 is focused by being supplied to the delivery eye 4 while adjusting the tension by the winding tension adjusting unit 2 (step S2).

  Next, the heating device 6 heats the resin of the tow prepreg 20 immediately before being wound around the liner 5 to 50 to 100 ° C., preferably 60 to 90 ° C. ( Step S3).

  The delivery eye 4 reciprocates in the direction parallel to the axial direction of the liner 5 and supplies the tow prepreg 20 to the liner 5 that is rotationally driven, whereby the tow prepreg 20 is wound around the liner 5 ( Step S4).

  Next, the resin of the tow prepreg 20 immediately after being wound around the liner 5 is cooled by the cooling air blown from the cooling device 7 (step S5). That is, the manufacturing apparatus 10 of the present invention again increases the viscosity of the resin that is lowered by the heating of the heating device 6 by cooling the resin of the tow prepreg 20 while winding the tow prepreg 20 around the liner 5. The controller 8 controls the temperature of the cooling air to 40 ° C. or lower, preferably 35 ° C. or lower.

  Next, the thermosetting resin is cured by heating the tow prepreg 20 with a heating device for thermosetting (not shown) (step S6). The curing conditions are not particularly limited. For example, the temperature is raised from room temperature to 150 ° C. at 1 ° C./min, heated for 1 hour, and then cooled to room temperature.

  As described above, in the present embodiment, the tow prepreg 20 is heated by the heating device 6 before being wound around the liner 5. For this reason, at the moment when the tow prepreg 20 is wound around the liner 5, the viscosity of the thermosetting resin of the tow prepreg 20 is lower than that before heating, that is, at room temperature. That is, the tow prepreg 20 is wound in a state in which a bundle of fibers tends to spread on the liner 5. In addition, the resin of the tow prepreg 20 having improved fluidity is in a state of easily penetrating between the tow prepregs 20, and bubbles existing between the fibers and in the resin are removed, and the adhesion between the tow prepregs 20 is improved. Enhanced. As a result, for this reason, it can be set as the composite container which has sufficient intensity | strength in which the space | gap is not formed.

  Further, the tow prepreg 20 whose resin viscosity has been reduced by heating is cooled by cooling air from the cooling device 7 while being wound around the liner 5. Since the viscosity of the resin is increased again by cooling the resin, the tow prepreg 20 becomes difficult to slip. As a result, the composite container can be formed into a desired shape.

  When the supply unit 1 is on the upstream side and the liner 5 is on the downstream side, in FIG. 3, the heating device 6 is illustrated as being disposed on the downstream side of the delivery eye 4. It is not limited to this. That is, the heating by the heating device 6 heats the resin of the tow prepreg 20 immediately before being wound around the liner 5 to heat the resin of the tow prepreg 20 to 50 to 100 ° C., preferably 60 to 90 ° C. As long as the viscosity is reduced, the heating device 6 may be disposed at any position. Therefore, the heating device 6 may be disposed on the upstream side of the delivery eye 4.

  In this example, a composite container was manufactured by the method for manufacturing a composite container of the present invention under the following conditions.

  As the resin to be impregnated with tow, 90 parts by weight of bisphenol A type epoxy resin, 10 parts by weight of phenol novolac type epoxy resin, 18 parts by weight of dicyandiamide and 9 parts by weight of 3- (3,4-dichlorophenyl) -1,1-dimethylurea Were mixed. The viscosity of this resin composition was 80 Pa · s at 25 ° C. and 0.3 Pa · s at 80 ° C. While this resin composition was heated to 50 ° C., 24000 filaments of carbon fiber T800SC manufactured by Toray Industries, Inc. were impregnated and wound on a supply roll 11 (bobbin) to obtain a tow prepreg 20 having a resin content of 28%.

  While the bobbin of the tow prepreg 20 was heated at 50 ° C. by the heating device 6, it was wound around the aluminum 7 L liner 5 having an outer diameter of 250 mm at the central portion by filament winding (FW). The FW condition was a hoop winding of the liner 5 with a rotation speed of 60 rpm and a tension of 50 N. Only when the FW approached the trunk end, the wound portion was cooled by blowing.

  Thereby, it was able to wind without the trunk | drum end part shifting | deviating to the dome side.

  In this example, a composite container was manufactured by the method for manufacturing a composite container of the present invention under the following conditions.

  As a specimen, an aluminum liner (length: 345 mm, outer diameter: 100 mm, inner volume: 2.1 liters, material A6061-T6) manufactured by SAMTECH was used.

  An epoxy-based thermosetting resin (epoxy resin, trade name Toho Dite EE50 (manufactured by Toho Earthtec Co., Ltd.)) is applied to the entire outer surface excluding the base portion of the liner. And then cured at room temperature for 24 hours to form a peeling inhibitor layer.

  After curing, a tow prepreg 20 using the following resin composition is prepared, filament winding is performed under the same conditions as in Example 1, and a container is manufactured. The body end is wound without shifting to the dome side. I was able to.

(Resin composition)
The thermosetting resin of this example is bisphenol F type epoxy resin (liquid at 25 ° C .: epoxy equivalent 158 g / ep, Epototo YDF-8170 manufactured by Tohto Kasei Co., Ltd.), 290 parts by weight, methylhexahydrophthalic anhydride (methyl 308 parts by weight of Kashima HHPA, Shin Nippon Rika Co., Ltd., Licacid MH-700), 6.1 parts by weight of 2-ethyl-4-methylimidazole (Curesol 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and 890 parts by weight of an inorganic filler What was obtained by melt-kneading was used. The viscosity of the thermosetting resin in this composition was 85 Pa · s at 25 ° C. and 1 Pa · s at 80 ° C.

DESCRIPTION OF SYMBOLS 1 Supply part 2 Winding tension adjustment part 3 Speed sensor pulley 4 Delivery eye 5 Liner 6 Heating apparatus 7 Cooling apparatus 8 Control part 10 Manufacturing apparatus 11 Supply roll 20 Toe prepreg

Claims (6)

In a method for manufacturing a composite container, a fiber is pre-impregnated with a thermosetting resin and wound around a liner to manufacture a composite container.
Heating the resin impregnated in the fiber before the fiber is wound around the liner to reduce the viscosity of the resin below the viscosity before heating;
A cooling step of cooling the resin while winding the fiber around the liner after the heating step, and increasing the viscosity of the resin reduced in the heating step. .   The method for manufacturing a composite container according to claim 1, wherein, in the heating step, the resin is heated at a temperature at which the resin is prevented from being instantaneously cured.   The manufacturing method of the composite container according to claim 2, wherein in the heating step, the resin is heated so that a temperature of the resin is 50 ° C. to 100 ° C.   The manufacturing method of the composite container of any one of Claim 1 thru | or 3 whose temperature of the cooling air for cooling the said resin is 45 degrees C or less in the said cooling process.   The method for producing a composite container according to any one of claims 1 to 4, wherein the fiber pre-impregnated with the thermosetting resin is a tow prepreg.   The method for producing a composite container according to claim 5, wherein the viscosity of the tow prepreg is 5 Pa · s to 100 Pa · s at 25 ° C and 0.1 Pa · s to 1.2 Pa · s at 80 ° C.

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