JPS6359519A - Fiber reinforced drawn rod - Google Patents

Abstract

PURPOSE:To facilitate the fixing of the position of a carbon fiber two and at the same time cancel the untwisting torque and contrive to enhance the high straightness by a structure wherein reinforcing fiber filament bundles, which constitute the cross section, are arranged so as to form a radially symmetrical multilayer structure. CONSTITUTION:Reinforcing fiber filament bundles forming a central layer A and a peripheral layer B are impregnated with matrix resin solution and, after excess resin being squeezed out of the bundles, passed through a delivery guide so as to form the central layer and the peripheral layer and, after that, passed through a heating die for forming. Further, the resultant bundles are drawn through a two-step gripping system or caterpillar system drawing mechanism so as to be hardened and shaped simultaneously. When thermoplastic resin is employed as the matrix resin, the reinforcing fiber bundles forming the central layer and the peripheral layer are stratified by the delivery guide, and at the same time impregnated with molten resin and passed through the heating die so as to be shaped simultaneously with the resin impregnation in order to be drawn through the drawing device. Further, in order to obtain a high straightness after grinding, the preferable strain is 0.6mm or less at the middle of a span of 600mm in the stage or a stock rod.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a solid fiber-reinforced pultruded rod that can be used for various industrial applications such as fishing rod tips, axles for radio-controlled cars, various support rods, spring materials, and robot parts. Regarding.

[Conventional technology]

Pultruded rods reinforced with high-strength, high-modulus fibers such as carbon fiber have been used for various purposes, but their light weight,
Taking advantage of its high rigidity, it is ground into a tapered square shape and is often used as the tip of fishing rods. The straightness of a fishing rod tip after grinding is an extremely important factor in determining its commercial value, and those obtained by conventional pultrusion methods did not necessarily provide good straightness.

[Problem that the invention seeks to solve]

As a result of various studies to improve straightness performance, the present inventors found that
It has been found that the presence of reinforcing fibers such as carbon fibers has a significant effect on the straightness of pultruded rods. In particular, as a result of our study to obtain a high-strength, high-modulus fiber pultruded rod that has a high degree of straightness after taper grinding, we found that when using carbon fiber multifilament, it is said that it is desirable to have no twist. It's here (Japanese Patent Publication No. 54-21465, 5
No. 4-80372), however, in a pultrusion molded product consisting of a simple untwisted reinforcing fiber filament and a matrix resin, yarn fluctuation occurs during molding, making it difficult to obtain a product with high straightness at a high yield. The present inventors have discovered that straightness can be stably improved by creating a specific filament distribution structure within a pultruded rod, and have arrived at the present invention.

By providing a specific twisting structure, the present invention facilitates position fixing of carbon fiber tows, cancels untwisting torque, and achieves a high degree of straightness.

[Means for solving problems]

That is, the gist of the present invention is that, in a solid pultruded rod made of reinforcing fibers and a matrix resin that binds the reinforcing fibers, reinforcing fiber filament bundles constituting the cross section of the rod are arranged so that a bundle of reinforcing fiber filaments forms a center-symmetric multilayer structure. Reinforced pultruded rod.

The formed rod of the present invention includes a circular cross-section with a diameter of 1 to 10 m, a triangular to m-square regular polygonal cross-section, and a center-symmetric deformed cross-section thereof.

The reinforcing fibers used in the present invention are carbon fibers, glass fibers, wholly aromatic polyamide fibers, alumina fibers, boron fibers, SIC fibers, etc., and have a tensile strength of 100 to 7 m" or more, preferably 200 kg/state! or more, and a tensile modulus of elasticity. It is a high-strength, high-elastic modulus fiber of 5 t/m" or more, preferably 20 t/m" or more.

Moreover, the central layer (A) constituting the cross section of the pultruded rod of the present invention
, in the peripheral layers (B,, B!, Bn), the reinforcing fiber filament bundles used may be made of materials having the same properties and the same form, or may be made of materials with different properties and forms.

For example, as the material constituting the center layer (A), a circular bundle of untwisted filament bundles of reinforcing fibers, a thick denier unidirectionally twisted filament bundle made by gathering untwisted filaments and twisting them in one direction, or a filament bundle of S or A twisted yarn aggregate made by twisting in two directions and combining them appropriately, a multi-twisted filament bundle made by combining multiple filament bundles with one-way pre-twisting and twisting them in the opposite direction to the first twisting, and non-twisted or twisted filament bundles. A filament bundle, etc. that has been made into an entangled convergence structure by fluid injection treatment is used, and the material constituting the peripheral layer (Bn) is an untwisted filament bundle of reinforcing fibers, a filament bundle twisted in S or 2 directions, or a filament bundle twisted in S or 2 directions. A combination assembly of twisted filament bundles, a multi-twisted filament bundle made by combining multiple filament bundles with one-way pre-twisting and twisting them in the opposite direction to the pre-twisting, and entangling by fluid injection treatment on untwisted or twisted filament bundles. Filament bundles having a convergent structure can be used in appropriate combinations.

The twisted filament bundle used in the present invention has a twist coefficient L/D (L is the twist pitch and D is the apparent diameter of the fiber) of 1.
A value in the range of 0 to 1000 is preferable in terms of strength and straightness of the molded product.

For example, when the central layer (A) and peripheral layer (Bn) constituting the present invention are used after performing taper grinding, the central layer determines the strength, rigidity, straightness, etc. of the tip, and the middle layer and the outermost layer seems to play a role in determining the characteristics of the middle and base parts.

Therefore, the material and form of each layer can be set according to the intended shape, and the number and thickness of layers can also be designed and set as appropriate.

Among the multilayer structures in the present invention, the simplest structure is a two-layer structure consisting of a center layer (A) and a peripheral layer (B,), followed by a center layer (A) and an intermediate layer (B, ). , outermost layer (B,
) It is a three-layer structure consisting of

A more complex multilayer structure can be obtained by dividing the middle layer and the outermost layer, but from a practical standpoint, it is difficult to obtain the expected effect even with a five-layer structure or more.

Although the ratio of the thickness of the center layer and each layer can be set appropriately, the center layer is particularly important in determining the characteristics of the tip of the tapered grinding body at the tip, and is preferably located at the center ffjj(A)%.

Among the configurations of these fiber-reinforced pultruded rods, (a) a multi-twisted filament bundle, which is a bundle of unidirectional pre-twisted filaments and a plurality of filament bundles twisted in opposite directions, is arranged in the center layer, and S is placed in the peripheral layer;
Alternatively, a combination assembly of filament bundles twisted in two directions is arranged, or a filament bundle is arranged in the center layer with an interlaced convergence structure obtained by fluid injection treatment on untwisted or twisted filament bundles, and S or Z is arranged in the peripheral layer. A configuration in which a combination of directionally twisted filament bundles is arranged is particularly preferable from the viewpoint of obtaining a formed rod that has little distortion in the center and hardly bends even when taper-ground.

Matrix resins that bind filaments include thermosetting resins such as unsaturated polyester resins, vinyl ester resins, acrylic resins, and epoxy resins, nylon, polyester, polycarbonate, PPS, PES, and PEE.
A thermoplastic resin such as K can be used.

In addition, calcium carbonate at a rate of 1 to 10% as necessary,
Powders such as aluminum hydroxide and Teflon powder, milled fibers such as glass fiber and carbon fiber, glass beads, and phenol resin beads can be used in combination as fillers. The filler plays an important role in suppressing the formation of scale inside the die and preventing the occurrence of chipping of the product.

The method for manufacturing a pultrusion molded rod of the present invention will be specifically explained with reference to the case where a thermosetting resin is used as the matrix resin.

The reinforcing fiber filament bundles forming the center layer and the peripheral layer are impregnated with a matrix resin solution, the excess resin is squeezed out, and the reinforcing fiber filament bundles forming the center layer and the peripheral layer are passed through a delivery guide and passed through a heating die for molding in two stages. The pultruded rod of the present invention is obtained by drawing it out through a grip-type or endless track-type drawing mechanism, curing it, and shaping it at the same time.

When a thermoplastic resin is used as the matrix resin, the reinforcing fiber filament bundles forming the center layer and the peripheral layer are impregnated with molten resin while being separated by a delivery guide, and passed through a heated die and shaped at the same time as the impregnation. , through the previously described drawing device to obtain the pultruded rod of the present invention.

In the present invention, in order to obtain a high degree of straightness after grinding, the strain at the center per 600 silk length is set to 0.0 at the stage of the raw material rod.
The length is preferably 6 m or less.0 [Examples] The present invention will be specifically described below with reference to Examples.

The "straightness pass rate" with tip runout of 3 mx or less is 0.
7fl, taper ground to original 33.2 wx thickness 1
Hold the base of a 000w long drawing rod so that it can rotate, rotate it once, measure the tip deflection, and determine the percentage of tip deflection diameter of 3 Ill or less as the pass rate.

Example 1 Tensile strength: 350 kg/m2, tensile modulus: 24 t/w
, x” 6000 carbon fiber filaments with a filament diameter of approximately 7 μ are converged to an untwisted carbon fiber tow of 3 to 577
By adding a twist of M, impregnating it with unsaturated polyester resin, dividing it into a center layer (A) and a peripheral layer (B) through a delivery guide, introducing it into a thermoforming die, and pulling it out by a gripper-pulling mechanism. A carbon fiber reinforced pultruded rod of approximately 3B diameter was obtained. Its cross-sectional configuration was as shown in FIG. This molded product exhibits good straightness with an average distortion of less than 0.4 mx at the center per 600 crane lengths, and can be used for various purposes.It also has a 0.6-inch wing at the tip and a thickness of 2.8 silk at the base. Even with taper grinding, there is almost no bending, and the straightness, strength,
It was suitable as a fishing rod tip for snailfish, which has excellent fish sensitivity.

Example 2 Tensile strength 300 kl/lry", tensile modulus 30 t
12,000 meso-external carbon fiber filaments with a filament diameter of approximately 7μ are converged into a non-twisted carbon fiber tow (
A) was prepared, and the cross-sectional configuration as shown in FIG. 2 was prepared in the same manner as in Example 1, except that the main fiber was in the center and the standard type carbon fiber tow (B) used in Example 1 was placed around it. A pultruded rod was obtained.

This product has an average distortion of 0.3 at the center per 600mm length.
5n+ shows good straightness, tip 0.7 m, base 2
．． The one taper-ground to a thickness of 8 m had almost no bending, was slender and rigid, and was suitable as a fishing rod tip with excellent straightness, strength, and fishing sensitivity.

Example 3 1577M to the same carbon fiber tow used in Example 1
S-twist is applied, carbon fiber-fed tow (A) with a low twist number of 3 to 577M is placed in the center, and twisted yarn (B') is arranged in the periphery.
In the same manner as in Example 1, a pultrusion-molded rod having a cross section configuration as shown in FIG. 3 was obtained. The wooden product showed good straightness with an average distortion of 0.30 at the center per 600 sn length, and 0.30 at the tip.
Even when tapered to a thickness of 6 fl, base part 2, and 8 vx, almost no bending occurred.

Example 4 1s of the same standard carbon fiber tow used in Example 1
T/M S-twisted yarn and three of these S-twisted yarns are combined into one in two directions.
5 T/M twisted triple-twisted yarn, medium elastic carbon fiber prepared in Example 2, 1o T/M S-twisted yarn and 2-twisted yarn, and two of these yarns combined to make 10 T/M reverse twist. The double-twisted yarn thus prepared was prepared and pultruded rods having various two-layer structures each having a diameter of about 3 mm were obtained in the same manner as in Example 1.

The straightness and length of these products as raw material rods,
After grinding to a diameter of 0.7 m at the tip and a diameter of 2.8 tm at the base, the amount of deflection of the tip was measured, and the results shown in Table 1 were obtained.

Table 1 In the examples of the present invention, it was found that, compared to a simply drawn and pultruded product of carbon fibers, the central structure was stabilized by forming a two-layer structure, and the straightness after polishing was significantly improved. In addition, it has been found that the straightness of the material rod can be improved by using a multi-twisted yarn that is twisted in the center, then twisted in the opposite direction.

Example 5 Tensile strength 350 kg/m", tensile modulus 24 t/m"
600 carbon fiber filaments with a filament diameter of approximately 7μ
0 converged untwisted carbon fiber tow with 15 T/M S
After twisting, the ratio of twist pitch (L) to tow diameter (D),
A twisted yarn having a L/l) of approximately 150 was obtained.

This twisted yarn is pulled together to form a center structure and a periphery-center symmetrical structure, and is drawn through a heated circular cross-section die impregnated with vinyl ester resin to form a circular solid drawing with a diameter of approximately 3 fl. A shaped rod was obtained.

This circular solid drawing rod has 0 distortion in the center per 600W length.
．． It is less than 6 vg and the tip is 1.0! Ill, former part 2.
A fishing rod tip material with almost no bending was obtained even after 8 rounds of taper polishing.

However, when the circular solid pultruded rod was finished into a tapered abrasive product having a thinner tip with a tip diameter of 0.6 mm and a diameter of 2.8 fi, slight bending occurred at the tip.

Example 6 The untwisted carbon fiber tow used in Example 5 was aligned with the twisted yarn tow so that three of them constituted a central axis. After impregnated with vinyl ester resin, the tow was passed through a heated circular die and pulled. By punching, a circular solid pultruded rod having a diameter of about 3n+ and a central distortion of 0.4 beads or less per 600n length was obtained. When this pultruded rod was finished into a tapered abrasive product having a tip length of 0.6 m and a thin base portion 268B, a highly straight fishing rod tip material was obtained.

Comparative Example 1 The untwisted carbon fiber tows in Example 5 were arranged so as not to form a center layer, and the same procedure as in Example 5 was carried out to form approximately 3 squares in diameter.
A circular solid pultruded rod having a center strain of 0.611 or less per length of 600W was obtained.

When tapered abrasive products with a tip of 1.0 IK and a base of 2.8 IK were produced from this pultrusion rod, products with good straightness and products with one bend were produced at a ratio of about 50%.

Example 7 After applying S twist of 15 T/M to the untwisted carbon fiber tow in which 6000 carbon fiber filaments used in Example 5 were bundled, the two fibers were combined to have a twist of 15 T/M. By applying two twists, 12,000 double twist yarns were obtained.

Using twisted yarn, this 21 is passed through a heated circular cross-sectional die impregnated with vinyl ester resin in the same manner as in Example 5 so as to form a center structure and a peripheral center symmetrical structure, and then pulled out. As a result, a circular solid pultrusion rod having a diameter of about 3 mm was obtained. This circular solid drawn rod has a center distortion of 0.4 disks per 600fl length, and is a fishing rod tip material that hardly bends even after taper polishing of 0.8 m at the tip and 2.8 mm at the base. was gotten.

Example 8, Comparative Examples 2 and 3 A carbon fiber filament with a tensile strength of 350 Yu/l 1K2 and a tensile modulus of 24 and a diameter of about 7μ is 600
An untwisted carbon fiber tow (Fo) with 0 fibers converged is twisted in the S direction at a ratio of 15 T/M to form a unidirectionally twisted yarn bundle (Fo).
I got it. Similarly, a yarn bundle (F,) twisted at 15 T/M in two directions was obtained.

In addition, a total of 3 S direction twisted yarn bundles (Fl) are 15 in 2 directions.
A 3-strand twisted yarn bundle (F,) was obtained by ply twisting at T/M.

A matrix resin stock solution obtained by blending an unsaturated vinyl ester resin with a peroxide catalyst and a filler consisting of aluminum hydroxide is prepared, and the above carbon fiber tow (F1? F'tl) is prepared.
FS) is impregnated with a resin liquid, and introduced into a thermoforming die through a delivery guide so that F is in the center and F is in the center, and Fl I Fl form a pair to form an intermediate layer B and a peripheral layer B. - By pulling out with a pulling mechanism, the diameter of carbon fiber with a volume content of 60% is approximately 3.5n.
A carbon fiber-reinforced pultruded rod was obtained. Its cross-sectional configuration is the fourth
It was as shown in the figure. This molded product showed good straightness with an average distortion of 0.4 ms or less at the center per 600n length. A 1000m long product with a tip of 0.7m and a base of 3
．． Even when taper grinding to a thickness of 2 dew, there is almost no bending, and the straightness pass rate with tip runout of 3 w or less is over 90%, and it has extremely high straightness, strength, and fishing sensitivity. It was suitable as a fishing rod tip.

In this example, a centrosymmetric multilayer structure could be easily obtained by dividing the resin-impregnated tow into layers using a delivery guide just before the die. Furthermore, the abrasion phenomenon caused by scale generation within the die was reduced by adding and blending aluminum hydroxide filler.

Example 9 (&) An untwisted filament bundle (F4) for layer construction was obtained by aligning three carbon fiber untwisted tow F0 described in Example 8, applying a sizing agent, and shaping it into a circle. .

(bl (al) Three non-twisted tows (Fo) similar to al were aligned and subjected to S twist of 10 T/M to obtain a unidirectionally twisted thick denier filament bundle (F,).

(cl Carbon fiber filament having the same characteristics as the carbon fiber untwisted tow described in Example 8) A carbon fiber tow in which 3000 carbon fiber tows were bundled was woven into a 20 T/M S-twisted yarn bundle (F, ) and a 20 T/M (7 ) Z twisted yarn bundle (F, ), (pm) −
A filament assembly was obtained by combining three and four (FW).

(dl) Three untwisted tows (Fo) were aligned and subjected to air jet treatment to obtain an interlace entangled yarn bundle (F,).

The various carbon fiber tows described in Example 8 and above (al to (di) were passed through the same process as in Example 8 to form a centrosymmetric multilayer structure similar to that shown in FIG. 4 having a diameter of about 3.5 nm. A carbon fiber-reinforced pultrusion molded rod was obtained.Table 2 shows the results of determining the material straightness of these molded products and the straightness pass rate with tip runout of 3fi or less.

For comparison, untwisted tow (Fo
), the data for a drawn pultrusion rod of twisted tow (F6) is shown.

Table 2 Example 10 Various carbon fiber filament bundles shown in Example 9; ■Glass fiber tow twisted yarn; ■Fully aromatic polyamide fiber (Kepler, trademark manufactured by DuPont) double-twisted yarn bundle; ■Alumina fiber hot to low twisted yarn bundle; (2) SiC fiber-free heat-twisted yarn bundle and (2) Boron fiber hot-to-low-twisted yarn bundle were prepared, and in the same manner as in Example 8, a pultrusion molded rod having a center-symmetrical multilayer structure and high material straightness was obtained. The straightness pass rate of these pultruded rods with a tip runout of 31 m or less was determined and was as shown in Table 3.

Table 3 [Effects of the Invention] The pultruded rod of the present invention is characterized in that reinforcing fibers are arranged in a plane constituting its cross section so as to form a center-symmetric multilayer structure, and more preferably in part or all of the reinforcing fibers. By using twisted yarn, the reinforcing fiber bundles do not become entangled with each other during the pultrusion process under tension, making it easier to form an aligned state.This allows for high straightness of the forming material and processing as paper tip material by taper grinding. The present invention is extremely useful because it exhibits the characteristic that a high degree of straightness can be obtained even after processing, and the high-productivity forming method called pultrusion can be effectively utilized in the industrial world.

[Brief explanation of drawings]

1 to 5 are cross-sectional configuration diagrams showing an example of the pultruded rod of the present invention. +1 Figure-) = 4

Claims (1)

[Claims] Fiber-reinforced pultrusion characterized in that, in a solid pultrusion-molded rod made of reinforcing fibers and a matrix resin that binds the reinforcing fibers, reinforcing fiber filament bundles constituting the cross section are arranged to form a center-symmetric multilayer structure. molded rod.