JPH0547170B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a fiber-reinforced resin fishing potato, which has particularly high strength, high elasticity, high impact resistance, light weight, and low cost.Furthermore, it can be colored in any color during manufacturing, and is suitable for use. In particular, it relates to fiber-reinforced resin fishing potatoes that are free from the risk of being struck by lightning. Glass fiber reinforced resin, which is made by reinforcing thermosetting resin with glass fiber, has been widely used as a material for fishing potatoes because it has high strength and elasticity, is relatively lightweight, and is easy to handle. ing. However, with the recent development of carbon fiber and its performance superior to glass fiber, the use of carbon fiber-reinforced resin for high-grade fishing potatoes is increasing. However, this carbon fiber-reinforced resin fishing potato is not without its drawbacks, and there are still some problems that remain to be solved. The biggest problem is that because carbon fiber is highly conductive, it acts like a lightning rod when used, inducing lightning strikes. In addition, carbon fiber is more expensive than glass fiber, and since carbon fiber itself is black, it is difficult to classify the quality, use, etc. by coloring when producing fishing potatoes, and carbon fiber reinforced Although resin has a lower specific gravity than glass fiber-reinforced resin, it is considerably heavier than water, so there is the problem that if it is accidentally dropped into seawater, it will sink in a short period of time. The present inventors focused on these circumstances, and in particular, improved the problems mentioned above with carbon fiber-reinforced resin fishing potatoes, such as lightning strikes, price, coloring, specific gravity, and improved strength, elasticity, etc. Various studies have been carried out in an attempt to develop fishing potatoes that can satisfy these requirements. The present invention has been completed as a result of such research, and its composition has a tensile strength of at least 20 g/denier and a tensile strength of at least 500 g/denier.
The gist is that the main reinforcing material is a high molecular weight polyethylene fiber having a tensile modulus of elasticity of g/denier and having countless longitudinal grooves on the fiber surface. The polyethylene fiber used as a reinforcing material in the fiber-reinforced resin fishing potato of the present invention has a flexible polymer chain, and has at least 20 g/denier, preferably
It has a tensile strength of 30 g/denier or more, especially 40 g/denier or more, and a tensile modulus of at least 500 g/denier, preferably 800 g/denier or more, especially 1000 g/denier or more, where the tensile strength is 20 g/denier or more. If it is less than denier or the tensile modulus is less than 500g/denier,
It has inferior strength and elasticity as a fishing potato, and cannot compete with glass fiber-reinforced resin fishing potatoes and carbon fiber-reinforced resin fishing potatoes. The flexible molecular chain referred to in the present invention refers to a molecular chain consisting of molecular bonds that can rotate when subjected to stress or heat, and is a molecular chain that constitutes wholly aromatic polyamide, wholly aromatic polyester, etc. is a rigid molecular chain and is not included in the flexible molecular chain referred to in the present invention. When polymers containing these rigid molecular chains are oriented in the fiber axis direction, their tensile strength increases, but their impact strength tends to decrease. Therefore, it is essential to solve these problems that the high molecular weight polyethylene fiber used as the reinforcing material for the fishing potato of the present invention is composed of flexible polymer chains. The polyethylene fiber used in the present invention is particularly high molecular weight polyethylene having a weight average molecular weight of 5 x 10 ⁵ or more, which is advantageous in terms of price and ease of spinning, and particularly has an impact strength of 3 x 10 ^-4 joules/denier. As mentioned above, it has also been found that the impact strength of the sweet potato is further improved when the content is preferably 4×10 ^-4 joules/denier or more. The matrix of the fiber-reinforced composite material of the present invention is
thermosetting polymer materials, thermoplastic polymer materials,
Suitable matrix materials include, for example, unsaturated polyester resins, epoxy resins, rubbers, etc., and low-temperature curing types are particularly suitable. Polyethylene fibers used as reinforcing materials are
Since the fiber itself has low heat resistance, in this case, vulcanization without softening is performed using already developed low-temperature curing technology or low-temperature vulcanization technology within a range that does not exceed the temperature at which the fiber softens (approximately 130°C). For example, when the matrix is an epoxy resin, rapid curing can be achieved by using a special catalyst such as an amine imide compound. The polyethylene fiber of the present invention must have numerous vertically long grooves on the fiber surface.
Polyethylene fibers that do not have multiple grooves are not preferred because they do not have good adhesion to the polymer compound used as the matrix. This multi-row groove is
The solvent can be applied by controlling the amount of solvent evaporated when drawing a polyethylene gel thread containing an appropriate amount of solvent. Furthermore, as a means of improving adhesion,
It is also very effective to treat the surface of the fiber with fluorine gas or with epoxy group-containing polyolefin, carboxylic acid group-containing polyolefin, chlorinated polyolefin, etc. before mixing with the matrix. The multi-row grooves mentioned here are countless multi-row grooves arranged in the fiber axis direction, and the multi-row grooves include 2 or more grooves, especially 5 to 5 grooves per 10 μm average distance in the outer circumferential direction of the cross section of the fiber. By arranging 50 pieces, the above-mentioned effect is clearly exhibited. The polyethylene fiber used as a reinforcing material for the fiber-reinforced resin fishing potato of the present invention may be a long fiber,
It may also be short fibers or pulp fibers cut into appropriate lengths. When used as long fibers, it is sufficient to simply align them. Plain weave, satin weave,
It can also be used as a woven fabric with various structures such as twill weave. Furthermore, if the above-mentioned polyethylene fiber reinforcing material is used alone without being used in combination with other reinforcing materials (especially carbon fiber), no matter what color tone or color is used as a matrix, the color tone will be the same for the reinforcing material. It is not impaired by the fibers, and the performance of the fibers can be fully demonstrated. However, in some cases, other fibers such as synthetic fibers such as polypropylene, polyacrylonitrile, and poly(vinylidene fluoride), wholly aromatic polyamide fibers, or glass/carbon fibers may also be used in combination with the present invention. It is possible as long as it does not cause any damage. The polyethylene fibers for reinforcing materials used in the present invention can be combined with the matrix resin after undergoing a spinning process and in the form or state that is normally available, either as is or after drying treatment. In addition, processing agents such as oils, finishing agents, etc. used in the silk-spinning process, which are necessary for the process, may be removed by extraction, etc. Furthermore, coupling agents, surface modifiers, or It is also possible to pre-coat with epoxy resin or the like and then combine it with matrix resin. In particular, treating the fiber surface with fluorine gas, epoxy-containing polyolefin, carboxylic acid group-containing polyolefin, chlorinated polyolefin, etc., as explained above, can improve adhesion with the matrix resin. Extremely effective. Next, a method for producing fiber-reinforced resin fishing potatoes according to the present invention will be briefly described. First, the fiber-reinforced resin is made by combining, for example, high molecular weight polyethylene with flexible polymer chains (for example, ultra-high molecular weight polyethylene with a weight average molecular weight of 1 x 10 ⁵ or more, preferably 1 x 10 ⁶ or more) with decalin, xylene or paraffin. After completely dissolving the polyethylene solution in a solvent such as the above at a temperature below the boiling point of the solvent, it is extruded into the air at room temperature, into water, or into a hollow tube equipped with a cooling device at a temperature at which the polyethylene solution does not solidify in the spinning device. Since the extruded yarn contains a solvent, it is heated in that state to an extent that the yarn does not melt, and then stretched in one or multiple stages so that the total stretching ratio is 10 times or more, preferably 20 times or more. Polyethylene fibers can be obtained by stretching and can be easily obtained by combining them with a matrix resin, either as is or by subjecting the fiber surface to a treatment to improve adhesion. The method for producing sweet potatoes in combination with matrix resin is not substantially different from the method for producing glass fiber-reinforced resin sweet potatoes or carbon fiber-reinforced resin sweet potatoes, and known methods can be applied as they are.
For example, a method of spraying or impregnating a fiber bundle aligned in one direction with a matrix resin or its solution and forming it into a potato shape, or a method in which the fibers are made into a woven fabric such as plain weave or satin weave and then the matrix resin is applied Alternatively, a method may be employed in which the solution is sprayed or impregnated, and then the material is rolled up to form a sweet potato shape and hardened. Furthermore, when forming the above-mentioned composite material, it is also possible to directly mold the matrix resin deposits on the reinforcing fibers by heating (pressurizing if necessary); In the case of thermosetting resins such as saturated polyester resins, the matrix resin is pre-impregnated into reinforcing fibers or fabrics, known as prepregs or polymics.
After curing to an intermediate stage called "R-stage", it is also possible to heat and pressurize the intermediate molding material under predetermined conditions. The fiber-reinforced resin fishing potato of the present invention is configured as described above, and the characteristics of the carbon fiber-reinforced resin fishing potato,
In particular, it has mechanical properties comparable to strength, elasticity, bending rigidity, etc., and since the conductivity of polyethylene fiber itself is low, there is extremely little risk of lightning strikes, etc., and polyethylene fiber is colorless to white. By mixing a coloring agent into the matrix, it can be colored in any desired color, and it can be classified by color according to the purpose (type of fishing fish, etc.), grade, etc. In addition, the fishing sweet potato of the present invention has a smaller specific gravity and is lighter than carbon fiber reinforced resin fishing potatoes as well as glass fiber reinforced resin fishing potatoes, so it is easy to transport and handle, and has a specific gravity relatively close to that of seawater. Even if it is accidentally thrown into the sea, it will not sink immediately and will remain afloat for a considerable time, making it easy to recover. In this case, if a void is formed in the center to the extent that it does not impair the mechanical properties such as bending strength required for the sweet potato,
Needless to say, subsidence when seawater is dropped can be more reliably prevented. Furthermore, since the present invention uses polyethylene fibers with good impact resistance for reinforcement, there is no risk of breakage even if subjected to impact during handling, and in addition, it is cheaper than carbon fiber reinforced resin fishing potatoes. It has many features such as being able to provide Hereinafter, reference examples regarding the manufacturing method and performance of the fiber-reinforced resin (composite material) used in the present invention will be shown, and then a manufacturing example of the fishing potato of the present invention will be explained. The method for measuring physical properties used in the evaluation of the following reference examples is as follows. [Tensile strength, tensile modulus and impact strength of fiber] According to the method specified in JIS-L 1013 (1981). [Bending strength and impact strength of composite material] According to the method specified in JIS-K 6911 (1978).
However, the size of the specimen is 3 mm in height, 25 mm in width, and length.
It was set to 63.5mm. Reference Example 1 Ultra-high molecular weight polyethylene having a flexible polymer chain with a weight average molecular weight of 1.8×10 ⁶ is dissolved in decalin to obtain a spinning stock solution, and then the spinning stock solution is heated in a spinning device at a temperature at which the polyethylene solution does not solidify. It is extruded from a spinneret into the atmosphere at room temperature and cooled to form a gel-like fiber. This gel-like fiber was stretched at a high magnification at various stretching ratios at a temperature at which the gel-like fiber would not melt, and a 1000d/200f multilayer film having the characteristics shown in Experiment Nos. 1 to 3 (invention) in Table 1 was drawn. Got filament. The surface of each multifilament was pretreated with water vapor for 30 seconds, and then exposed to 5% fluorine gas at room temperature for 30 minutes. The treated multifilaments were aligned using the filament winding method, and then mixed with an epoxy resin solution [Araldite LY564
(manufactured by Ciba Geigy)]. Next, these were cured at 80°C for 4 hours, and Experiment No. 1~ in Table 1 was prepared.
A composite material having the properties shown in 3 was obtained. Next, the 1000d/200f multifilament used in Experiment No. 1 was placed in a 20% dispersion of a copolymer of ethylene and glycidyl methacrylate (weight ratio 95:5) until the adhesion rate of the copolymer was 3% owf. It was immersed to make it look like this. The treated multifilaments were aligned by a filament winding method and embedded in an epoxy resin solution [Araldite LY564 (manufactured by Ciba Geigy)]. Then heat these to 80℃
After curing for 4 hours, a composite material having the properties shown in Experiment No. 4 in Table 1 was obtained. Next, as a comparative example, high molecular weight polyethylene having a flexible polymer chain with a weight average molecular weight of 1 x 10 ⁶ was dissolved in decalin to make a spinning stock solution, and then the spinning stock solution was heated in a spinning device at a temperature at which the polyethylene solution did not solidify. The fibers are then extruded from a spinneret into the air at room temperature and cooled to form gel-like fibers. This gel-like fiber was stretched at a lower stretching ratio than in Experiments Nos. 1 to 3 at a temperature at which the gel-like fibers were not fused.
A 1000d/200f multifilament having the characteristics shown below was obtained. After the surface of the multifilament was treated with water vapor for 30 seconds, it was treated with fluorine gas under the same conditions as in Experiments Nos. 1 to 3, and a composite material with epoxy resin was created under the same conditions as in Experiments Nos. 1 to 3. . The material properties of this composite material are shown in Experiment No. 5. Furthermore, for comparison, Table 1 shows Experiment No. 6 and Experiment No. 1 in Table 1.
1500d/1000f fully aromatic polyamide (polyparaphenylene terephthalamide) fibers and 1200d/1000f carbon fibers having the fiber properties shown in 7 were embedded in an epoxy resin solution (Araldite LY564), respectively. A composite material was obtained by molding under the same molding conditions as No. 3. The properties of these composite materials are also listed as Experiment No. 6 and Experiment No. 7.

【table】

[Table] As is clear from Table 1, the composite materials used in the present invention (Experiments Nos. 1 to 4) have well-balanced and high levels of bending properties and impact properties. It can be seen that this is extremely superior to Experiment No. 6, in which the reinforcing fibers are wholly aromatic polyamide fibers, and Experiment No. 7, in which the reinforcing fibers are carbon fibers. In addition, an experiment was conducted in which the same fibers as in Experiment No. 1 were used as reinforcing agents, and the fibers were treated with epoxy-containing polyolefin to improve surface adhesion before being mixed with the matrix.
Composite material No. 4 showed remarkable improvements in both bending properties and impact properties compared to composite material No. 1 in the experiment. Furthermore, the composite material of Experiment No. 5, which does not satisfy the fiber characteristic values specified in the present invention, has a fiber tensile height of 18 g/d and a tensile modulus of 370 g/d.
It can be seen that the improvement in both bending properties and impact properties is not significant. Reference Example 2 Ultra-high molecular weight polyethylene with a weight average molecular weight of 1.9 x 10 ⁶ was solution-spun, and the resulting gel fiber was drawn in multiple stages at a high magnification, resulting in a tensile strength of 32 g/d,
A 600D/100F polyethylene mulch with a tensile modulus of elasticity of 790 g/d and an impact strength of 4.2 x 10 ^-4 joules/d, with multiple grooves arranged on the fiber surface at least two per 10 μm of average distance in the outer circumferential direction of the fiber cross section. Got filament. In order to compare cases with and without multi-grooves on the fiber surface, solution spinning was carried out using polyethylene of the same high molecular weight as in the case with multi-grooves, and the resulting gel fiber was drawn using a solvent. Multi-stage stretching at high magnification by controlling the amount of evaporation of
×10 ^-4 joule/d, the appearance of multi-row grooves on the fiber surface is less than 2 per 10 μm of average distance in the outer circumferential direction of the cross section of the fiber, and virtually no multi-row grooves are observed.
A 600d/100f polyethylene multifilament was obtained. Using each of these multifilaments,
Each was woven into a 2×2 basket fabric. The former, ie, the fabric woven from fibers with multiple grooves, had a basis weight of 414 g/m ² , and the latter, ie, the fabric woven from fibers without multiple grooves, had a basis weight of 412 g/m ² . After impregnating each fabric with a liquid consisting of 100 parts of unsaturated polyester resin [Yupica 7512 (manufactured by Upica Japan)] and 1 part of benzoyl peroxide,
By laminating 10 sheets and hot pressing at 100°C, a molded product with a thickness of 5 mm and a fiber content of 65% by weight was obtained. In the former case, the bending strength of a molded product made of fibers with multiple grooves is 112Kg/mm ² , and the Izot impact strength is 370Kg/mm 2 .
cm/cm, and the bending strength of the latter, that is, the molded product made of fibers without multiple grooves, was 92 Kg/mm ² and the Izot impact strength was 323 Kg·cm/cm. As is clear from this reference example, it can be seen that by using fibers having a large number of grooves on the surface, the adhesion between the polyethylene fibers and the matrix resin can be significantly improved. Experimental Example The multifilaments (1000d/200f) after the fluorine gas treatment obtained in Experiments Nos. 1 to 4 of Reference Example 1 were arranged parallel to each other in a sheet shape, and then mixed with an epoxy resin solution [Araldite LY564 (manufactured by Ciba Geigy)] (manufactured by Ciba Geigy) (impregnation rate 40%) and each of the above multifilaments are plain woven and impregnated in the above epoxy resin solution (impregnation rate 40%)
A fabric prepreg (B) was prepared. Next, after applying a silicone mold release agent to a steel mandrel with an outer diameter of 8 mm, the fabric prepreg (B) is wrapped twice around the outer periphery of the mandrel, and then the prepreg (A) is placed on top of the fabric prepreg (A) so that the fiber axis direction is on the mandrel. was wrapped four times in the longitudinal direction, and the fabric prepreg (B) was further wrapped twice on top of it. Next, a wrapping tape coated with a silicone mold release agent is wound on top of the prepreg wound layer, and then heated at 80°C for 4 hours to harden the epoxy resin of the prepreg, and then the mandrel is removed and the wrapping is removed. Then, a tube of sweet potato was obtained. This raw pipe was cut into 300 mm pieces, and the bending strength and bending elastic modulus were measured using a universal testing machine "AUTOGRAPH" IS-5000 manufactured by Shimadzu Corporation. For comparison, prepregs (A) and woven prepregs (B) were obtained in the same manner as above except that the carbon fiber used in Experiment No. 7 of Reference Example 1 was used as the filament, and then fished in the same manner. A potato tube was manufactured and its bending strength and bending elastic modulus were measured. As a result, no substantial difference was observed in terms of bending strength and flexural modulus between the sweet potato reinforced with polyethylene fibers and the sweet potato reinforced with carbon fiber. In addition, the former (fishing potato tubes of the present invention) are all milky white, and it is clear that they can be easily colored by adding a coloring agent to the epoxy resin, but the latter (conventional fishing potato tubes) was black, and it seemed difficult to color it with a coloring agent. Furthermore, the specific gravity of the latter was approximately 1.6, which was considerably higher than that of water, whereas the latter had a specific gravity of approximately 1.2, making it extremely lightweight. Furthermore, the latter has a good electrical conductivity of 1×10 ² Ω ^-1 cm ^-1 , while the former has a conductivity of 1
×10 ^-15 Ω ^-1 cm ^-1 , which is rather close to an insulating material, and it is clear that there is almost no danger of lightning strikes.

Claims (1)

[Scope of Claims] 1 The main reinforcing material is a high molecular weight polyethylene fiber having a tensile strength of at least 20 g/denier and a tensile modulus of at least 500 g/denier, and having countless longitudinal grooves on the fiber surface. A fiber-reinforced resin fishing potato characterized by: (2) The fiber-reinforced resin fishing potato according to claim 1, wherein the polyethylene fiber has an impact strength of at least 3 x 10 ^-4 joules/denier. 3. The fiber according to claim 1 or 2, wherein the polyethylene fiber is surface-treated with at least one compound selected from epoxy group-containing polyolefin, carboxylic acid group-containing polyolefin, and chlorinated polyolefin. Reinforced resin fishing sweet potato.