JP2010084312A - Entangled glass strand and method for producing the same, and draw molded material of fiber reinforced resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide glass strands capable of sufficiently reinforcing concave-convex parts of screw heads and being produced in economically excellent production cost when producing a fiber reinforced resin composite material composing a screw material such as a bolt, and draw molded materials of a fiber reinforced resin obtained by using the glass strands. <P>SOLUTION: An entangled glass strand S in which two or more glass strands are mutually entangled is provided. In the glass strand, the entangled yarn count of the entangled glass strand to the sum total value of yarn counts of two or more glass strands is large in the rage of 3.0-18.0% both inclusive, and tensile strength according to JIS R3420 (2006) is not less than 100 MPa. The method for producing the entangled glass strands S is to loosen the strands to be larger so that the entangled yarn count against the strand count is in the range of 3.0-18.0% both inclusive. The draw molded material of the fiber reinforced resin contains the entangled glass strands S at 30-50 vol.%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an entangled glass strand, a method for producing the entangled glass strand, and a glass fiber reinforced resin pultruded material having high mechanical strength obtained by using the entangled glass strand.

  Glass fibers used as a structural material are used in various applications due to their excellent functions, and the value of fiber reinforced resin composites using glass fibers is extremely high. Fiber reinforced resin composites that use highly versatile glass fibers such as E-glass are cheaper and easier to use and easier to use than other fiber reinforced resin composites such as carbon fibers or alumina fibers. Because of this, the range of use has been extended to a wide range. Although composite glass fiber is inconspicuous, its value as a structural material is extremely important in various fields.

  The main purpose of using glass fibers as a structural material is to improve the strength of fiber reinforced resin composites. For this reason, glass fibers are used as various members such as building materials and structural materials used for applications requiring high strength. Various methods are used for molding such a fiber reinforced resin composite according to the application. For example, in the reinforcement in the two-dimensional direction, spray-up and SMC that cuts and uses glass roving, various injection methods using glass fabrics and mats, etc. can be mentioned. And the filament winding method. Among them, the pultrusion molding and the filament winding method are suitable for unidirectional reinforcement, that is, reinforcement having directivity, and the product is used after thoroughly examining the reinforcement direction.

  A product obtained by pultrusion using a unidirectional reinforcing material having such directivity is excellent in tensile strength characteristics in the direction in which the fibers are arranged, but there are cases in which satisfactory performance cannot be exhibited by itself. For example, with regard to the strength of members that require complex structures, such as structures having screw thread parts such as bolts and nuts, this molding method is sufficient for the direction of the force acting on these members. Cannot handle. Therefore, in order to avoid such a problem, many inventions have been made so far. For example, in Patent Document 1, a rod body of fiber reinforced resin in which a reinforcing fiber string formed by knitting or twisting a plurality of reinforcing fiber yarns is arranged at least in a screw forming portion is formed, and the dedicated body is formed into a predetermined screw material. An invention relating to a method of manufacturing a synthetic resin screw material that is inserted into a mold and forged in the longitudinal direction is disclosed.

  Further, in Patent Document 2, a core body is constituted by a concavo-convex structure composed of a core material in which filaments are gathered and a filament provided on the outer periphery thereof, and a screw material is constituted by the core body and a synthetic resin liquid impregnated therein. Further, there is disclosed an invention in which a screw body is formed from a suitably hardened screw material, and a male thread portion of the screw body is formed of a filament having an uneven structure to form a fiber reinforced synthetic resin bolt.

  Patent Document 3 describes a light-weighted bolt / nut that improves the strength of the threaded portion and also has chemical resistance, and is radially oriented in the axial direction of the bolt or nut on the threaded portion of the bolt or nut. An invention relating to plastic bolts and nuts in which a quality reinforcing material is embedded is disclosed.

  Further, in Patent Document 4, in order to improve the problem that the reinforcing effect in the length direction inherent to the fiber in the invention of Patent Document 2 cannot be sufficiently exhibited, a plurality of fibers are arranged substantially in parallel in the axial direction of the bolt. In the fiber reinforced synthetic resin bolt, an invention of a fiber reinforced synthetic resin bolt having a configuration in which fibers are disposed in a plane substantially perpendicular to the bolt axis is disclosed.

JP-A 63-224930 JP 7-279933 A JP 7-217629 A JP 2003-56536 A

  However, the inventions disclosed so far are not sufficient. A molded product obtained by a manufacturing method such as Patent Document 1 or Patent Document 2 needs to have a high fiber content because of its configuration, and compression molding is low in productivity, both of which tend to increase costs. Is a big one. In addition, the configuration shown in Patent Document 3 or Patent Document 4 is troublesome in the manufacturing method, and thus has a problem of cost increase. That is, when considering the improvement of the strength in the other direction of the fiber reinforced resin material having the directivity reinforced in one direction, while considering the point of how to orient the fibers other than in one direction, It is necessary to ensure productivity when realizing the configuration. In order to improve productivity, it is important that the method allows continuous production. In consideration of these points, when manufacturing a fiber reinforced resin material reinforced in one direction, the structure of the glass fiber used has no manufacturing problems when using the pultrusion molding or the filament winding method. It is important that it does not occur.

  In view of the situation, the present invention is a fiber that can sufficiently reinforce the uneven portion of a screw thread when manufacturing a fiber reinforced resin material constituting a composite material having a complicated structure such as a screw material such as a bolt. An object of the present invention is to provide an entangled glass strand that has a structure and can be produced economically at an excellent manufacturing cost, a method for producing the stranded glass strand, and a glass fiber reinforced resin pultruded material obtained by using the entangled glass strand. It is.

  The present inventor has conducted research related to glass fibers used for obtaining a composite material having a strength performance that is difficult to cope with only with a reinforcing property having directivity in one direction such as a screw material for many years. And in this research, as a method for producing a glass fiber reinforced resin composite material for obtaining a glass fiber reinforced resin composite material that is economically easy to produce glass fibers and composite materials and that can realize sufficiently high reinforcement. , Selecting pultrusion, and finding glass fiber in which a plurality of fibers that can impart anisotropy to fiber orientation in the pultrusion process are entangled as an optimum glass fiber that can be applied to this pultrusion process. The contents are disclosed.

  The entangled glass strand of the present invention is an entangled glass strand in which two or more glass strands are entangled with each other, and the entangled glass strand has 3.0% of the entangled glass strand relative to the total value of the two or more glass strands. The tensile strength according to JIS R3420 (2006) is 100 MPa or more, which is large within the range of 18.0% or less.

  Here, it is an entangled glass strand in which two or more glass strands are entangled with each other, and the entangled count of the entangled glass strand is 3.0% or more and 18.0% with respect to the total value of the count of the two or more glass strands. The point that the tensile strength according to JIS R3420 (2006) is 100 MPa or more which is large within the following range will be described below. The entangled glass strand is a state in which two or more glass strands in which a plurality of glass filaments are bundled are entangled spirally with each other in the strand direction, and none of the strands form a straight core wire. It is a glass strand exhibiting. In the present invention, the “entangled count” represents the count of the strands in the entangled state, and the “counter” represents the count of each strand after being divided and unwound from the entangled state (that is, before entangled). Is. That is, the entangled glass strand of the present invention has two or more glass strands in which a plurality of glass filaments are bundled, and these glass strands are entangled with each other in a slack state. And the entanglement count of the entangled glass strand is larger than the total value of the strand count of each of the two or more glass strands constituting the entangled glass strand within a range from 3.0% to 18.0%. Furthermore, when measurement of the tensile strength in the longitudinal direction of the entangled glass strand is performed according to JIS R3420 (2006), the value is 100 MPa or more. That is, the entanglement count of the entangled glass strand is determined by the degree of looseness of each glass strand constituting the entangled glass strand, and the total value of each strand before entanglement, that is, each glass strand constituting the entangled glass strand It is larger than the sum of the numbers. This means that the size of the entanglement count is in the range of 103% to 118% when the total value of the counts of the strands before entanglement is 100. In other words, the entangled glass strand is a tangled count of the entangled glass strand after the glass strand is entangled with respect to the total value of the count of each glass strand divided and unwound from a plurality of strands constituting the entangled glass strand, It is in the range of 3.0 to 18.0%.

  As described above, as a method for obtaining an entangled glass strand by loosening the filaments constituting the glass strand and then entwining a plurality of glass strands in a state where the filament is loosened, in the present invention, for example, from two directions It is only necessary to perform interlacing processing of air mixed fibers in which strands are inserted into nozzles through which compressed air flows, and more preferably, a two-feed method in which glass strands are introduced and entangled from two directions may be employed. In this two-feed method, it is possible to loosen the filament of the glass strand by passing it through compressed air in a state where there is a difference between the insertion amount and the winding amount of the glass strand. At this time, when a difference is caused between the insertion amounts between the glass strands to be inserted, a glass strand forming an axis and a glass strand entangled with the glass strand are formed, in addition to the slackness of the filaments constituting each glass strand, When these glass strands are loosened and entangled, a larger slack can be formed. In this case, the glass strands in the loosened state of the filament can be entangled by inserting them into a nozzle through which compressed air flows by inserting them into a nozzle through which compressed air flows. Since the number of glass strands to be inserted can have a tendency to be easily entangled, it is preferable to increase the number of glass strands. However, when the strand is passed through such compressed air, the filament is broken and broken and cut simultaneously with the loosening of the filament, resulting in a decrease in the tensile strength of the processed strand. As for the air fiber mixing method, the interlacing process has been described above, but a taslan process or a process using a swirling airflow may be used as necessary.

  From the above viewpoints, according to the inventor's research on the glass strand entanglement suitable when adopting molding based on the pultrusion method or the filament winding method, the value is determined by the entanglement count of the entangled glass strand. Further, the entangled glass obtained by increasing the entangled glass strand within a range of 3.0% or more and 18.0% or less than the total value of the counts of the two or more glass strands before being deflated. It has been found that a strand having a tensile strength according to JIS R3420 (2006) of 100 MPa or more can exhibit excellent performance.

    The increase in the entanglement count of the entangled glass strand is less than 3.0% of the total value of each of the two or more glass strands before the relaxation, that is, before relaxation, of the two or more constituting the entangled glass strand. Since the degree of looseness (also referred to as the degree of relaxation) is small, even if the tensile strength in one direction is high, the strength in the direction perpendicular to that direction is not sufficiently high. As a result, the entangled glass strands thus obtained are insufficient for use as, for example, a screw material. On the other hand, when the increase in the entanglement count of the entangled glass strand exceeds 18.0% of the total value of the respective glass strands before loosing each of two or more of the entangled glass strand, When the fibers are passed through the compressed air during the production of the strands, the filaments are easily damaged by contact between the filaments or contact with the nozzle wall. For this reason, when the tensile strength of the obtained entangled glass strand is measured, the variation becomes large, the quality of the tensile strength is not stabilized, and the yield rate may be lowered. Moreover, if the tensile strength according to JIS R3420 (2006) of the entangled glass strand is less than 100 MPa, it may be difficult to exhibit sufficient mechanical performance in actual use, which is not preferable.

  In order to check the count of each of the two or more glass strands constituting the entangled glass strand, the entangled glass strand is released and the count of each strand is measured. The strand count is a numerical value expressed in grams per 1000 m of the strand length, and the entangled glass strand is a numerical value expressed in grams per 1000 m of the entangled glass strand length. Therefore, when the size of the entangled glass strand with respect to the total value of the glass strands constituting the entangled glass strand is expressed in%, before the entangled count of the entangled glass strand is entangled Is a value obtained by multiplying 100 by the value divided by the total value of the counts of the glass strands.

  As a specific method for confirming the slack state of each strand constituting the strand with respect to the obtained entangled glass strand, for example, the following may be performed. First, the obtained entangled glass strand is drawn by a measuring instrument A shown in FIG. 2 so that the most tensioned filament is aligned with a load of 100 g in the longitudinal direction of the strand and cut into a length of 1 m. To do. What is necessary is just to prepare a 100-g load with a weight etc., for example. That is, for example, 50 g of weights may be suspended at both ends to align the strands. Here, the measuring instrument 10 shown in FIG. 2 (A) has a steel plate T provided with a support P and a cutting blade C, and the entangled glass strand is shown in FIG. 2 (A). When cut by the cutting blade C, the 1-m long entangled glass strand is accurately cut. Next, the mass of the 1-m entangled glass strand after cutting is measured, and the entangled count of the entangled glass strand is calculated. The entanglement count is a numerical value expressed in grams per 1000 m of a strand length measured by using a reference device such as a measuring instrument.

Next, the total value of the counts of the strands constituting the entangled glass strand is measured as follows. First, an operation of dividing and unwinding a plurality of strands constituting the entangled glass strand into respective strands is performed. As a method of dividing and unwinding every entangled strand, first, the end of the entangled glass strand is fixed with an adhesive tape or the like so that the position of the filament does not shift. Locate looking for the most slack portion that entanglement fixed entangled glass strands, for securing the strands S ₁ of one as shown in FIG. 2 (B) in a portion slack, put the needle H, one other interlaced strands strand S ₁ and divides unwinding. At the time of unwinding, the entangled portion is twisted, so the needle H is moved along the strand length direction while rotating the end fixed with the adhesive tape or the like in the direction R that can be unwound. Then, the entangled strands are divided and unwound in order. If there is a part that is further loosened with respect to the entangled strands that have been divided and unwound, the same operation is repeated to gradually unravel the entangled strands. For each strand constituting the entangled strands thus split and unwound, the count is measured using the inspection scale A shown in FIG. That is, a load of 100 g is applied in the longitudinal direction of the strands, the strands that have been loosened by the entanglement process are aligned, their lengths are measured, the mass of each strand is measured, and the entangled glass is measured based on these measurements. The count of the glass strand before constituting the strand can be obtained. The total value can be calculated by summing the count values of the respective glass strands.

  As another method, the count of each glass strand constituting the entangled glass strand may be obtained by the following procedure. For each strand constituting the entangled strands split and unwound by the above-described method, first, the method B (cross-sectional method) described in “7.6 Single Fiber Diameter” of JIS R3420 “General Test Method for Glass Fiber” (2006) ) To measure the single fiber (monofilament) diameter and the number of filaments of each strand. Since the density of the glass is found from the type of the glass material, the count 1 before processing is calculated from the single fiber diameter and the number of filaments according to the following equation (1).

  Moreover, the ignition loss and moisture content of the entangled glass strand are measured according to JIS R3420 (2006), and the count 2 before processing is calculated by the following equation (2).

  The overall count increase rate can be calculated from the total value of the counts 2 before processing of the strands constituting the entangled glass strands thus obtained and the entangled counts of the entangled glass strands measured previously.

  In addition to the above, the entangled glass strand of the present invention is the total value of the glass strands of the group of small slackness and the total value of the number of glass strands of the group of large slackness among all the strands constituting the entangled glass strand. If the ratio is greater than 1: 1 and within a range of 1: 3 or less, the slack glass strand is effective in the direction perpendicular to the one direction in addition to the directivity in one direction. In the process of reinforcing and compounding glass strands into resin materials, it is difficult for the glass filaments constituting the entangled glass strands to be broken, so that a composite material that sufficiently satisfies the design strength can be obtained. It becomes. Moreover, since the ratio of the entangled strands with large slackness in the entangled glass strands increases, the glass strands are more orientated in the other direction in the drawing process when the composite resin material is formed.

  The glass strands of the group of small slackness or the glass strands of the group of large slackness are all in a state where one entangled glass strand is released and compared with each other per 10 m of entangled glass strand, the degree of slackness is small and the strand length This means a group of short strands and a group of strands having a large degree of looseness and a long strand length. Incidentally, in the present invention, “group” is used to represent one glass strand, or a bundle of one or more glass strands, that is, one or more glass strand bundles. That is, one group may be one glass strand or a bundle of two or more glass strands.

  The ratio of the total number of counts of the glass strands of the group of small slackness to the total number of counts of the glass strands of the group of large slackness among all the strands constituting the entangled glass strand is greater than 1: 1, When the total value of the glass strands of the group of small slackness is 1, the total value of the number of the glass strands of the group of large slackness is more than 1 and 3 or less. The count of the glass strand is configured to be within a predetermined range so as to be in the range up to the value. When the ratio of the number of the glass strands of the group of small slackness to the glass strand of the group of large slackness is larger than 1: 1 and exceeds the range of 1: 3 or less, that is, the number of the glass strands of the group of small slackness When the total value is 1, when the total value of the counts of the glass strands having a large slack is 1 or less, sufficient composite reinforcement cannot be achieved even if combined with the resin. On the other hand, when the total value of the glass strands of the group of small slackness is 1, when the total value of the glass strands of the group of large slackness exceeds 3, as described above, the glass strands are combined. This is not preferable because there is a problem that a desired strength is not obtained because a problem such as cutting occurs in an operation, for example, a pultrusion operation.

  If the entangled glass strand of the present invention is used for a fiber reinforcement by the pultrusion method in addition to the above, since the production of the composite material is performed by the pultrusion molding conventionally used, It is not necessary to provide such facilities, and since the technology related to the pultrusion method accumulated so far can be applied, a stable fiber reinforced material can be obtained economically and preferably.

  When the pultrusion method is used to obtain a fiber reinforcement, a fiber reinforced resin material in which strands are arranged in the drawing direction is obtained by impregnating a glass strand with resin, passing it through a heated mold, and drawing it out. It is done. Therefore, the tensile strength in the drawing direction is very high. However, the strength in directions other than the drawing direction is weak, for example, bending strength and shear strength are weak. In order to improve the bending and shear strength, it is important to orient the strands in a direction other than the drawing direction. By using the entangled glass strand of the present invention, that is, the glass strand in which the loose strands are entangled with each other, it is possible to orient the fibers in a direction other than the drawing direction in the step of drawing the fibers in the pultrusion molding. In addition, if this method is used, the productivity is good and the production can be performed with high efficiency. Further, when glass fiber is used as a fiber in pultrusion molding, there is a problem that the filament is cut. However, as described above, the ratio of the entangled count with the glass strand having the largest slackness is larger than 1: 1, and 1: 3. If it is within the following range, it can also be improved. Thus, the entangled glass strand of the present invention has a configuration particularly suitable for the pultrusion method.

The glass composition of the entangled glass strand of the present invention is not particularly limited as long as desired performance can be exhibited. However, it is preferable to apply the present invention to the present invention since the manufacturing method is established for E glass that is inexpensive and used in the largest amount. In addition to E glass, the glass composition is expressed in terms of oxide percentage by mass, for example, SiO ₂ 54 to 65%, ZrO ₂ 14 to 25%, LiO ₂ 0 to 5%, Na ₂ O 10 to 17%, K _2. O 0-8%, RO (however, R = Mg + Ca + Sr + Ba + Zn) 0-10%, TiO ₂ 0-7%, Al ₂ O ₃ 0-2%, more preferably SiO ₂ 57-64%, ZrO ₂ 16-24%, LiO ₂ 0.5-3%, Na ₂ O 11-15%, K ₂ O 1-5%, RO (provided R = Mg + Ca + Sr + Ba + Zn) 0.2-8%, TiO _{2 0.5%} to _5%, acid resistance indicating the _Al 2 O 3 0 to 1% can also be applied to the AR glass fibers having alkali resistance. In addition to the above, D glass, S glass, or other newly developed glass materials may be applied as necessary.

  The method for producing an entangled glass strand of the present invention is a method for producing an entangled glass strand in which two or more glass strands are entangled to obtain an entangled glass strand in a state where the glass strands are entangled with each other, and each glass strand before entanglement The entangled glass strand is produced by entanglement such that the entanglement count increases within a range of 3.0% or more and 18.0% or less with respect to the total value of the counts.

  Here, it is a manufacturing method of the entangled glass strand which entangles two or more glass strands and obtains the entangled glass strand in a state where the glass strands are entangled with each other, and the total value of each glass strand before entanglement The entanglement of the entanglement count so as to increase within the range of 3.0% or more and 18.0% or less is as follows. That is, in order to obtain a glass strand in which two or more glass strands in a relaxed state are entangled with each other, the entanglement of the glass fibers after entanglement with respect to the total value of the counts of the glass strands before making the entangled glass strands The state where the glass strands are loosened so that the tensile strength according to JIS R3420 (2006) of the glass fiber after being entangled is larger than the range of 3.0% or more and 18.0% or less, and is 100 MPa or more. Thus, entangled glass strands are obtained by entanglement.

  When manufacturing the entangled glass strand, if the increase in the entangled glass strands after the slackening is less than 3.0% after the slackening is less than the total value of the number of each glass strand before loosening However, it is difficult to ensure sufficient strength other than unidirectional strength when forming a composite material, without providing an anisotropy to the fiber orientation in the pultrusion process. Further, when the entangled glass strand is produced, if the increase of the entanglement count after the relaxation is more than 18.0% after the relaxation of the total count of the strands before the relaxation, It is not preferable because the glass filament is likely to be broken or cut during molding, and sufficient strength may not be exhibited.

  The entanglement count of the entangled glass strand after being relaxed is larger than the total value of the count before the relaxation of all the glass strands constituting the entangled glass strand by 3.0% or more and 18.0% or less. This can be realized by adjusting the amount of glass strand inserted and the amount of winding when producing the entangled glass strand by the two-feed method.

  In the manufacturing method of the entangled glass strand of the present invention, in addition to the above, the glass strand of the small slack group among all the glass strands constituting the entangled glass strand, the count increase rate A with respect to the count of the glass strand before loosening 1.5% or more and 8.0% or less, and the increase rate B of the glass strands of the group of large slacks with respect to the entanglement number of the glass strands before loosening is 4.0% or more and 28.0% or less If the ratio of A and B is in the range of 1: 2 to 1:10, it is preferable because a pultruded material having stable strength can be obtained when a pultruded material of glass fiber reinforced resin is obtained.

  When producing entangled glass strands, to increase the looseness while maintaining the tensile strength by the two-feed method, the rate of increase A in the number of glass strands in one direction is 1.5% to 8.0%. More effective when loosened to increase in the range, and loosened and entangled so as to increase the glass strand count increase B in the range from 4.0% to 28.0% from the other direction. In particular, the strands can be oriented in a direction other than the drawing direction. Moreover, it is more preferable that the ratio of the ratio of the strands having a small slackness and the strands having a large slackness is 1: 2 to 1:10. In order to make a large difference in the ratio of such slackness, it is conceivable that the strand once slackened with compressed air by the two-feed method is further entangled with compressed air or simultaneously entangled with compressed air. However, it is preferable to adjust by the amount of insertion into compressed air and air pressure at the time of confounding. When entangled with compressed air so as to achieve the above-mentioned slack ratio, the strands with small slackness act like shafts, and the strands with large slackness are greatly entangled with the shaft portion to become strands with greater slackness.

  Since the glass fiber reinforced resin pultruded material of the present invention contains the entangled glass strand of the present invention in a volume percentage display of 30% or more and 50% or less, the appearance as a structure is high without any problem. It has moldability and can exhibit desired performance in terms of performance with respect to various strengths.

  When the glass fiber reinforced resin pultruded material contains the entangled glass strand of the present invention in a volume percentage of less than 30%, it becomes impossible to maintain the shape of the product when performing pultrusion molding, and the obtained molded body In some cases, there is a molded article having a nest. On the other hand, when the glass fiber reinforced resin pultruded material has a content of the entangled glass strand of the present invention exceeding 50% in terms of volume percentage, the strand volume at the time of drawing becomes large, and the fiber orientation is forcibly drawn. As a result, the anisotropy of the strand is difficult to occur, and the effect of loosening the strand of the present invention cannot be obtained. As described above, the glass fiber reinforced resin pultruded molding material can easily orient the fibers in a direction other than the drawing direction by adjusting the entangled glass strand of the present invention to 30% or more and 50% or less by volume percentage display. It is possible to obtain a molded article of excellent quality without any problem in appearance. In a normal glass fiber reinforced resin pultruded material, if the strand used for reinforcement is reduced to 50% or less by volume percentage as in the present invention, voids are generated in the molded body, and the shape of the molded body cannot be maintained. It can lead to defects. When a suitable amount of the glass strand of the present invention is used, the strand becomes bulky in a slack state, and thus, when fully obtained the role of maintaining the shape of the pultruded molded body and further obtaining a molded product that does not require much strength characteristics Even so, the amount of glass fiber can be reduced, so that the manufacturing cost can be reduced. From the above viewpoint, the glass fiber reinforced resin pultruded molding material of the present invention is more preferably the above-described one as long as it contains the entangled glass strand of the present invention in a volume percentage display, more preferably 35 to 45%. This is preferable because an effect can be easily obtained.

  If the glass fiber reinforced resin pultruded material of the present invention is used as a screw material in addition to the above, even if the thread is processed by cutting the fiber reinforced resin composite material, etc. Since the cutting of the glass strand can be remarkably reduced, a screw material having high strength can be manufactured economically and inexpensively.

  When the glass fiber reinforced resin pultruded material of the present invention is used as the screw material, the strand is oriented in a direction other than the drawing direction in the pultrusion, so that bending and shear strength are improved in addition to the tensile strength in the drawing direction. Is made. In order to effectively utilize such characteristics, the screw material is a glass fiber reinforced resin pultruded material particularly suitable in the present invention. In other words, it is effective in producing a bolt or the like by preparing a pultruded rod using the glass strand of the present invention and cutting the unevenness of the thread portion. In this case, the helical structure formed by the thread of the screw material is improved in the strength of the thread processed on the surface of the bar due to the anisotropy of the entangled glass strand, so Strength and tensile strength as a screw material are remarkably improved. Moreover, if it is the form of the fiber of this invention, glass fiber will not be cut | disconnected at the time of pultrusion by selecting the best conditions.

  Such screw materials are used in various applications. For example, in a screw material used in the corrosion-resistant FRP field, when a fiber reinforced resin composite material is cut, a glass strand is exposed on the cut surface, but even in such a case, it has acid resistance and alkali resistance. When AR glass fiber is used, the cut surface exhibits excellent durability, and thus is effective in expanding the application of the glass strand or fiber-reinforced resin composite material of the present invention. The entangled glass strand composed of the AR glass fiber is formed into the form of the glass strand of the present invention, so that the filament constituting the strand is not cut and can be pultruded, and a functional fiber-reinforced resin composite material It is because it can obtain.

  (1) As described above, the entangled glass strand of the present invention is an entangled glass strand in which two or more glass strands are entangled with each other, and the entangled glass strand with respect to the total count of the two or more glass strands. The entanglement count is large within the range of 3.0% or more and 18.0% or less, and the tensile strength according to JIS R3420 (2006) is 100 MPa or more. It is possible to orient the fibers in a direction other than the direction. For this reason, when manufacturing the fiber reinforced resin material which comprises composite materials like screw materials, such as a volt | bolt, it can fully reinforce with respect to the external force added to the uneven part of a screw thread.

  (2) The entangled glass strand of the present invention is the sum of the counts of the glass strands of the group of small slackness in all the glass strands constituting the entangled glass strands and the sum of the numbers of the glass strands of the group of large slackness. If the ratio to the value is greater than 1: 1 and within the range of 1: 3 or less, the fiber orientation can be further changed while maintaining the tensile strength, and the desired strength can be obtained.

  (3) Moreover, if the entangled glass strand of the present invention is used for a fiber reinforcement by the pultrusion method, it is actually used at an economically inexpensive cost while suppressing the cutting of the glass fiber which is a problem at the time of molding. A composite material having superior strength can be obtained, and a composite material exhibiting desired mechanical performance can be obtained.

  (4) The method for producing an entangled glass strand according to the present invention is a method for producing an entangled glass strand in which two or more glass strands are entangled to obtain an entangled glass strand in a state where the glass strands are entangled with each other, each before entanglement. Since the entangled glass strand is produced by entanglement so that the entanglement count becomes larger in the range of 3.0% or more and 18.0% or less with respect to the total value of the glass strands of The glass strand fiber is less likely to be cut when the rouge method is applied, and as a result, the molded product obtained by applying the pultrusion method has a mechanical strength over time. It can be obtained.

  (5) The manufacturing method of the entangled glass strand of the present invention has a count increase rate A with respect to the count of the glass strands before loosening of the glass strands of the small slack group among all the glass strands constituting the entangled glass strands. 1.5% or more and 8.0% or less, the increase rate B of the glass strands of the group of large slack with respect to the number of the glass strands before loosening is 4.0% or more and 28.0% or less, and A If the ratio of B to B is in the range of 1: 2 to 1:10, an entangled glass strand that exhibits desired performance can be obtained by adjusting the amount of insertion into compressed air and the air pressure during entanglement. Therefore, an entangled glass strand having a predetermined anisotropy can be efficiently produced according to the performance required as a method of manufacturing a composite material or the performance of a molded composite material. Rukoto can. Further, in the production method of the present invention, it is possible to loosen the fiber greatly while maintaining the tensile strength, and when the composite material is produced by a molding method such as pultrusion, the orientation of the fiber can be changed and adjusted more greatly. Easy.

  (6) Since the glass fiber reinforced resin pultruded material of the present invention contains the entangled glass strand of the present invention in a volume percentage display of 30% to 50%, not only the tensile strength in the drawing direction but also bending, A glass fiber reinforced resin composite with improved shear strength can be obtained. In addition, the pultruded glass fiber reinforced resin composite material of the present invention is used as a screw material. Due to the anisotropy of the fiber, very high thread strength is obtained, and tensile strength when combined with bolts and nuts. Is significantly improved. The pultruded glass fiber reinforced resin composite material of the present invention exhibits high strength performance at an economical production cost, and can be applied to many structural materials.

  (7) If the glass fiber reinforced resin pultruded material of the present invention is used as a screw material, very high thread strength is obtained due to the anisotropy of the fiber, and when combined with a bolt and a nut, The tensile strength of is significantly improved. And since it has this high tensile strength, the glass fiber reinforced resin pultruded molding material of the present invention can obtain various inexpensive screw materials that are not easily deteriorated with time and have high durability.

The photograph of the entangled glass strand of this invention. It is explanatory drawing regarding the measurement of an entangled glass strand, Comprising: (A) is explanatory drawing of a measuring machine, (B) is explanatory drawing which concerns on the unraveling of an entangled glass strand.

  Hereinafter, the entangled glass strand of the present invention, the production method thereof, and the glass fiber reinforced resin pultruded material using the strand will be specifically described based on examples.

  Tables 1 and 2 show the performance of the entangled glass strand corresponding to the examples of the present invention and the glass fiber reinforced resin pultruded material using the entangled glass strand. In Tables 1 and 2, “AR” as the glass composition indicates that the entangled glass strand is a material of the AR glass composition, and “E” is the so-called nothing. It represents that the material is an E glass composition of alkali glass.

The entangled glass strands having the configurations shown in Table 1 and Table 2 are produced by the following procedure. First, a glass strand was continuously drawn out from a glass melting furnace using a heat-resistant bushing device and wound into a DWR (single strand) form. These entangled glass strands indicated as “AR” in Tables 1 and 2 are AR glass fibers (SiO ₂ 61.0% by mass percentage, ZrO ₂ 19.5%, LiO ₂ 1.5%. Na ₂ O 12.3%, K ₂ O 2.6%, CaO 0.5%, TiO ₂ 2.6%), and “E” represents E glass fiber (mass percentage notation SiO ₂ 58 %, Na ₂ O 0.3%, K ₂ O 0.1%, CaO 24.2%, TiO ₂ 0.2%, MgO 1.3%, SrO 0.1%, Al ₂ O ₃ 8.6%, B ₂ O ₃ 7.1%). At the time of winding, a sizing agent prepared and prepared in advance was applied to the surface of the glass filament drawn from the bushing using a roll method so that the loss on ignition was 0.1 to 0.8%. The component of the sizing agent includes a phthalic acid polyester resin or a bisphenol A type epoxy resin, and is composed of a methacrylic silane coupling agent (manufactured by Nippon Unica Co., Ltd.) and a polyamine lubricant. This DWR is obtained by concentrating several hundred glass filaments having a diameter of about 13 μm, adjusting the count to be 260 to 420 tex, and drying.

  The DWR thus obtained has a nozzle that entangles two or more glass strands with each other by using compressed air, and a two-feed type glass strand entanglement machine that can adjust the feeding speed and the winding speed of the glass strands respectively. The entanglement processing was performed by using. Specifically, the number of DWRs constituting each glass strand that is sent out from two directions so as to have the configuration shown in Table 1 is adjusted, the glass strands released from these DWRs are drawn out, and the compressed air The winding operation was performed by passing a flowing nozzle and using a winder. The count ratio was calculated according to the following equation (3) from the total count of the strands of the largely loosened group and the total count of the strands of the less slackened group, measured according to the count of JIS R3420 (2006).

In addition, the glass strands fed from each direction were entangled while adjusting the condition of the feeding speed and the winding speed so as to have a count increase rate as shown in Table 1. At this time, the pressure condition of the compressed air was adjusted in order to adjust the rate of increase in the strand count or to optimize the entangled state between the glass strands in the two directions. Specifically, the pressure of the compressed air used when feeding the glass strands so as to be entangled was adjusted to be in the range of 3 to 10 kgf / cm ² . In addition, when the winding speed condition is 250 m / min or less, the glass strands are easily adjusted to loosen each other. The glass strands thus entangled are measured according to JIS R3420 (2006) strand counts, and the respective entanglement counts constituting the entangled strands after processing with the respective strand counts before processing, According to the following formulas 4 and 5, the count increase rate and the count increase rate ratio were calculated. By the way, in this embodiment, the strands of unrelaxed strands before processing and the entanglement counts of the respective entangled strands constituting the entangled strands after processing are used. For example, the tangled glass strands after processing are used. Can be obtained by using a measuring instrument as described above to obtain a strand having a predetermined length, and then obtaining information on the unlaxed strand entanglement count before processing by a confirmation means for performing decomposition and unraveling.

With respect to the entangled glass strand in which the loose state of the glass strand was adjusted as described above, the maximum tensile load was measured according to the tensile strength measurement method of JIS R3420 (2006). The test was performed at a fulcrum distance of 250 mm and a tensile speed of 300 mm / min. The tensile strength was determined from the obtained tensile load using the entanglement count and density (E glass: 2.6 g / cm ³ , AR glass: 2.8 g / cm ³ ).

  Moreover, about ten entangled glass strands of 1 m obtained as described above, a release operation is performed to release the glass strands constituting the entangled glass strands, and the number of glass strands and the single fiber diameter. When measurement was performed and further calculated according to the equations (1) and (2), it was confirmed that the value of the entanglement count of the entangled glass strand was of a quality according to the design.

  The entangled glass strands thus obtained were immersed in a resin tank while being bundled from several tens to several hundreds. The entangled glass strand impregnated with the resin was passed through a mold at a speed of 120 mm / min, and pultruded. At this time, the fiber amount of the entangled glass strand was set to an amount sufficient to enter the mold entrance when the entangled glass strand impregnated with the resin was passed through the mold. The resin for forming the composite material is a vinyl ester resin (Lipoxy (registered trademark) R-802, manufactured by Showa Polymer Co., Ltd.), and is passed through a mold having an entangled glass strand set at about 140 ° C. As a result, a drawn bar was obtained. Thereafter, the drawn bar material was subjected to cutting of the unevenness of the thread portion by using a predetermined cutting device, and an M12 bolt was obtained.

  The screw material tensile load was measured as described above. First, two nuts (metal) are attached to the bolts made of the obtained pultruded glass fiber reinforced resin composite material. At this time, the distance between the two nuts was adjusted to 100 mm. In this state, using an autograph manufactured by Shimadzu Corporation, one nut was fixed to the pedestal, a wire was applied to the other nut and pulled upward at a speed of 5 mm / min, and the maximum load value was measured. After completion of the test, the test piece was incinerated in an electric furnace at 620 ° C. for 3 hours, and the volume percentage of the glass strand was determined from the mass reduction rate.

  As a result of the above evaluation, sample No. For 1 to 26, the count increase rate of the whole entangled glass strand is 3.7% or more and 17.5% or less, and the count increase rate of the strand with small slack is 1.8 to 8.0% and large slack The strand count increase rate is 5.4% or more and 25.1% or less, the count increase rate ratio is in the range of 1: 2.9 to 1: 8.6, and the count ratio is also 1: 1. .10 to 1: 2.93. That is, the rate of increase in the count of the entire entangled glass strand is 3.7% or more and 17.5% or less, which means that the entanglement count of the entangled glass strand with respect to the count of the glass strand is 3.0% or more and 18.0% or less. Within the scope, the requirement of the present invention is that it is an entangled glass strand. Also, the count ratio is within the range of 1: 1.10 to 1: 2.93, which means that the total value of the glass strands in the group with less slackness and the total value of the glass strands in the group with large slackness. The ratio of “1” is larger than 1: 1 and satisfies the requirement of 1: 3 or less. And the measurement result of the tensile strength according to JIS R3420 (2006) about this entangled glass strand was 120 MPa or more, and pultrusion molding was possible without thread breakage. And since the fiber volume percentage of the molded glass fiber reinforced resin pultruded material is not less than 32% and not more than 44%, when the screw material tensile load is measured, even the one with the smallest maximum load value is 10012N or more. It has been found that a sufficiently high tensile load can be obtained.

  On the other hand, as a comparative example, the sample No. 27-31 were prepared. Sample No. which is a comparative example. 27-31 produced the entangled glass strand in the same procedure as the Example, and obtained the glass fiber reinforced resin pultrusion molding material. Moreover, also about the test method of the various evaluation tests about a comparative example, it evaluated according to the setting and specification similar to an Example. As a result, as shown in Table 3, the count increase rate of the strands with small slackness is 0.4% and the count increase rate of the strands with large slackness is 2.4%. Sample No. 27 having a larger entanglement count after loosening by 1.5% showed a high tensile strength of 798 MPa, but a screw material strength of 7701 N. In addition, in the sample No. in which the rate of increase in the count of the strand having a large slack is 3.4% and the ratio of the rate of increase in the count is 1: 1.1. As for 28, the tensile strength was as high as 624 MPa, but the screw material strength was as low as 8204 N. In addition, sample No. with a ratio of the count increase rate of 1: 1.6. For 29, the tensile strength was as high as 423 MPa, but the screw material strength was as low as 8450 N. In addition, sample No. in which the count ratio of the strand having a large slack and the strand having a small slack is 1: 4.48. Sample No. 30 was 19.8% larger in the entanglement count after the relaxation than the total value of the counts of the respective strands before the relaxation. No. 31 had a tensile strength of 82 MPa and 78 MPa, which was less than 100 MPa. Many yarn breaks occurred during pultrusion molding, and molding was impossible.

  As described above, sample No. which is an example of the present invention. For Samples 1 to 26, Sample No. By comparing 27 to 31, the entangled glass strand of the present invention does not cause a decrease in strength due to the cutting of the glass strand even when the pultrusion method is applied when forming the composite material. Therefore, it was revealed that a glass fiber reinforced resin pultruded material having high screw material tensile strength can be formed.

  Here, the case where it is mainly applied to the pultrusion molding method is specifically described, but the entangled glass strand of the present invention is suitable for a glass fiber reinforced resin composite material molded by the filament winding method in addition to the pultrusion molding. It has properties. In the embodiments of the present invention, as an example of a glass fiber reinforced resin composite material, a case where it is applied to a screw has been described. However, other forms of composite materials such as plate materials, columnar materials, tubular materials, etc. Even when used as the present invention, the present invention exhibits high mechanical performance.

DESCRIPTION OF SYMBOLS 10 Measuring machine T Steel plate C Cutting blade P Strut R Rotating direction of entangled glass strand H Needle S Entangled glass strand S ₁ Strand which comprises entangled glass strand

Claims (7)

An entangled glass strand in which two or more glass strands are entangled with each other,
The entanglement count of the entangled glass strand with respect to the total value of the counts of the two or more glass strands is large within a range of 3.0% or more and 18.0% or less, and the tensile strength according to JIS R3420 (2006) is 100 MPa or more. An entangled glass strand characterized by that.   The ratio between the total value of the glass strands of the group of small slackness in all the glass strands constituting the entangled glass strand and the total value of the number of glass strands of the glass strand of the large slackness is larger than 1: 1, The entangled glass strand according to claim 1, wherein the entangled glass strand is in a range of 3 or less.   The entangled glass strand according to claim 1 or 2, which is used for a fiber reinforcement by a pultrusion method. Two or more glass strands are entangled, and a method for producing an entangled glass strand to obtain an entangled glass strand in a state where the glass strands are entangled with each other,
The entangled glass strand is manufactured by entanglement so that the entanglement count becomes larger within the range of 3.0% or more and 18.0% or less with respect to the total value of the glass strands before entanglement. The manufacturing method of the entangled glass strand characterized by the above.   Among the glass strands constituting the entangled glass strand, the glass strands of the small slack group have a count increase rate A of 1.5% or more and 8.0% or less with respect to the number of the glass strands before being slackened. The increase rate B of the glass strand of the large group of the glass strand relative to the count of the glass strand before being loosened is 4.0% or more and 28.0% or less, and the ratio of A to B is 1: 2 to 1:10 It exists in the range, The manufacturing method of the entangled glass strand of Claim 4 characterized by the above-mentioned.   A glass fiber reinforced resin pultruded material comprising the entangled glass strand according to any one of claims 1 to 3 in a volume percentage display of 30% to 50%.   The glass fiber reinforced resin pultruded material according to claim 6, which is used as a screw material.