KR20160132212A - Carbon balance and whereby the shaft and the shaft made of the manufacturing method for the drawing comprises a nanotube - Google Patents

Abstract

Disclosed are a resin for drawing comprising a carbon nanotube, and an arrow shaft manufactured by using the same, and a manufacturing method of an arrow shaft. The resin for drawing comprises: a bisphenol A epoxy resin; an acid anhydride-based curing agent; aluminum hydroxide; a black pigment; a releasing agent; and a carbon nanotube. The resin for drawing is prepared by vertical drawing method to manufacture an arrow shaft, and has increased adhesive strength. Also, the resin for drawing has reduced bending, and can be manufactured in a large quantity.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a pulling resin containing carbon nanotubes and a method of manufacturing a shaft and a shaft,

The present invention relates to a shaft, and more particularly, to a shaft which is made of a carbon fiber to which carbon nanotubes are added, that is, a shaft made of an epoxy resin, is drawn by a drawing process to reduce the warpage, A carbon fiber including a nanotube, and a method of manufacturing a shaft and a shaft manufactured thereby.

In general, an arrow combines arrowheads on the shaft of a shaft of a hollow tube, and combines a pattern for holding an arrow on the bow protrusion at the rear end. The shaft has three or four collar on the outer periphery of the shaft, , And hunting.

These shafts vary widely from natural materials such as bamboo to carbon fiber sheets containing carbon fibers, and in recent years, most of archery and hunting arrows are made of carbon fiber sheets.

In general, an arrow that leaves the bow protest receives a thrust, which is the force that the protest pushes the rear end of the arrow. Such arrows experience paradoxic phenomena when flying away from the bow protest toward the target. Paradox refers to the phenomenon that an arrow flies from left to right in the initial stage of flight shortly after leaving the bow.

When the arrow is fired, the motion of the arrow is instantaneously transmitted to the arrow as the arrow moves away from the shaft. Therefore, the arrow does not withstand this force and the arrow bends from the pressure point, and the shaft is restored to its original state by the restoring force of the shaft. . The arrow repeats these movements and flies until the inertial energy disappears.

When the arrow is flying, it receives a lot of air resistance. The air resistance on the arrow is largely frictional resistance due to the shape resistance due to the difference of the pressure acting on the front and back surface of the arrow and the friction between the surface of the arrow and air.

Conventional game or hunting arrows are smoothly processed so that not only flight safety but also flying distance of arrows are limited. Therefore, it is required to improve the stability of arrows and the flying distance by improving the shape of the arrows.

Prior arts to meet the above-mentioned demands include Korean Patent Registration No. 10-0396590, Korean Patent Registration No. 10-0655934, and Korean Patent Registration No. 10-0655951.

In the 'method of manufacturing the shaft and the shaft manufactured by the above method' of Korean Patent No. 10-0396590, a shaft having a structure in which the inelastic sheet consisting of the first elastic sheet, the second elastic sheet and the fiber is laminated from the center of the shaft Lt; / RTI >

A plurality of carbon fiber sheets are laminated in such a manner that the carbon fiber arrays are arranged so as to intersect with each other, and then the cross-linked carbon fiber fiber sheet is attached to the outermost layer, So that the sharp surface is not exposed.

On the other hand, in the "shaft" of the Korean Patent Registration No. 10-0655951, a non-elastic sheet such as a fiber sheet is attached on the front side of the shaft and the rear side of the shaft, and a carbon fiberglass fiber sheet Thereby improving the strength of the arrow and increasing the gastrointestinal effect.

Most of the arrows including the prior art of the above-mentioned patent documents are manufactured by a sheet rolling method and a pultrusion method. The sheet rolling method uses a low productivity and a tapered mandrel Sometimes the center of gravity changes, and it is mainly used for the game, and the price is high. On the contrary, a conventional drawing method using a drawing resin composed of 89% by weight of an unsaturated polyester resin, 10% by weight of a vinyl ester resin and 1% by weight of a phenolic resin can be mass-produced, There is a problem that the straightness is lowered due to the bending of the bass, and the bass is usually used for low-cost practice. In addition, a shaft may be manufactured using an epoxy resin, an adhesive, or FRP, which can not be manufactured by a drawing method.

In addition, carbon fibers are used for arrows recently, and a very large amount is expected in view of the demand for arrows. Aluminum arrows and glass fibers are still dominant, but they are increasing rapidly due to their modulus and weight. Of course, carbon fiber has been used for athletes for various competitions for more than 10 years, and paradoxes, especially for athletes, have a close relationship with performance.

The paradox of arrows interferes with the straightness, which is much better with the use of high-elastic carbon fiber, but it is expensive in terms of price, and is in the process of being imported, so it is worth researching for other items or future players.

Korean Patent No. 10-0396590 (2003. 09. 02. Announcement) Korean Patent No. 10-0655934 (2006. 08. Announcement) Korean Patent No. 10-0655951 (2006. 12. 08. Announcement)

The present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a pulling resin containing carbon nanotubes capable of doubling the adhesive force and reducing warpage and mass production, The purpose is to provide.

In order to accomplish the object of the present invention as described above, the drawing resin containing carbon nanotubes according to an embodiment of the present invention may include a bisphenol A epoxy resin, an acid anhydride curing agent, an aluminum hydroxide filler, A black pigment, a mold release agent, and a carbon nanotube.

The drawing resin containing carbon nanotubes according to another embodiment of the present invention may include bisphenol A epoxy resin of 45 to 55 wt%, an anhydride curing agent of 36 to 44 wt%, a curing agent of 4.5 to 5.5 wt% By weight of aluminum hydroxide, 2.7 to 3.7% by weight of black pigment, 1.35 to 1.65% by weight of a mold release agent and 0.45 to 0.55% by weight of carbon nanotubes have.

In the drawing resin containing carbon nanotubes according to the embodiment of the present invention, the carbon nanotubes have a purity of 94 to 96% (0.02 to 0.04 g / cm 3), a bulk density of 38 to 42% And has a length of 10 to 11 mu m and a diameter of 9 to 11 nm.

The acid anhydride-based curing agent in the drawing resin containing carbon nanotubes according to the embodiment of the present invention is composed of 80% by weight of MNA (methyl nadic anhydride) and 20% by weight of PMDA (Pyro Mellic aianhydride) do.

Another object of the present invention is achieved by a method of manufacturing a shaft using a drawing resin, wherein a shaft is manufactured by a drawing method using a drawing resin including carbon nanotubes.

In the present invention, the additive comprising aluminum hydroxide, black pigment and releasing agent constituting the drawing resin is characterized by having a viscosity of 550 to 650 cps.

According to the present invention, it is possible to produce a shaft with a drawing resin in which carbon nanotubes are added to a bisphenol A epoxy resin, an acid anhydride curing agent, aluminum hydroxide, a black pigment and a releasing agent by a drawing method to obtain a sophisticated product with improved quality The production yield can be increased to 85%, the continuous or simultaneous production is possible, and the sticking power of the arrow, that is, the shaft is doubled and the warping phenomenon is reduced, and mass production is possible.

Hereinafter, preferred embodiments of the present invention will be described in more detail.

The arrows can be classified into three types, ie, a game, a general game, and a hunting game, and they are classified according to grain, straightness, and spine. In the following examples, hunting arrows using domestic carbon fibers will be described as an example (based on TKK, effect T-700).

Unsaturated polyesters and vinyl ester resins excellent in workability are used as drawing resins because they are easier to process than epoxy resins and have high productivity. Since the arrow has a good linearity and a high elasticity rate, it forms an expensive market, so an epoxy resin is used.

Such a drawing resin includes a bisphenol A epoxy resin, an acid anhydride curing agent, an aluminum hydroxide filler, a black pigment, a mold release agent, and a carbon nanotube .

Preferably, the drawing resin containing carbon nanotubes is prepared by mixing 45 to 55 wt% of bisphenol A epoxy, 36 to 44 wt% of an acid anhydride-based curing agent, 4.5 to 5.5 wt% of aluminum hydroxide filler), 2.7 to 3.7% by weight of a black pigment, 1.35 to 1.65% by weight of a mold release agent and 0.45 to 0.55% by weight of carbon nanotubes.

Carbon nanotubes (CNTs) are surface treated with sulfuric acid. They are used by stirring in a homomixer in an epoxy resin and a chamber. These carbon nanotubes have a purity of 94 to 96% (0.02 to 0.04 g / cm3), a bulk density of 38 to 42%, a length of 9 to 11 m and a diameter of 9 to 11 nm.

Preferably, the carbon nanotubes have a purity of 95% (0.02 to 0.04 g / cm3), a bulk density of 40%, a length of 10 m, and a diameter (diameter) of 10 nm.

The acid anhydride-based curing agent is composed of 80% by weight of MNA (methyl nadic anhydride) and 20% by weight of PMDA (Pyro Mellic acid anhydride).

As described above, the epoxy resin added with the carbon nanotubes is elevated to 170 Kgf / cm 2 at 120 Kgf / cm 2 without the addition of the carbon nanotubes.

As an additive, aluminum hydroxide, black pigment and release agent are also used in the horizontal drawing method, and the viscosity suitable for the vertical drawing machine is 550 to 650 cps which is slightly higher than that of the horizontal drawing machine.

As described above, the drawing resin including the bisphenol A epoxy resin, the acid anhydride curing agent, the aluminum hydroxide, the black pigment, the releasing agent and the carbon nanotube had a tensile strength of 75 MPa, a tensile elastic modulus of 3 MPa, an elongation of 3%, a flexural strength of 130 MPa, A flexural modulus of 3,000 Pa, and a temperature of 130 DEG C (DSC DEG C / min).

A vertical drawer may be applied in the process of manufacturing the shaft with the drawing resin as above. The vertical drawer is vertically fixed to maintain the center of the mandrel in order to prevent the mandrel from warping due to its own weight, so that the manufacturing process can be controlled so that the quality of the manufactured product can be uniformly maintained.

Also, the vertical drawer is controlled by precise process control so that the mold including the mandrel and the puller pulling the hardened drawing shaft are aligned, and the horizontal shaft is maintained in a constant level, and the temperature and the heating Adjust the length of the plate. In addition, the vertical drawer needs to be careful because the structure of the vertical drawer is different from the structure guided to the mold entrance after resin impregnation and the problem that the resin flows downward after impregnation is more difficult than the horizontal drawer.

Such a vertical drawer is advantageous for a product having a large diameter, easy to work, and unlike a horizontal drawer having no influence of rotation, the vertical drawer is advantageous for a small-diameter product, but the molding process for the resin flow is troublesome and is affected by rotation.

In an embodiment of the present invention, bisphenol A epoxy resin, 40 wt% acid anhydride curing agent, 5 wt% aluminum hydroxide filler, 3 wt% black pigment, 1.5 wt% A resin for drawing comprising a weight% of a mold release agent and 0.5% by weight of carbon nanotubes was prepared. Particularly, the acid anhydride-based curing agent was prepared from 80% by weight of MNA (methyl nadic anhydride) and 20% by weight of PMDA (Pyro Mellic acid anhydride).

A shaft was manufactured using the pulling machine with the drawing resin prepared as above.

The drawn resin thus prepared had a tensile strength of 75 MPa, a tensile elastic modulus of 3 GPa, an elongation of 3%, a flexural strength of 130 MPa, a flexural modulus of 3GPa, and a temperature of 130 DEG C (DSC DEG C / min).

The shafts manufactured by the drawing resin have a modulus of elasticity of 150 Gpa, an elongation of 1.1%, a moisture content of 2.53, a compression load of 39.03 kpt, and a bending load of 45.52 kpt.

[Comparative Example 1]

In an embodiment of the present invention, bisphenol A epoxy resin, 40 wt% acid anhydride curing agent, 5 wt% aluminum hydroxide filler, 3 wt% black pigment, 1.5 wt% A resin for drawing comprising a weight% of a mold release agent and 0.5% by weight of carbon nanotubes was prepared. In particular, the acid anhydride-based curing agent was prepared from 100% by weight of MNA (methyl nadic anhydride).

A shaft was manufactured using the pulling machine with the drawing resin prepared as above.

The drawn resin thus prepared had a tensile strength of 60 MPa, a tensile elastic modulus of 2 GPa, an elongation of 5%, a flexural strength of 100 MPa, and a flexural modulus of 1.5 GPa.

The shaft made of the drawing resin has an elastic modulus of 110 Gpa, an elongation of 2%, a compressive load of 20 kgf, and a bending load of 30 kgf.

[Comparative Example 2]

In an embodiment of the present invention, bisphenol A epoxy resin, 40 wt% acid anhydride curing agent, 5 wt% aluminum hydroxide filler, 3 wt% black pigment, 1.5 wt% A resin for drawing comprising a weight% of a mold release agent and 0.5% by weight of carbon nanotubes was prepared. Particularly, the acid anhydride-based curing agent was prepared from 50% by weight of MNA (methyl nadic anhydride), 30% by weight of PMDA (Pyro Mellic acid anhydride) and 20% by weight of BTDA (Benzenetrimellidic hydride).

A shaft was manufactured using the pulling machine with the drawing resin prepared as above.

In this case, the drawing resin had poor physical properties such as tensile strength, tensile elasticity, elongation, flexural strength, flexural modulus and heat distortion temperature, and the shaft made of resin for drawing had a modulus of elasticity, elongation, , Bending load, and so on.

In addition, when the acid anhydride-based curing agent is composed of 80 wt% of MNA and 20 wt% of BTDA, or 60 wt% of MNA, 20 wt% of BTDA and 20 wt% of PMDA, The properties of the shaft become lowered.

As described above, the present invention can be applied to the production of arrows, that is, the shaft, by the same tow of the carbon fiber, that is, depending on the number of fiber strands such as 3k, 6k, 12k, 24k, The yield of the drawing is different. In the embodiment of the present invention, 12k is taken as an example considering the unit price and the yield. As with other processes, the drawing success using the epoxy resin varies depending on the process control for the expansion and shrinkage during the curing process, and the carbon nanotube modification also affects the durability and the physical properties of the finished product.

The results of the physical property test of the pullout shaft obtained in the above embodiment of the present invention are shown in Table 1 below.

Test Items unit Test result Remarks Modulus of elasticity Gpa 153.00 ASTM E399 Elongation % 1.10 ASTM E399 Water absorption rate % 2.53 ASTM E399 Eccentricity (straightness) inch 0.021 ASTM E399 Compressive load kgf 39.03 ASTM E399 Rapid load kgf 45.52 ASTM E399

For the physical properties test, tensile was measured using ASTM E399, and the water absorption rate was measured after storage at 23 ° C and 50% relative humidity for 12 hours. After immersion in water at 23 ° C for 24 hours, ) Was fixed at both ends of 711.2 mm (27 "), and the change in the center position was measured with a laser measuring device in the vertical direction with respect to the sample. The bending was measured at a bending distance of 400 mm at three points bending, And a load was applied in the circumferential direction of the test piece.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is possible. Accordingly, the spirit of the present invention should be understood only in accordance with the following claims, and all equivalents or equivalent variations thereof are included in the scope of the present invention.

Claims (7)

A carbon nanotube comprising a bisphenol A epoxy resin, an acid anhydride curing agent, an aluminum hydroxide filler, a black pigment, a mold release agent, and a carbon nanotube, Included drawing resin. 45 to 55% by weight of a bisphenol A epoxy resin,
36 to 44% by weight of an acid anhydride-based curing agent,
4.5 to 5.5 wt% aluminum hydroxide filler,
2.7 to 3.7% by weight of a black pigment,
1.35 to 1.65 wt% of a mold release agent and
A drawing resin comprising carbon nanotubes composed of 0.45 to 0.55% by weight of carbon nanotubes. 3. The method according to claim 1 or 2,
The carbon nanotubes may include,
A purity of from 94 to 96% (0.02 to 0.04 g / cm3)
A bulk density of 38 to 42%
A length of 9 to 11 mu m and
Wherein the carbon nanotube has a diameter of 9 to 11 nm. 3. The method according to claim 1 or 2,
Wherein the acid anhydride-based curing agent is composed of 80% by weight of MNA and 20% by weight of PMDA (pyromellic dianhydride). A shaft formed by a drawing resin comprising the carbon nanotubes of any one of claims 1 to 4. A method of manufacturing a shaft for a shaft using a pulling resin, wherein the shaft of claim 4 is manufactured by a vertical drawing method using a pulling resin containing the carbon nanotubes of any one of claims 1 to 4. The method according to claim 6,
Wherein the additive including aluminum hydroxide, black pigment, and releasing agent constituting the pulling resin has a viscosity of 550 to 650 cps.