JP2009039962A - Composite pipe and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite pipe which has excellent dimensional tolerance and is free from the generation of particles. <P>SOLUTION: This composite pipe 1 is of a two-tier structure made up of a hollow pultrusion piece 2 obtained by impregnating a plurality of fibrous yarns with a heat-curable resin composition and curing the impregnated intermediate product while allowing it to pass through a heating mold and a metal pipe 3 fixed to at least, both ends of the outer surface of the hollow pultrusion piece 2. Further, this composite pipe is fabricated by a centerless machining process. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composite pipe in which a metallic pipe is covered on the outer surface of a hollow pultruded product and a method for manufacturing the same, and in particular, a composite suitable for a transport shaft used for transporting an antenna, a liquid crystal panel or the like of a mobile phone base station. Regarding pipes.

  Hollow pultruded products are widely used for shafts and the like used in devices for conveying electronic parts such as printed boards, liquid crystals, and shadow masks. In particular, the shaft used in the semiconductor transfer device has a severe warp and torsion standard and is required to be within 0.3 mm / m, and the product diameter has a final tolerance of h7.

  Conventional shafts typically use high-rigidity metals, but due to the increased size of the equipment, it is necessary to reduce the weight more than before, and hollow pultrusion molding using carbon fiber as the base material and epoxy resin Many products have been used.

  Until now, molded products obtained by impregnating and curing glass fibers and carbon fibers with a thermosetting resin have been performed by the hand lay-up method and the filament winding method. However, since the hand lay-up method is a manual operation and the filament winding method has complicated processes, both methods have poor productivity, high molding costs, and poor dimensional accuracy.

  Further, as a method for improving the pultrusion molding method, a method of superimposing and molding a mat layer on the drawn roving has been proposed, but a method for improving the dimensional system is not disclosed (for example, patents). Reference 1).

In addition, as an example of performance improvement by the outer diameter decoration of a pultruded molded product, there is an example of forming an artificial marble layer on the outer surface of a fiber-reinforced resin molded body, but no consideration is given to improving dimensional accuracy (for example, patents) Reference 2).
JP-A-8-34066 JP 7-137187 A

  In the case of such a conveying shaft, a roller and a bearing are attached to the shaft, but the dimensional tolerance between the component and the shaft is strict at the time of attachment, and the dimensional tolerance cannot be cleared only by molding. Therefore, dimensional tolerance can be cleared by centerless processing the surface of CFRP, but in this case, a problem of particles occurs.

  Accordingly, an object of the present invention is to provide a composite pipe that has excellent dimensional tolerance and does not generate particles.

  As a result of diligent investigations to solve the above problems, the present inventors have cleared the dimensional tolerances, and the CFRP surface is not contaminated by particles generated from the surface of the CFRP. The present invention has been completed by finding that the problem can be solved by covering the surface of the substrate with a metal pipe and then performing centerless processing.

  That is, the composite pipe of the present invention comprises a hollow pultruded product obtained by impregnating a plurality of fiber yarns with a thermosetting resin composition and cured while passing through a heating mold, and the hollow pultruded molded product. It has a two-layer structure consisting of metal pipes fixed on at least both ends of the outer surface, and is centerlessly processed.

  Further, the method for producing a composite pipe of the present invention includes a step of impregnating a plurality of fiber yarns with a thermosetting resin composition and curing the composition while passing through a heating mold to obtain a hollow pultruded molded product, It comprises a step of covering and fixing a metal pipe on at least both ends of the outer surface of the product, and a step of centerless processing a hollow pultruded product to which the metal pipe is fixed.

  As a similar shape to the present invention, there is a composite pipe in which a prepreg is wound around a mandrel, inserted into a SUS pipe and cured in that state, and the inside is CFRP and the outside is SUS. Costs and costs increase.

  According to the composite pipe of the present invention, the dimensional tolerance is cleared, and particles are not generated from the surface of the CFRP to contaminate the conveyed product, for example, excellent in dimensional accuracy such as a conveying shaft, and the like. Products that require high reliability can be provided at low cost. Furthermore, since the composite pipe of the present invention is formed such that the carbon fibers are unidirectional in the longitudinal direction, the pipe shaft is less bent in the vertical direction.

  Hereinafter, the present invention will be described in detail.

  The composite pipe of the present invention has a two-layer structure in which a plurality of fiber yarns are impregnated with a thermosetting resin composition and cured while passing through a heating mold, and at least both ends of the outer surface of a hollow pultruded product covered with metal pipes For example, as shown in FIG. 1, the composite pipe 1 is formed by covering a metal pipe 3 on the outer surface of a hollow pultruded product 2. FIG. 1 is a cutaway view showing an enlarged end portion of the composite pipe 1.

  The hollow pultruded molded product 2 can be carried out in the same manner as the production of an ordinary hollow pultruded molded product, in which a plurality of fiber yarns are impregnated with a thermosetting resin composition and cured while passing through a heating mold. The production of the hollow pultruded product will be described.

  The thermosetting resin composition used in the present invention can use a thermosetting resin such as an epoxy resin, a vinyl ester resin, or an unsaturated polyester resin as a base resin, and is preferably a vinyl ester resin.

  Examples of the thermosetting resin composition include (A) a vinyl ester resin, (B) a crosslinking agent, (C) a low shrinkage agent, (D) an inorganic filler, and (E) a release agent. (F) The thing containing an organic peroxide as an essential component is preferable.

  The (A) vinyl ester resin used in the present invention can be used without particular limitation as long as it is generally used as a molding material. For example, D-953 (Dainippon Ink Industries, Ltd., product) Name). Such (A) vinyl ester resin is obtained by reacting (a) an acidic component and (b) an epoxy resin component.

  Here, examples of the acid component (a) include unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, and sorbic acid, and phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, A mixture of two or more dibasic acids such as tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, and adipic acid can also be used.

  In addition, as the (b) epoxy resin component, as long as it has two or more epoxy groups in one molecule, it can be widely used without being limited by molecular structure, molecular weight, etc. Specifically, Examples thereof include an epoxy resin having a bisphenol type, novolak type or biphenyl type aromatic group, an epoxy resin in which a polycarboxylic acid is glycidyl etherified, and an epoxy resin having an alicyclic group in which an epoxy group is condensed to a cyclohexane derivative. These epoxy resins can be used individually or in mixture of 2 or more types. Furthermore, as an epoxy resin component, in addition to these, a liquid monoepoxy resin can be used as a combined component as required.

  It is preferable that the compounding quantity of this (A) vinyl ester resin is the range of 70-90 mass% in a thermosetting resin composition.

  As the (B) cross-linking agent used in the present invention, any one having a double bond polymerizable with the (A) vinyl ester resin can be used. For example, styrene monomer, divinylbenzene, diallyl phthalate monomer, methacrylic acid Examples include methyl and triallyl isocyanurate. It is preferable that the compounding quantity of this (B) crosslinking agent is the range of 1-2 mass% in a thermosetting resin composition.

  As the (C) low shrinkage material used in the present invention, polyethylene resin, saturated polyester resin, rubber, polyethylene, etc., which are thermoplastic resins, can be used. From the viewpoint of chemical resistance, light weight, and low shrinkage, polyethylene is used. A resin is preferred. Among these, a polyethylene resin powder having a glass transition point of 70 to 120 ° C. is particularly preferable for improving chemical resistance and molding shrinkage. It is preferable that the compounding quantity of this (C) low shrinkage | contraction material is the range of 0.5-1.5 mass% in a thermosetting resin composition.

  Examples of the (D) inorganic filler used in the present invention include those usually used such as barium sulfate, calcium carbonate, aluminum hydroxide, silica, and glass balloon, and are not particularly limited. The blending amount of the (D) inorganic filler is preferably in the range of 10 to 28% by mass in the thermosetting resin composition.

  The (E) mold release agent used in the present invention may be any mold release agent that is usually used as a molding material. Examples thereof include commercially available silicone oils, and among these, epoxy-modified silicone oils are preferred. It is preferable that the compounding quantity of this (E) mold release agent is 0.01-2 mass% in a thermosetting resin composition.

  The organic peroxide (F) used in the present invention is not particularly limited as long as it is a compound that is usually used as a curing agent for vinyl ester resins, and examples thereof include benzoyl peroxide and di-t-butyl peroxide. And isobutyryl peroxide. It is preferable that the compounding quantity of this (F) organic peroxide is the range of 0.1-2 mass% in a thermosetting resin composition.

  In this vinyl ester resin composition, when polyethylene is used as the low shrinkage material, it can satisfy chemical resistance, light weight and dimensional stability, can satisfy long-term reliability as a support product, and can be drawn at low cost. It can be manufactured as a molded product. The same applies to the case where an unsaturated polyester resin is used as the base resin.

  Next, the fiber yarn used in the present invention is obtained by converging the fibers, and is particularly limited as long as it can be obtained by the fiber yarn that has been conventionally used for producing a pultruded product. Examples thereof include fiber yarns made of glass fibers, carbon fibers, xylon fibers, wholly aromatic polyester fibers, chemical-resistant organic fibers, and the like. As this fiber yarn, commercially available products can be applied. Examples of the glass fiber include E-glass fiber, T-glass fiber, D-glass fiber, etc., and carbon fiber as PAN type and PITCH type. As the aramid fiber, those commercially available as fiber base materials, such as para-type and meta-type fibers, can be applied.

  In addition, the fiber yarns used here, particularly glass fibers and carbon fibers, are preferably subjected to sizing treatment with a silane coupling material on the surface to maintain chemical resistance, and as a sizing agent that performs this sizing treatment Examples thereof include agents having low reactivity with an alkali component and good wettability with respect to a matrix resin. Specifically, a silane coupling agent such as methacryl silane or ureido silane or a mixture thereof is preferable.

  As the fiber base material, the above fiber yarn may be used alone or a plurality of types may be mixed. In particular, a glass fiber and a carbon fiber may be used alone or as a mixture of glass fiber and carbon fiber. It is preferable to use it as a material.

  The fiber yarn content is preferably 50 to 80% in terms of the average volume content (volume ratio) of the fiber substrate in the molded product. If it is less than 50%, the rigidity of the molded product becomes poor, and if it exceeds 80%, a portion where the resin composition is not impregnated in the fiber reinforcing material is formed, and the physical properties of the pultruded product are deteriorated.

  The mixing of the thermosetting resin composition for pultrusion and the fiber yarn is preferably performed by impregnating the fiber yarn with the thermosetting resin composition so that the resin composition adheres to the fiber yarn. Since it is necessary for the fiber yarn to be able to withstand the pulling force at the time of pultrusion molding, it is preferable to use the fiber yarn configuration with the fiber yarn roving oriented in the drawing direction.

  And in the manufacturing method of the pultruded article used here, the thermosetting resin composition varnish is impregnated into the fiber yarn obtained by converging a plurality of the above-mentioned fibers, for example, 50 to 500 fibers, The fiber reinforced resin composition is passed through a heating mold, the thermosetting resin composition is cured, the outer shape is adjusted according to the shape of the mold, and the molded article is formed. Depending on the resin composition used, the heating temperature and the drawing speed can be selected as appropriate.

  Here, the fiber yarn impregnated with the thermosetting resin composition is directly drawn into the mold and passes through the heated mold to be cured by heating and molded into a predetermined shape. The mold used sometimes is not particularly limited as long as it is a mold used for pultrusion molding, and may be heat-cured by a conventionally used method.

  The mold in the present invention is heated and controlled by a heater or the like in order to obtain a pultruded product by curing the resin. Here, the temperature of the mold is preferably 70 to 170 ° C. If the mold temperature is less than 70 ° C., the fiber reinforced resin composition is easily pulled out in an uncured state, and if it exceeds 170 ° C., the curing reaction occurs rapidly, so cracks and warpage of the molded product are poor. This will increase the possibility of causing

  At this time, it is preferable that the drawing time (time to pass through the mold) is within a range of 0.5 to 3.0 minutes. The range of 10 to 120 cm / min is preferable, and the range of 20 to 35 cm / min is particularly preferable. When the drawing speed is less than 10 cm / min, curing in the molding die is completed at an early stage, and resistance at the time of drawing becomes large and stable continuous molding cannot be performed. On the other hand, the drawing speed is 120 cm. When it exceeds / min, the fiber-reinforced resin composition is easily pulled out in an uncured state.

  That is, in the pultrusion molding, the fiber reinforced resin composition is continuously drawn into a heated mold, and the resin is subjected to a predetermined temperature while passing through the mold to be cured, and at a predetermined outlet from the mold outlet. Pull out in time. The apparatus used in the pultrusion molding may be configured in the same manner as a commonly used pultrusion product manufacturing apparatus, and can be used without any particular limitation. Moreover, it is preferable that a metal mold | die part is what was demonstrated above.

  Thereby, the cured resin composition can be efficiently cured and can be molded with good operability. The molded product thus obtained can be made into a molded product having a small volume shrinkage and excellent appearance and physical properties by mixing a low shrinkage agent.

  The metal pipe 3 can be made of stainless steel, iron, titanium, or the like, but stainless steel is particularly preferable. Thereby, it is possible to obtain a pultruded product having a uniform wall thickness, high roundness, little warping, and excellent lightness, molding shrinkage, and outer dimensions.

  Since the metal pipe 3 may be any one that can be used by being put on the hollow pultruded product 2, the inner diameter of the metal pipe 3 corresponds to the outer diameter of the hollow pultruded product 2 at this time. . Here, the term “corresponding to the outer diameter” means that the hollow drawn product 2 can be inserted into the metal pipe 3 and fixed with an adhesive. Further, at this time, the thickness of the metal pipe 3 is not particularly limited, but if it is too thin, the strength becomes insufficient, and the life of the shaft becomes short, and if it is too thick, the cost increases. Therefore, the thickness is preferably 0.3 to 1.5 mm. Incidentally, the thickness of the hollow pultruded product is preferably 1.5 to 3 mm in order to ensure the sufficient strength of the main structure of the shaft.

  These fixings are performed by inserting the pultruded product 2 with the adhesive 4 applied to the outer surface thereof into the metal pipe 3 and curing the adhesive 4 so that the pultruded product 2 and the metal pipe 3 Adhere and fix. At this time, the adhesive 4 may be applied not to the outer surface of the pultruded product 2 but to the inner surface of the metal pipe 3.

  Examples of the adhesive include an epoxy resin adhesive, a polyester adhesive, and a vinyl acetate adhesive, and in particular, by heating when the adhesive is cured to form a composite pipe, by temperature change due to natural cooling. The hollow pultruded product 2 and the metal pipe 3 each have a different warp due to the difference in linear expansion coefficient, but it is an adhesive that has elasticity after curing so that it can be relaxed and the connection between the two can be stably maintained. Preferably there is.

  The metal pipe 3 may be a composite pipe having a two-layer structure that covers at least both ends of the outer surface of the hollow pultruded product 2 and preferably covers the entire outer surface. Moreover, when it was made to have covered on both ends, it is preferable to cover at least the part of 50-100 mm from an edge part.

  By performing centerless processing of the composite pipe 1 obtained by fixing the metal pipe 3 in this way, it is possible to achieve high dimensional accuracy useful for a conveyance shaft and the like, and to reduce the dimensional tolerance. it can. In the composite pipe of the present invention, not the hollow pultruded product 2 but the metal pipe 3 is processed by centerless processing, so that no contamination by particles occurs.

  Moreover, the size of the composite pipe 1 obtained in this way is, for example, when applied to a conveying shaft, the outer diameter is about 10 to 30 mm, and the shaft length is about 1000 to 2000 mm. It is preferable.

  Hereinafter, the present invention will be specifically described by way of examples.

Example 1
As thermosetting resin components, 22 parts by mass of vinyl ester resin (Dainippon Ink Industries, trade name: UE3505), styrene monomer (trade name: Styrene monomer, manufactured by Nippon Yupica Co., Ltd.) 0.35 parts by mass, polyethylene (Product name: Flowsen UF-1.5, manufactured by Sumitomo Seika Co., Ltd.) 0.25 parts by mass, barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., product name: precipitated barium sulfate-100), 3.7 parts by mass, Organic peroxide 1 (Nippon Yushi Co., Ltd., trade name: Perbutyl O) 0.06 parts by mass, Organic peroxide 2 (Nippon Yushi Co., Ltd., trade name: Perhexa HC) 0.35 parts by mass, mold release Agent (manufactured by Kozakura Shokai Co., Ltd., trade name: INT-1850HT [organic acid, glyceride, synthetic resin condensate]) 0.35 parts by mass in a kneader (disper) and kneaded for about 20 minutes A thermosetting resin molding material was obtained.

  Next, 60 carbon fibers UT-500-24K (manufactured by Toho Tenax Co., Ltd., trade name) are impregnated into a resin tank containing the obtained thermosetting resin molding material as a base material. The impregnated carbon fiber is passed through an extrusion molding jig, and then continuously heated to 160 ° C., sent to a core mold (length: 800 mm, inner diameter: 15 mm), and sufficiently cured, 20 cm / min. The hollow pultruded molded product was continuously obtained by drawing at a speed of, and this was cut with a cutting device to obtain a pultruded molded product with a volume ratio of carbon fiber of 70%. A core jig (length: 500 mm, outer shape: 10 mm, set temperature: 140 ° C.) was installed so as to come into contact with the fiber from 10 cm before the mold.

  The roundness, warpage, and outer dimensions of the obtained hollow pultruded product were measured, and the results are shown in Table 1.

  Next, a stainless steel pipe (material: SUS304, external dimensions: φ16 mm, length: 1500 mm) is covered with an adhesive as shown in FIG. A composite pipe was manufactured. The dimensional accuracy at this time is shown in Table 2.

(Comparative Example 1)
The hollow pultruded product obtained in the same manner as in Example 1 was subjected to centerless processing without attaching a stainless steel pipe to the hollow pultruded product so as to obtain an outer dimension of φ14 mm. The dimensional accuracy is shown in Table 3.

  In addition, the composite pipe of Example 1 does not generate particles from the outer surface, and is suitable for a conveyance shaft. On the other hand, in the pultruded product subjected to centerless processing of Comparative Example 1, particles are generated from the outer surface. This occurred and contaminated the object to be conveyed during conveyance.

It is the elements on larger scale which showed the structure of the edge part of the composite pipe of this invention. It is a side view of the composite pipe of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Composite pipe, 2 ... Hollow drawing molded product, 3 ... Metal pipe, 4 ... Adhesive

Claims (6)

  A hollow pultruded product obtained by impregnating a plurality of fiber yarns with a thermosetting resin composition and cured while passing through a heating mold, and fixing over at least both ends of the outer surface of the hollow pultruded product A composite pipe having a two-layer structure comprising a metal pipe and a centerless process.   2. The composite pipe according to claim 1, wherein the hollow drawn product has a thickness of 1.5 to 3.0 mm, and the metal pipe has a thickness of 0.3 to 1.5 mm.   The composite pipe according to claim 1 or 2, wherein the metal pipe is made of stainless steel.   The composite pipe according to any one of claims 1 to 3, wherein the fiber is composed of glass fiber and / or carbon fiber.   The thermosetting resin composition comprises (A) a vinyl ester resin, (B) a crosslinking agent, (C) a low shrinkage agent, (D) an inorganic filler, (E) a release agent, and (F 5. The composite pipe according to claim 1, wherein an organic peroxide is an essential component. Impregnating a plurality of fiber yarns with a thermosetting resin composition and curing while passing through a heating mold to obtain a hollow pultruded molded product;
A process of covering and fixing a metallic pipe on at least both ends of the outer surface of the hollow pultruded product,
Centerless processing a hollow pultruded product to which the metal pipe is fixed;
A method for producing a composite pipe, comprising:

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