TW496821B - Product molded out of fiber reinforced plastics - Google Patents

Abstract

The four multiple-sheets are each made by sticking an ionomer film on one side of a prepreg sheet comprising reinforced fibers dipped in epoxy resins. Above-mentioned four multiple sheets are one after another put around the 6, 6 nylon-tube putting on the mandrel. Then the mandrel is pulled out, the four multiple sheets are transformed to a tubular member. The tubular member is molded by heating under pressure into a circular tubular product.

Description

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 ^ __ _____B7 V. Description of the Invention (1) — ^ ^ [Technical Leadership to which the Invention belongs] The present invention relates to the use of Fiber-reinforced plastic molded products for sports goods and industrial products of Taguchi Rinai Nagoya Temple with robot arms. [Previous technology] Fiber-reinforced plastic molded products for various sports and industrial products are required to have properties such as light weight, high strength, and high vibration attenuation. The strength (bending strength, impact strength, etc.) f affects the longevity of the molded product, and the higher the strength, the higher the durability of the molded product. On the other hand, when the molded product is a combination of tennis rackets, vibration attenuation has a great influence on the feeling of playing and the impact of the human body when playing. If the vibration attenuation is excellent, the feeling when playing It becomes soft, and at the same time, the so-called tennis elbow damage to the human body can be suppressed. In addition, when the molded product is a robotic arm, excellent vibration attenuation can reduce the time required for the robot to stand still, thereby reducing work efficiency. Many fiber-reinforced plastic molded products using epoxy resin as a matrix resin have been proposed for improving the strength and vibration damping (vibration attenuation) of the matrix resin. [Problems to be Solved by the Invention] By using hardening containing long aliphatic groups and rubber-like properties ^: 丨 / 黍 Addition of compounds with elastomeric properties, bituminous substances, glycols and other plasticizers In lacquering, a molecular group that can exhibit rubber elasticity is introduced into oxygen compounds, etc., in an attempt to strengthen it. < Mitsuichi Koshiichi, "Door Knife" 38 (3), 200 (i989), 堀 内 伸, "Functional Material" This paper 5 is suitable for ~~~~ —- f Please read the precautions on the back before filling in this page ) Bookbinding • d 496821 Α7 Β7 V. Description of the invention (2) '15 (7) 22 (1995) >. In addition, in order to achieve strong service, it is made of aromatic polyamines-polybutadiene-acrylonitrile block copolymers containing phenanthrene hydroxyl groups, epoxy resin modifiers, and inorganic or organic fibers. A fiber-reinforced composite epoxy resin composition has been proposed (Japanese Unexamined Patent Publication No. 4-Jiangxi Gazette). However by. Although the molded products obtained from the proposals such as Hai have excellent strength and rigidity, they have not been able to obtain ideal results regarding vibration relief. On the other hand, in Japanese Unexamined Patent Publication No. 6-155464, in order to improve the vibration-reducing properties, it is proposed to use an isobutylene rubber as a main component of a vibration-damping resin film to be embedded in epoxy resin-impregnated carbon fiber in layers. Made into a tennis racket. However, the tennis racket produced according to this proposal has poor adhesion between the vibration-damping resin film and the carbon fiber layer impregnated with the epoxy resin, so that the strength and rigidity of the molded product are greatly reduced. As described above, although many proposals have been made to improve the performance of fiber-reinforced plastic molded products using epoxy resin as a matrix resin, molded products that satisfy both strength and vibration attenuation properties have not been obtained. For the truth. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) 4 In view of the above situation, the present invention is based on a matrix resin made of epoxy resin, and provides strength and vibration attenuation倶 佳 's fiber-reinforced plastic molded products are the subject. [Means for solving problems]

Fiber-reinforced plastic molded products, such as tennis rackets and golf clubs, are hollow-tube shaped articles made of resin-reinforced fiber-reinforced laminates. Such a hollow molded product is important in terms of impact resistance and vibration attenuation, in addition to a simple bending mode, including a twisted mode. For example, the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) A7 — ~~ -—. ~~ ——____ B7 V. Description of the invention (3) — Tennis racket frame facing outward The bending in the direction, that is, the bending in the vertical direction with respect to the surface facing the tennis racket, in order to meet the deformation, distortion occurs in the hollow frame. In the coupling of golf clubs, the deformation is not merely a simple bending, but a twist. However, once bending occurs, as shown in FIG. 8, the shearing force 2 occurs between the resin impregnated reinforcing fiber layers laminated on the resin impregnated with the force 1 in the twisting direction, as shown in FIG. 8, that is, the laminated resin The shearing force generated between the impregnated reinforcing fiber layers greatly affects the impact strength and vibration attenuation of the hollow molded product. The inventor of the present case focused on the shearing force occurring between the laminated resin-impregnated reinforcing fiber layers of the hollow molded article, in order to reduce the shear direction displacement between the laminated resin-impregnated reinforcing fiber layers and effectively absorb the shearing force. The present invention has been intensively studied on the material and laminated structure of the molded product repeatedly. That is, the present invention is as described in item 丨 of the scope of the patent application. The matrix resin is a molded article of fiber-reinforced plastic composed of epoxy resin. A fiber-reinforced plastic molded article having at least a part of an ionic polymer film in between. The above ionic polymer film printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is a film formed by bridging metal ions between molecules of an ethylene-methacrylic acid copolymer, for example, Hemi blue (~ ⑼ manufactured by Mitsui DuPont Chemical Co., Ltd. , Trade name) is applicable (item 2 of the scope of patent application). This ionic polymer film has high reactivity with epoxy groups, shows excellent adhesion to epoxy resins, and at the same time has a large elasticity, is strong, and has excellent impact resistance. ^ Paper 1 scale CNS A4 specification (21Gx 297mm) ------- ΑΊ ~~~~ -_____ B7 V. Description of the invention (4)-The above metal ions include Na, K , Mg, Z4. In particular, Zn ions are most suitable in order that the ionic polymer film can have good adhesion to the epoxy resin. In addition, the thickness of the ionic polymer film is not particularly limited, but a range of 30 to ⑽ is suitable. As described above, in the fiber-reinforced plastic molded product of the present invention, the ionic polymer film interposed between the epoxy-impregnated reinforcing fiber layers and the epoxy-impregnated reinforcing fiber layer of the epoxy resin are strongly adhered to each other, and the epoxy laminated on top and bottom The displacement in the shearing direction between the resin-impregnated reinforcing fiber layers is reduced, and due to the elasticity of the ionic polymer film, the vibration accompanying the shearing force occurring between the epoxy-impregnated reinforcing fiber layers can be effectively absorbed. Therefore, the impact strength and vibration attenuation of the molded product can be greatly improved. The glass transition temperature range of the above ionic polymer film is preferably 0 ~ 60c > c (item 3 of the scope of patent application). In general, the loss coefficient (tan δ) of an ionic polymer film near the glass transition temperature becomes larger; therefore, if an ionic polymer film with a glass transition temperature of 0 to 60 ° C is used, the temperature (generally In terms of the actual outdoor or indoor ambient temperature using tennis rackets, golf clubs, robotic arms, etc .: about 5 ~ 35. 0), it can show significant vibration absorption by the ionic polymer film. In addition, the 'molded product is made by laminating an ionic polymer film on one side of a prepreg sheet impregnated with a reinforced fiber impregnated epoxy resin; the composite sheet is laminated and wound into a hollow tube, and the epoxy resin is made by It is suitable to be formed into a hollow tube by curing (item 4 of the scope of patent application). In this way, only the heavy-wound composite sheet will be used, and there will be no ionic polymer film and ionic polymerization. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm)

In the case of direct contact of the polymer film, the ionic polymer film can be interposed between the Wei resin impregnated reinforced fiber layer on the lower layer and the epoxy resin impregnated on the upper layer and the fiber layer. Therefore, the ion polymer film and epoxy resin The reaction j rate was good, and the impact strength and vibration attenuation of the molded product were improved by π. In addition, the above ionic polymer film is arranged along the circumferential direction of the tube ^ %% over 1 week, and the two ends of the ionic polymer film in the direction of the circle are printed by the department of the Central Consumers' Bureau of Consumer Consumption Cooperative. It is better to sandwich the prepreg sheet and overlap it (the fifth item in the patent scope). 2. Epoxy resins impregnated with reinforcing fibers are epoxy resins using amines, phenols, and compounds containing carbon-carbon double bonds as precursors. In particular, those having two or more epoxy groups in one molecule are suitable. Specific examples of epoxy resins using amines as precursors include tetraglycidyl diamino diphenyl methylamine, tris-epoxy-phenylaniline, and tri-epoxy ^ 1 m —Hydroxyaniline, triglycidylhydroxytoluidine, various isomers. Specific examples of epoxy resins using phenols as precursors include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol $ epoxy resin, and phenol block ring. Oxygen resin, cresol block epoxy resin, resorcinol block resin, etc. Specific examples of the epoxy resin using a compound containing a carbon-carbon double bond as a precursor include an alicyclic epoxy resin and the like. As the so-called latent curing agent for epoxy resin, which is used in combination to harden the epoxy resin, amines, acid anhydrides, imidazoles and the like are suitable. Specific examples of amines include 4,4, diaminodiphenylhydrazone, 3,3 ,, diaminodiphenylfluorene, cyanoguanidine, etc. Specific examples of acid anhydrides include tetrahydrophthalic anhydride, etc .; imidazole Specific examples include 2-n-heptyldecylimidazole and the like. In addition, these amines, anhydrides, -------- I (Please read the precautions on the back before filling this page)

、 1T 丨 Lu *! I m m This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm

496821 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (other than imidazoles, for example, N, N-dialkylurea derivatives, n, n-dialkylthiourea derivatives, N- The use of aminoethylpiperazine, melamine, guanamine, trigasification side complex, tris (dimethylamine phenol), etc. is also preferable. These hardeners can be used alone or in combination of two or more. As a hardening accelerator, for example, alcohol-based, phenol-based, thiol-based, dimethylurea-based, cycloaliphatic-based, imidazole-based, etc. In addition, in order to reduce costs, a well-mixed filler can usually be used. For example, calcium carbonate, silicon dioxide, talc, mica, diatomite, perlite, asbestos, alumina, etc. The hardening temperature of the soil oxygen resin can be changed depending on the type of hardener. Although there is no particular limitation, it is considered And moldability, its reactivity with ionic polymer films, and the melting point of ionic polymer films are preferably in the range of 14 ° to 160 ° C. Those who use it as a reinforcing fiber can use this leading city from High performance Fibers, such as carbon fibers, graphite fibers, glass fibers, aromatic polyamide fibers, silicon carbide fibers, alumina fibers, shed fibers, steel fibers, amorphous metal fibers, organic fibers, etc .; one or two of them can be used The combination of the above. Moreover, the shape of the fiber may be any of continuous fiber, long fiber, short fiber, or a combination thereof. There is no particular limitation on the configuration of the reinforcing fiber and the fiber direction, such as a single direction. It can be any of the following: random direction, sheet shape, cushion shape, fabric (cross) shape, and string shape. The manufacturing method of the molded product is not particularly limited, and the following methods are suitable. ① Strengthening Fiber dimensional prepreg impregnated with epoxy resin is laminated. This paper size applies Chinese National Standard (CNS) A4 (2l0x297 mm) (· Please read the precautions on the back before filling this page} · ， 可 496821 A7 --- ~-_B7_ V. Description of the invention (7 ^ a ~ ----- While applying pressure to the laminated body, at the same time-while curing the epoxy resin in this case, During the lamination stage of the prepreg sheet, an ionomer film is placed between the prepreg sheets. On one side of the prepreg sheet, an ionic polymer film is used to make a composite sheet, and It can also be laminated. As a prepreg, it is made by winding the continuous fiber impregnated with oxygen-free resin on the drum in one direction by the drum winding method. Continuous fiber prepreg sheet is preferred. 〃 ② Sleeve-shaped (hollow shaft) cords are laminated and formed into a tube, and the tube is impregnated with epoxy resin. When the tube is under pressure, the resin is hardened. In this case, it is at the stage of laminating the sleeve-shaped wire fiber, that is, the ion polymer film is placed between the sleeve-shaped wire and the rope; further, it is designed in advance The path through which the epoxy resin passes makes the impregnation of the epoxy resin throughout the entire laminate, and there is no ionic polymer film in the entire city between the lower sleeve-like cord and the upper sleeve-like cord. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ③ Use rovings impregnated with epoxy resin and wind the resin-impregnated reinforcing fibers with the filament winding method, and then apply pressure to harden the epoxy resin. This combination is related to the

, Laminate the ionic polymer film cut into a sheet or band shape so that the ★ ionic polymer film is between the reinforcing fiber layers. X In any of the above-mentioned manufacturing methods ① to ③, a resin-impregnated fiber-reinforced fiber laminate with an ionic polymer film placed between the outer winding layer and the layer of a flexible cylinder in a metal mold is formed, While applying pressure to the laminate with the flexible cartridge, the so-called thermoforming is performed = this paper size is suitable for financial and household materials (CNS) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 496821 A7 _________B7 V. Invention Explanation (8) Internal pressure method; it is also possible to wind the cord for pressing on the outer periphery of the laminated material of the resin-impregnated reinforcing fiber with an ionic polymer film interposed between the layers, and press the cord for the laminate on one side The material is pressurized and the so-called external pressure is performed while heating. In the "Internal Pressure", the remaining resin is discharged to the branch line of the metal mold. In the external pressure method, it is necessary to release the remaining resin to the gap between the pressing cords. Arrangement of the flowing ionic polymer film of these remaining resins. That is, avoiding the ionic polymer film completely covering the outermost layer of the laminate, and avoiding the configuration of the ionic polymer film such that the upper and lower ionic polymer films are in contact with each other. Therefore, for example, in the case of (1) above, the ionic polymer film is continuously arranged around the circumference of the sleeve for more than one week, and the two ends of the ionic polymer film in the circumferential direction sandwich the prepreg sheet and overlap each other. good. The ionic polymer film in the molded product is preferably placed between the fiber layers where the vibrational displacement is maximized when the ionic polymer film is not used. For example, in recent years, tennis rackets have tended to be lightweight, and rackets with an overall weight of only 250 to 270 g have appeared. Due to such a lightweight racket, the inelasticity is poor. Therefore, the balance is made into a heavy head to maintain its swing. performance. That is, the fiber-reinforced plastic layer makes a larger weight distribution on the tennis racket's face, especially the top part (see Figure 9). However, 'users have said that the vibration attenuation of such lightweight tennis rackets is poor.' Based on the results of research, due to the weight of the racket part, the amount of fiber on the grip side is larger than that of the racket. Since the amount of fibers on the surface side is small, it is known that the displacement of the secondary vibration mode in the outward direction in the abdomen becomes larger. This paper size applies to the Chinese National Standard (⑽) M specification (training η97 public holiday) 丨 -IC please read the precautions on the back before filling out this page)-Order printed by the Central Consumers Bureau of the Ministry of Economic Affairs Consumer Cooperatives 496821 A7 -___ Β7 V. Description of the invention (9) Figure 10 (A) (B) shows the i-th vibration mode and the second-vibration mode of the tennis racket frame facing outward. The abdomen of the above-mentioned second vibration mode refers to the i-th (b) ) In the figure, R1 (the mesh surface is regarded as the clock face, and the apex? Is near the 3 o'clock position at 12 o'clock) and R2 (near the junction of the grip G and the throat). Therefore, in such a tennis racket, if the abdomen of the secondary vibration mode is old and an ionic polymer film is interposed between the fiber layers of R2, the vibration attenuation property can be greatly improved. Moreover, in the case of a lightweight golf club whose overall weight is less than 55 g, the shape change that occurs when an external force is applied is also larger than that of a general club (overall weight: 56 to 90 g). In this case, especially if the ionic polymer film is inserted in the part where the stress is concentrated, its bending strength can be increased, and the durability of the club can be greatly improved. [Embodiments of the invention] The present invention will be described in further detail by the following examples and comparative examples. (Example 1) An epoxy resin impregnated carbon fiber prepreg (T800: P2053-122) ), According to the following process, a pipe with a total length of 60 () mm and an outer diameter (0) of 18.4 mm is a circular tube. First, on a 600mm X 59mm wide epoxy resin impregnated carbon fiber prepreg sheet, 200mm long X 59mm wide, tensile strength (JISK-6760) 245kg / cm2, breaking point elongation (JISK 676) 560%, flexural modulus (JIS K-7160), 1480 kg / cm2, Zn ion type ionic polymer film with glass transition temperature of 40 ° C, made into composite sheet. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) Order 496821 A7 B7 — —--—-.-. _ V. Invention Explanation (10) 'Similarly, an epoxy-impregnated carbon fiber prepreg sheet with a length of 600 mm x a width of 60 mm was made and an ionic polymer film with a length of 600 mm x a width of 60 mm was attached (made by Mitsui DuPont Co., Ltd., Hemi Blue 1652 (trade name)) composite sheet, 600 mm x 62 mm epoxy resin impregnated carbon fiber prepreg sheet attached with 600 mm x 62 mm ion polymer film (made by Mitsui DuPont Co., Ltd., Hemi Blue 1652 (commercial name)) composite sheet, and an epoxy-impregnated carbon fiber prepreg sheet with a length of 600 mm x 63 mm and an ionic polymer film with a length of 600 mm x 63 mm (Mitsui DuPont ( Stock), Haimi Blue 1652 (commercial name)) composite sheet. Secondly, the four composite sheets are placed on the side of each prepreg sheet so that the fiber direction between the prepreg sheet and the prepreg sheet is ± 24. In this way, the composite sheet is further laminated with an epoxy resin impregnated carbon fiber prepreg of the same size (length x width). Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs and then 'shown in Figure 1 (A), a 66,5 mm nylon cylinder 22 is covered on a 16.5 mm mold core 21, and the 66 nylon rubber cylinder 22 is sequentially wound. After the four composite sheets 23A to 23D, the core 21 is pulled out as shown in FIG. 1 (B) to produce a laminated material. Furthermore, the overlap amount of each composite sheet in the winding is 7 mm. As shown in FIG. 1 (C), the overlapping portion 25 of the composite sheet does not form an overlap between the wound layer and the layer. This is to make the pressure applied to the laminated material 24 as uniform as possible in the subsequent forming process so that the laminated material 24 does not form a part with a relatively large thickness. Next, the above-mentioned laminated body was placed in a metal mold having a circular cross-section, and was formed by heating at 15 ° C. and 40 minutes to form a tube having a circular cross-section. At this time, 7 kgf was applied to a 66 nylon cartridge. / cm2 of air pressure. 13 (-Please read the notes on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) V. Description of invention (11 A7 B7 Central Ministry of Economy Standards Bureau g <Industrial and Consumer Cooperatives Co., Ltd. (Example 2) Except that the ionic polymer film used is Na ion type, tensile strength (JIS K-6760) 305kg / cm2, breaking point elongation (JIS κ-676). ) 43%, flexural modulus (JISK-716), 2400kg / cm2, other than ionic polymer film (made by Mitsui DuPont Co., Ltd., Hemi blue (trade name)) with glass transition temperature o ° c A circular cross-section tube having the same structure as that of Example i (the dimensions, laminated structure, etc. of the epoxy resin-impregnated carbon fiber prepreg sheet, ionic polymer film, composite sheet, etc.) was made. (Example 3 ) Except for the ionic polymer film, which will be respectively contained in four composite sheets A tube with a circular cross-section was produced in the same manner as in Example i except that the length was 600 mm. (Comparative Example 1) Two pieces of four ionic polymer films were used and the soil direction was 24. The composite sheet made of prepreg sheets is laminated to make a tube with a circular cross-section by the same process as the example. The four composite sheets are two sheets of 600 mm long and 63 mm wide. A stack of two sheets, a stack of two sheets of 600 mm in length and a width of 62 mm, a stack of two sheets of 600 mm in length and a width of 60 mm, and two sheets of 600 mm in length and 59 mm in width The laminate (Comparative Example 2) was placed on the outermost layer of the laminate with an ion polymer film (Miami Blue 1652 manufactured by Mitsui Dupont Co., Ltd.), and the rest was made into a tube with a circular cross-section similar to Comparative Example 1. (Comparative Example 3) Please read the intent first and then write this page 1

The X shape is applicable to the CNS M standard (⑽ '公 297 public attack) V. Description of the invention (12 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs and printed by ionic polymer film instead of latex Isoprene rubber-based anti-vibration coating (the coating layer formed by Daicel Lu Xi W Seven Industry Co., Ltd., Angulian 7 &gt; Xi 10), the size used is the same as that of the ionic polymer film, and In Example i, four composite sheets were prepared in the same manner, and the four composite sheets were made into tubes with a circular cross-section by the same process as in Example 1. The above Examples 1 to 3 and Comparative Examples i to 3 were measured. The weight of the obtained round section &amp; was evaluated separately for its strength and vibration attenuation. The strength of the acoustic curve is shown in Figure 2, according to the standard of JJS-K7055, and according to the metal mold. With a span of 300 mm, the center of the entire length of the circular cross section tube n is aligned with the center of the span, and a load is applied by the press 25 from above the central point p, and the test rate is 50 mm / min. Three-point bending test and measurement. Impact characteristics (maximum impact) Weight and impact energy) are shown in Figure 3. • Cut the center of the circular section tube, and support the cut tube with a span of 185 mm according to the metal mold 10. A load cell is installed at the center of the span. The weight 32 of 32 falls freely, and calculates the maximum load required for failure and the impact energy required for failure from the load value at each time and the initial port velocity '. The vibration attenuation rate is shown in FIG. The center of ^ is fixed to the vibrator 41. The vibrator 41 applies vibrations of different frequencies to the tube. The laser displacement meter 43 is used to measure the vibration of the aluminum foil 42 attached to the end of the tube 20 mm. The laser displacement meter 43 introduces the measured value into the FFT (Fast Fourier Transfer Analizer) through the DFC (Doppler Frequency Tracker) to measure the attenuation rate of the ^ under vibration mode. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) 15 C Please read the notes on the back before filling this page)-Order 496821 A7 -_______ B7 V. Description of the invention (U) The following table 1 is the result obtained. [Table 1] Example 1 Example 2 Example 3 Comparison example 1 Comparative example 2 Comparative example 3 Weight (g) 49.5 49.3 51.6 48.0 49.1 52.6 Flexural strength (kgf) 96.5 88.8 95.7 71.3 74.6 26.1 Maximum impact load (kn) 0.49 0.42 0.51 0.32 0.34 0.09 Impact energy (J) 0.88 0.63 0.89 0.54 0.51 0.16 Vibration attenuation rate 1.06 0.84 1.23 0.29 0.33 2.14 As shown in Table 1, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, an implementation made by placing ionic polymer films on top of epoxy-impregnated carbon fiber prepreg sheets Compared with the circular cross-section tube of the comparative example, the circular cross-section tube of Examples 丨 to 3 has significantly improved bending strength and impact resistance (maximum impact load, impact energy). In addition, compared with the circular cross-section tube of Comparative Examples i and 2, the vibration attenuation performance is also greatly improved. In addition, the circular cross section of Comparative Example 3 obtained by coating the coating layer of the latex-shaped isobutylene rubber-based vibration-proof coating layer on top of the epoxy resin-impregnated carbon fiber prepreg &amp; shows excellent results. Vibration attenuation, but its bending strength and impact resistance (maximum impact load, impact energy) are significantly poor. From the above results, it can be seen that when an ionic polymer film is stacked on top of an epoxy resin-impregnated carbon fiber prepreg sheet to be molded, the strength and vibration attenuation of the molded product can be improved. (Example 4) As shown in Fig. 5 (A), using eight sheets of paper with a length of 1680 mm and a width of 70 mm applies to the Chinese National Standard (CNS) A4 specification centimeters) _ (-Please read the precautions on the back before reading Fill out this page}

Printed A7 by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ~~ —-~ -----_ —-__ V. Description of the invention (14) Epoxy resin impregnated carbon fiber prepreg sheet (τ800) : P2053 122) 51A ~ 51H, coated on the 66 nylon tube 22 of the mold core 21, and the fiber direction is 0 relative to the shaft core. , 〇. , 3〇. , 3〇. , 45. , 45. , 45. , 45. , And each was 30. With 45. The prepreg sheet is laminated and wound in such a manner that the fiber directions are staggered with each other between adjacent prepreg sheets, and the mold core is pulled out as shown in FIG. 5 (B) to form a laminated sheet 52. . Before laminating the carbon fiber prepreg sheet impregnated with the soil-oxygen resin, the outside surface of the first, third, fifth, and seventh prepreg sheets from the inner side will be grown to 1680 in advance. A Zn ion type ionic polymer film (manufactured by Nitsui DuPont Co., Ltd., Hemi Blue 1652 (trade name)) with a width of 70 mm and a thickness of 70 mm was attached to the ionic polymer film 50 and then laminated. Next, as shown in FIG. 6, the above-mentioned laminated material 52 is disposed in a metal mold 53 for tennis rackets. The air pressure of 7 kgf / cm 2 is applied to a 66 nylon rubber cylinder, and it is heated and molded at 150 ° C for 40 minutes. Into a thick frame of tennis racket. The yoke portion (forked portion) 54 is made of foamed polyurethane as the core material, and the core material is a product covered with a prepreg sheet. The resulting thick frame had a 110-square-foot area, a weight of 190 g, and a balance of 36 mm. (Comparative Example 4) An ionic polymer film was not placed, and the other parts were fabricated in the same manner as in Example 4 to produce a thick tennis racket with a weight of 194 g and a balance of 358 mm. The vibration attenuation of the thick frames of the tennis rackets of Example 4 and Comparative Example 4 prepared as described above was measured by the method shown in FIG. As shown in FIG. 7 (A), the netted tennis racket frame 70 is suspended by a cord 71 and hits the frame with an impact hammer 72. The paper size is applied to Chinese national standards when installed on the impact trip (CNS) A4 specification (210X297 mm) (Read the precautions on the back before filling out this page) 4, 11 496821 Α7 Β7 V. The force receiver (not shown) of the invention description (l5) measures the vibration input force (Force F); On the other hand, the vibration response (acceleration α) is measured by a velocity receiver 73 which is perpendicular to the frame surface at a portion 4 cm from the clamping end; these measurement values &quot; / F) are transmitted through The amplifiers 74 and 75 perform the analysis of the cycle number by a cycle number analysis device (Hughett Packard Force, dynamic signal analysis device) 76, find the transfer function in the range of the cycle number, and then calculate the outward direction. Vibration frequency and natural vibration frequency outward 2 times. Next, based on Fig. 7 (B), the attenuation rate (| :) is calculated by the following formula (1) (2). ○ (1/2) X (△ ω η) X 1 〇〇 ..... (1 ) W2 ..... (2) In Fig. 7 (B) and formula (1) (2), is the number of cycles at the resonance point, τ〇 is the width at Ding / 2, and τη is the wave at the resonance point The vibration attenuation rate (%) of the tennis racket frame of Example 4 was 0649, and the vibration attenuation rate (%) of the second vibration was 1_409; on the other hand, the vibration attenuation rate of the tennis racket frame of Comparative Example 4 was one time. (%) Is 0.237, and the secondary vibration attenuation rate (%) is 0.438 ° Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Please read the precautions on the back before filling in this page) From the above results, you can confirm that The fact that the vibration attenuation of a tennis racket frame formed by an ionic polymer film interposed between epoxy resin impregnated carbon fiber prepregs laminated on top and bottom is significantly improved. [Effects of the Invention] It can be understood from the above description, In the present invention, in a matrix resin based fiber-reinforced plastic molded product composed of epoxy resin, the fiber layer is impregnated with the epoxy resin laminated on top and bottom At least part of ions intervention

A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention Displacement in the direction, and at the same time, the elastic force of the ionic polymer phase can effectively absorb the vibration caused by the shearing force between the epoxy resin impregnated reinforcing fiber layers that are laminated on top and bottom. Therefore, the molding can be greatly improved. High-performance fiber-reinforced plastic molded products with high impact resistance and vibration attenuation properties. In particular, a composite sheet formed by attaching an ionic polymer film to one side of a reinforced fiber-impregnated epoxy resin prepreg sheet. When the composite sheet is rolled into a hollow tube, and the above-mentioned epoxy resin is cured to form a hollow homogeneous molded product, the reaction efficiency of the ionic polymer film and the epoxy resin is good, and the resistance of the molded product is excellent. The impact strength and vibration attenuation have been improved. [Simplified description of the figure] 3 ... head is the fiber-reinforced plastic molded product of Example 1 of the invention Schematic cross-section view of the W-preparing material manufacturing process of the W-shaped tube) Figure 2: Schematic diagram for measuring the flexural strength of fiber-reinforced plastic molded products. Figure 3: Load and impact of fiber-reinforced plastic molded products Schematic of the method for measuring the amount of defects. (The maximum impact method is shown in the Γ diagram .: Measurement method of vibration attenuation rate of fiber-reinforced plastic molded products. Figure 5: (A) ~ (B) are the fiber-reinforced plastic composition of 眚 r $ 月 实 月 例 4 to complete the present invention. Open (tennis racket thick frame). Schematic cross-sectional view of the manufacturing process of compensation layer material (Please read the precautions on the back before filling this page}

19 ^ 0821 ^ 0821 V. A7 B7 Description of Invention (Π) Figure 6: The laminated material shown in Figure 5 is formed by a metal mold to form a rough frame of a tennis racket. Figure 7: (A) is a schematic diagram of a method for measuring the vibration attenuation rate of a fiber-reinforced plastic molded product, and (B) is a schematic diagram of the relationship between the cycle number and the transmission function obtained by analyzing the vibration input force and the vibration stress of a tennis racket in a cycle . Fig. 8: Schematic diagram showing the relationship between the torsional force of a fiber-reinforced plastic hollow tube molded product and the shearing force generated between the resin impregnated reinforcing fiber layers stacked on top of each other. Fig. 9 is an explanatory diagram of a component part of a tennis racket. Fig. 10: (A) (B) is a schematic diagram of the primary vibration mode and the secondary vibration mode in the direction of the tennis racket frame outside the direction of Hugh J Pingyue. &lt; Explanation of Symbols] 21 Core 22 66 Nylon Cylinder 23Α ~ 23D Composite Sheet 25.. Laminate 26... Overlapping Γ Please read the notes on the back before filling this page) Set the central standard of the Ministry of Economic Affairs The paper size printed by the Bureau ’s Consumer Cooperatives applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) 20

Claims (1)

496821 A8 B8 C8 D8 Patent Application No. 8 71017 5 No. 6 Patent Reexamination Application Patent Range Amendment ^ Revision Date: July 1990 1. A fiber-reinforced plastic molded product whose matrix resin is made of epoxy resin ' And the full length or a part of the full length between the epoxy resin impregnated reinforcing fiber layers laminated on top and bottom is sandwiched with an ionic polymer resin film having a glass transition temperature of 0 to 60 c &gt;c; the film is an ethylene-isobutyl Dilute acid copolymers are bridged with metal ions between molecules; the thickness of the film is 30 // m to 100 / zm. 2. The fiber-reinforced plastic molded article according to item 1 of the patent application scope, wherein the ionic polymer resin film is continuously sandwiched between the reinforcing fiber layers by more than 1/3. 3 · —A kind of fiber-reinforced plastic molded product, which is a composite sheet made of a film made of ionic polymer resin on one side of a prepreg sheet made of epoxy resin impregnated with reinforcing fibers. After the composite sheet is wound on a core covered with nylon 66 and laminated, the core is pulled out and formed into a hollow laminated tube. The film made of the ionic polymer resin is made of ethylene-methacrylate ♦ Cross-linking of metals with metal ions selected from Zn, Na, K or Mg, and their glass transition temperature is 0 ~ 6 (rc, thickness is 30 // 111 or more, 100 // m or less. 4. For example, a fiber-reinforced plastic molded product according to the scope of the patent application No. 3, wherein the film made of the ionic polymer is arranged to continuously surround the hollow tubular body for more than one week, and the two ends of the film in the circumferential direction are Yanzhe prepreg sheets are stacked on top of each other. (Please read the notes on the back before filling this page)