WO2012002410A1

WO2012002410A1 - Carbon fiber wound tape and production method for same

Info

Publication number: WO2012002410A1
Application number: PCT/JP2011/064863
Authority: WO
Inventors: 高坂繁行; 朝見芳弘
Original assignee: ダイセルポリマー株式会社
Priority date: 2010-07-01
Filing date: 2011-06-29
Publication date: 2012-01-05
Also published as: JP5592775B2; CN102971363A; JP2012031371A; KR20130123295A; CN102971363B

Abstract

Disclosed is a carbon fiber wound tape wherein carbon fiber tape formed from a complex that includes a carbon fiber and an aromatic polyamide resin or an aliphatic polyamide resin is wound around a cylindrical core material. The width (W) of the carbon fiber tape found using the formula (I) is between 5-100 mm and the minimum diameter (D) of the cylindrical core material around which the carbon fiber tape of said width (W) between 5-100 mm is wound is found using the formula (II).　(I) 0.2×10^-3×N≦W≦2×10^-3×N (wherein N is the number of carbon fibers that make up the carbon fiber); (II) 4.5×F×t≦D≦50×F×t (wherein F is the carbon fiber amount, in the range of 20%-60% by mass, and t is thickness of the carbon fiber tape, in the range of 0.1-0.5 mm.)

Description

Carbon fiber wound tape and manufacturing method thereof

The present invention relates to a carbon fiber wound tape in which a carbon fiber tape is wound around a cylindrical core material, and a method for producing the same.
Background art

Since carbon fiber is lightweight and has high mechanical strength, it is widely used as a reinforcing fiber for resin materials applied to various applications.

Japanese Patent No. 3119699 is an invention of a method for producing a long fiber reinforced composite material, and paragraph No. 0007 shows continuous fibers such as glass fiber, carbon fiber, metal fiber, and aromatic polyamide fiber as examples of the fiber. Has been. However, only glass fibers are used in the examples, and it is not recognized that other fibers, particularly carbon fibers having greatly different mechanical strengths, can be produced in the same manner.

Japanese Patent No. 3386158 is an invention of a tape-shaped molding material obtained by impregnating a reinforcing fiber satisfying a predetermined conditional expression with a thermoplastic resin. In paragraph 0007, glass fibers, carbon fibers, aramid fibers, ceramic fibers, metal fibers, etc. are exemplified as reinforcing fibers. However, only glass fibers are used in the examples, and it is not recognized that other fibers, particularly carbon fibers having greatly different mechanical strengths, can be produced in the same manner. In addition, when the carbon fiber which satisfy | fills the conditional expression of Claim 1 is used, with the method of the Example of patent 3386158, a tape-shaped molded object cannot be manufactured in fact.

Japanese Patent Application Laid-Open No. 2007-76224 is an invention of an apparatus for producing a carbon fiber reinforced thermoplastic resin tape. The manufacturing apparatus is characterized by discharging fluff generated during the manufacture of a carbon fiber reinforced thermoplastic resin tape.

JP 2007-118216 A is an invention of a method for producing a carbon fiber reinforced thermoplastic resin tape. It is described that the obtained tape thickness is 130 μm or less, and the tape thickness exceeding 130 μm is inferior in bending strength (see Table 1). The invention disclosed in Japanese Patent Application Laid-Open No. 2007-118216 is intended to increase the bending strength by reducing the tape thickness based on the knowledge that the bending strength is inferior when the tape thickness is large.

When storing and transporting carbon fiber tape, it is difficult to handle it for a long time, so it is easy if it can be stored and transported in the state of the wound tape wound around the core material, and the workability during use is also improved. . Furthermore, depending on the type of work, a small-diameter winding tape may be easy to use, or a large-diameter winding tape may be easy to use.

However, as described in JP 2007-118216 A, conventionally, when the thickness of the carbon fiber tape is increased (when the thickness exceeds 130 μm), the bending strength is inferior (that is, when the thickness is increased, winding and storage is difficult). It was known. From this fact, it is sufficient to make the carbon fiber tape thin. However, it is technically difficult to make the carbon fiber tape too thin.

It is an object of the present invention to provide a carbon fiber-wrapped tape in which a carbon fiber tape is wound around a cylindrical core material, which can be easily stored and transported and can remarkably improve workability, and a method for producing the same. To do.

As a means for solving the problems, the present invention
A carbon fiber tape made of a composite containing carbon fiber and an aromatic polyamide resin or an aliphatic polyamide resin is a carbon fiber wound tape wound around a cylindrical core material,
The width (W) of the carbon fiber tape obtained from the formula (I) is in the range of 5 to 100 mm,
Provided is a carbon fiber wound tape in which the minimum diameter (D) of a cylindrical core member around which a carbon fiber tape having a width (W) in the range of 5 to 100 mm is wound is obtained from the formula (II).
0.2 × 10 ⁻³ × N ≦ W ≦ 2 × 10 ⁻³ × N (I)
(In formula (I), N is the number of carbon fibers constituting the carbon fiber.)
4.5 × F × t ≦ D ≦ 50 × F × t (II)
(In the formula (II), F is the amount of carbon fiber and ranges from 20 to 60% by mass, and t is the thickness of the carbon fiber tape and ranges from 0.1 to 0.5 mm.)

The present invention also provides a solution to other problems.
A method for producing the above carbon fiber-wrapped tape,
Introducing a focusing body containing one or more carbon fibers into a crosshead die;
A process of obtaining a tape-like composite in which carbon fibers and a thermoplastic resin are integrated by bringing a bundling body containing carbon fibers into contact with a molten resin in a cross-head die while being heated and pressurized. ,
A step of obtaining a carbon fiber tape by extruding the tape-shaped composite from the slit outlet of the cross-head die, supporting it from both sides in the thickness direction, and cooling;
A step of winding around the obtained carbon fiber tape cylindrical core material,
The manufacturing method of the carbon fiber winding tape which has this.

Since the carbon fiber tape of the present invention has a form in which the carbon fiber tape is wound around the core material, it can be easily stored and transported, and can be taken out and used in a necessary amount, so that the workability is also good.
The present invention can be used by cutting a carbon fiber tape having a required length from a carbon fiber wound tape during work to a desired length.
The present invention is useful as a reinforcing tape for parts such as automobiles. By repairing the parts necessary for the design by insert molding, sticking, lamination, etc., it becomes possible to reduce the weight of the parts by reducing the thickness and size of the parts. Furthermore, since deformation control of parts using directionality is possible, it is particularly effective in fields that require parts weight reduction, such as the automobile industry and the civil engineering and construction industry.

Schematic which shows the manufacture flow for demonstrating the manufacturing method of a carbon fiber winding tape. Schematic which shows the other manufacturing flow for demonstrating the manufacturing method of a carbon fiber winding tape.

In the figure, reference numeral 10 is a carbon fiber tape-like bundle, 11 is a carbon fiber tape, 20 is a crosshead die, 21 is an upper mold, 22 is a lower mold, and 25 is a molten resin supply line (supply). ), 26 indicates a slit outlet, and 31, 32, and 33 indicate cooling rolls, respectively.

<Carbon fiber wound tape>
The carbon fiber wound tape of the present invention is obtained by winding a carbon fiber tape many times (multiple layers) around a cylindrical core material.

The carbon fiber tape used in the carbon fiber wound tape of the present invention can be wound around a cylindrical core material, and has no change in appearance when at least the durability test 1 described in the examples is carried out (cracks, etc.) In which no change occurs even when the durability test 2 is further performed.

The carbon fiber wound tape (carbon fiber tape) of the present invention has a carbon fiber tape width (W) determined from the following formula (I) in the range of 5 to 100 mm.

0.2 × 10 ⁻³ × N ≦ W ≦ 2 × 10 ⁻³ × N (I)
(In formula (I), N is the number of carbon fibers constituting the carbon fiber.)
In addition, since the outer diameter of the commercially available carbon fiber is substantially the same diameter (about 7 μm), it is not considered in the formula (I).

The width (W) of the carbon fiber tape obtained from the formula (I) is, for example,
By using 25,000 carbon fibers, the width (W) of the carbon fiber tape can be in the range of 5 to 50 mm,
By using 50,000 carbon fibers, the width (W) of the carbon fiber tape can be in the range of 10 to 100 mm.

If the width (W) of the carbon fiber tape obtained from the formula (I) is not less than the lower limit (5 mm), the impregnation of the resin (aromatic polyamide resin or aliphatic polyamide resin) will be sufficient, so the carbon fiber tape itself When the strength is increased and the upper limit (100 mm) or less, the distribution of the carbon fibers in the tape becomes uniform, so that the function due to the inclusion of the carbon fibers is sufficiently expressed.
The width (W) of the carbon fiber tape determined from the formula (I) is preferably 10 to 80 mm, more preferably 10 to 50 mm.

The cylindrical core material used in the carbon fiber-wrapped tape of the present invention has a circular cross section in the width (diameter) direction, but may be polygonal (more than a triangle, but preferably hexagonal, octagonal, etc.). It may be oval.
The cylindrical core material can be made of paper, wood, plastic, metal, ceramics, or the like.

The minimum diameter (minimum outer diameter) (D) of the cylindrical core material is obtained from the formula (II). The minimum diameter (D) of the cylindrical core material can wind up the carbon fiber tape having the above-mentioned width (W) and does not cause a change in appearance when at least the durability test 1 described in the examples is performed ( The minimum value is such that no cracks or the like occur, and preferably the minimum value that does not cause a change even when the durability test 2 is performed.

4.5 × F × t ≦ D ≦ 50 × F × t (II)
(In the formula (II), F is the amount of carbon fiber and ranges from 20 to 60% by mass, and t is the thickness of the carbon fiber tape and ranges from 0.1 to 0.5 mm.)
In addition, when the cross-sectional shape of the cylindrical core is a polygon, for example, a hexagon, the length connecting the opposite corners is D, and in the case of an ellipse, the length of the major axis is D. .

The smaller the amount of carbon fiber (ie, the greater the amount of aromatic polyamide resin or the amount of aliphatic polyamide resin), the more flexible the carbon fiber tape is, and the easier it is to wind around the core material. That is, the smaller the amount of the aromatic polyamide resin or the aliphatic polyamide resin, the lower the flexibility and the difficulty of winding on the core material.
Furthermore, the carbon fiber tape is easy to manufacture when the thickness is large, but is difficult to wind around the core material, and when the thickness is small, the manufacture becomes difficult, but it is easy to wind around the core material.

Formula (II) calculates | requires the diameter (D) of the cylindrical core material which can wind and hold a carbon fiber tape from the relationship between the carbon fiber concentration (F) and thickness (t) of a carbon fiber tape.
Specifically, when carbon fiber tapes having various concentrations (F) and thicknesses (t) are wound around a core material having various diameters, the diameter (D of the core material when the appearance of the carbon fiber tape does not change) (D ) Is experimentally measured, and the formula (II) can be derived from the relationship between the concentration (F) and the thickness (t).

When the diameter is equal to or larger than the minimum diameter (D) of the cylindrical core material obtained from the formula (II), the carbon fiber tape is not cracked when wound and held. In addition, the minimum diameter (D) of the cylindrical core material is 25 mm among those satisfying the minimum diameter (D) obtained from the formula (II) from the viewpoint of ease of handling during transportation, storage, work, etc. It is preferable that it is above, and it is more preferable that it is 30 mm or more.
In addition, the upper limit of the cylindrical core material is not limited for the reason that the carbon fiber tape can be wound and does not cause cracks, etc., depending on the requirements of the manufacturing process, storage and transportation, work site, etc. For example, it can be set to 1000 mm or less, but is preferably 800 mm or less, more preferably 600 mm or less and 500 mm or less from the viewpoint of handling.

The carbon fiber tape used as the carbon fiber wound tape is composed of a composite containing carbon fibers and a polyamide resin.
Carbon fibers are well known, and PAN, pitch, rayon, lignin and the like can be used.

Aromatic polyamide is obtained from aromatic dicarboxylic acid and aliphatic diamine or aliphatic dicarboxylic acid and aromatic diamine, for example, polyamide MXD (metaxylylenediamine and adipic acid), polyamide 6T (hexamethylenediamine and terephthalic acid) ), Polyamide 6I (hexamethylenediamine and isophthalic acid), polyamide 9T (nonanediamine and terephthalic acid), polyamide M5T (methylpentadiamine and terephthalic acid), and polyamide 10T (decamethylenediamine and terephthalic acid).

As the aliphatic polyamide, polyamide 6, polyamide 46, polyamide 66, polyamide 11, polyamide 12, polyamide 1212, polyamide 1010, polyamide 1012, polyamide 1112, polyamide 610, polyamide 612, polyamide 69, polyamide 810, or the like can be used.

The carbon fiber wound tape of the present invention is wound around a cylindrical core material, and can be used as a carbon fiber tape by drawing out an appropriate length and cutting it to a desired length during operation. .

The carbon fiber tape taken out from the carbon fiber wound tape of the present invention can be used as a reinforcing material for various resin moldings.

The carbon fiber tape taken out from the carbon fiber wound tape of the present invention can be made into a sheet-like fabric by applying a method such as plain weave, twill weave, satin weave, etc. Can also be processed.
Moreover, the carbon fiber tape taken out from the carbon fiber wound tape of the present invention can be knitted into a cylindrical shape.

Since the carbon fiber tape taken out from the carbon fiber wound tape of the present invention, the sheet and the cylindrical body obtained from them, etc. contain an aromatic polyamide resin, they can be transformed into a desired shape by heating. .

<Method for producing carbon fiber wound tape>
A method for producing a carbon fiber-wrapped tape will be described with reference to FIGS.
In the first step, the bundling body 10 including one or more carbon fibers is introduced into the crosshead die 20 while being supported by the feed rolls 15 and 16.
The bundle 10 is preferably a carbon fiber bundle having a fiber diameter of 5 to 24 μm and a number of fibers of 1000 to 200,000, more preferably 3000 to 150,000.
As this carbon fiber bundle, a commercially available carbon fiber bundle (for example, 30K = 30,000) may be used as it is, or a plurality of commercially available carbon fiber bundles are used in combination (for example, 10K = 10,000 fiber bundles). 3 bundles may be used in combination with 30,000).
Further, the bundling body 10 may use the carbon fiber bundle as it is, or the surface of the carbon fiber bundle is surface-treated with a bundling agent so as to be in a temporarily fixed state (the bundle is not scattered and the subsequent opening operation is impaired. It may be a state of being integrated to a certain extent).

Next, in the cross head die 20, the bundling body 10 containing carbon fibers is brought into contact with the molten resin (molten aromatic polyamide resin) in a heated and pressurized state while opening.

The converging body 10 may be opened by any method that can apply pressure to the converging body 10 in the thickness direction. In the present invention, the cross head die 20 in which the upper die 21 and the lower die 22 are combined is used. .

The cross-head die 20 includes an upper die 21 having a wave-shaped unevenness 21a formed continuously in the length direction, and a wave-shaped unevenness formed so as to be fitted to the wave-shaped unevenness 21a of the upper mold 21. A lower die 22 having 22a is combined.

The upper mold 21 (or the lower mold 22) is provided with a molten resin introduction line (introduction hole) 25, and the molten resin is supplied to the passing gap of the focusing body 10 between the upper mold 21 and the lower mold 22. It can be done.

The upper mold 21 and the lower mold 22 are each provided with heating means to heat the focusing body 10 passing through the passage gap. The heating temperature at this time is a temperature equal to or higher than the melting point of the resin (aromatic polyamide resin) supplied from the introduction line (introduction hole) 25.

When the converging body 10 passes through the passage gap between the upper die 21 and the lower die 22, the aromatic polyamide resin melted between the carbon fibers is opened in the process of zigzag passing through the gap between the

irregularities

21a and 22a. Impregnated.

Thereafter, the composite body in which the focusing body 10 and the aromatic polyamide resin are integrated is extruded from the slit outlet 26 of the crosshead die 20 into a tape shape (carbon fiber tape 11). At this time, the thickness and width of the carbon fiber tape 11 are adjusted by adjusting the size of the slit outlet 26.

Then, it is taken up while being cooled by cooling

rolls

31, 32, 33 arranged as appropriate, and wound around a cylindrical core material to obtain a carbon fiber wound tape.
In FIG. 1, the cooling rolls 31, 32, and 33 are arranged at positions where they do not come into contact with each other via the carbon fiber tape 11, and either one surface of the carbon fiber tape 11 is cooled first, and then the other surface is To be cooled.
In FIG. 2, the cooling rolls 31 and 32 are each arrange | positioned in the position which contact | abuts via the carbon fiber tape 11, and both surfaces of the carbon fiber tape 11 are cooled simultaneously.

Production example (Manufacture of carbon fiber tape)
A carbon fiber tape having the carbon fiber concentration and thickness shown in Table 1 was manufactured by the flow shown in FIG.

[Carbon fiber bundle 10]
Trading card yarn, T700S (manufactured by Toray Industries, Inc.)
[Aromatic polyamide resin]
PA MXD6, Reny 6002 (Mitsubishi Engineering Plastics Co., Ltd.)
[Aliphatic polyamide resin]
PA66, UBE nylon 2015B (manufactured by Ube Industries)
PA612, VESTAMID DX9308 (manufactured by Daicel-Evonik)

<Production conditions when using PA MXD6>
Feeding speed of focusing body 10: 5 m / min Heating temperature of crosshead die 20: 290 ° C. (however, in the case of PA 66 and PA 612, 300 ° C.)
Slit outlet: width (tape thickness) 0.1-0.6mm x length (tape width) 10-50mm
Surface temperature of cooling roll 31: 80 ° C (however, in the case of PA66 and PA612, 85 ° C)
Surface temperature of cooling roll 32: 80 ° C (however, in the case of PA66 and PA612, 85 ° C)
Surface temperature of cooling roll 33: 60 ° C

Using the carbon fiber concentration (F) and thickness (t) of each carbon fiber tape obtained, the outside of the cylindrical core material from the formula (II): 4.5 × F × t ≦ R ≦ 50 × F × t Table 1 shows the diameter (D) obtained.

From the results in Table 1, for example, when the carbon fiber concentration (F) is 20% by mass and the thickness (t) is 0.4 mm, it can be wound around a core material having a diameter (D) of 36 mm.

Examples 1 to 6 and Comparative Example The following durability test 1 was performed on the carbon fiber (CF) tapes shown in Tables 2 and 3 manufactured using carbon fibers and an aromatic polyamide resin (MXD6). The results are shown in Tables 2 and 3.

Endurance test 1
The carbon fiber wound tape was manufactured by using the apparatus shown in FIG. 1 and mechanically winding the core material having the diameters shown in Tables 2 and 3 so as to form 3 to 5 layers. The winding end was fixed with an adhesive tape. The obtained carbon fiber-wrapped tape was wound up with each layer in a dense state by visual observation. The obtained carbon fiber wound tape was subjected to the durability test 1 shown below.
The carbon fiber wound tape was kept at room temperature (20 to 25 ° C.) in an atmosphere of humidity (50%) for 24 hours (one day) or more.
Thereafter, all the carbon fiber tape was fed out from the carbon fiber wound tape, and the surface was observed with the naked eye to observe whether there was a change such as a crack. The results are shown in Tables 2 and 3.

Comparative Example A is an example in which the concentration of carbon fiber is outside the scope of the present invention (6% by mass), and as a result of non-uniform fiber dispersion, the fiber spacing is too wide, resulting in poor appearance, Sufficient mechanical properties due to blending were not obtained, resulting in product defects.
Examples 1 to 6 and Comparative Examples 1 to 6 are examples of pairs. In Examples 1 to 6, there was no occurrence of cracks because the core material satisfying the minimum diameter (D) shown in Table 1 was used, but Comparative Examples 1 to 6 had a minimum diameter (D). Since a core material with a small diameter was used, cracks were generated.

Endurance test 2
Each of the tapes of Examples 1 to 6 shown in Tables 2 and 3 is the original shape as soon as one end of the tape is fixed and the other end is grasped and rotated by 180 ° and then deformed, and then the other end is released. Recovered. Even when this was repeated 10 times or more, no change was observed in the appearance of the tape.

Examples 7 and 8 and Comparative Example The above durability test 1 was performed on the carbon fiber (CF) tape shown in Table 4 manufactured using carbon fiber and aliphatic polyamide resin (PA612, PA66). The results are shown in Table 4.

In the tapes of Examples 7 and 8 shown in Table 4, when the above durability test 2 was performed, no change was observed in the appearance of the tape even when repeated 10 times or more.

Claims

A carbon fiber tape comprising a composite containing carbon fibers and an aromatic polyamide resin or an aliphatic polyamide resin is a carbon fiber wound tape wound around a cylindrical core material,
The width (W) of the carbon fiber tape obtained from the formula (I) is in the range of 5 to 100 mm,
A carbon fiber-wrapped tape, wherein the minimum diameter (D) of a cylindrical core member around which a carbon fiber tape having a width (W) in the range of 5 to 100 mm is wound is obtained from the formula (II).
0.2 × 10 −3 × N ≦ W ≦ 2 × 10 −3 × N (I)
(In formula (I), N is the number of carbon fibers constituting the carbon fiber.)
4.5 × F × t ≦ D ≦ 50 × F × t (II)
(In the formula (II), F is the amount of carbon fiber and ranges from 20 to 60% by mass, and t is the thickness of the carbon fiber tape and ranges from 0.1 to 0.5 mm.)
The carbon fiber wound tape according to claim 1, wherein the width (W) of the carbon fiber tape is 10 to 80 mm.
The aromatic polyamide resin according to claim 1 or 2, wherein the aromatic polyamide resin is selected from polyamide MXD6, polyamide 9T, and polyamide 10T, and the aliphatic polyamide resin is selected from polyamide 6, polyamide 66, polyamide 610, and polyamide 612. Carbon fiber wound tape.
A method for producing a carbon fiber wound tape according to any one of claims 1 to 3,
Introducing a focusing body containing one or more carbon fibers into a crosshead die;
Tape-like composite in which tape-like carbon fiber and thermoplastic resin are integrated by bringing the bundle containing carbon fiber into contact with the molten resin in the cross-head die in a heated and pressurized state. Obtaining a step,
A step of obtaining a carbon fiber tape by extruding the tape-shaped composite from the slit outlet of the cross-head die, supporting it from both sides in the thickness direction, and cooling it,
A step of winding around the obtained carbon fiber tape cylindrical core material,
The manufacturing method of the carbon fiber winding tape which has this.
The crosshead die has an upper mold having wave-shaped irregularities formed continuously in the length direction, and a lower mold having wave-shaped irregularities formed so as to be fitted to the wave-shaped irregularities of the upper mold. The molds are combined, and one of the molds is provided with a molten resin introduction hole,
The method for producing a carbon fiber wound tape according to claim 4, wherein the opening of the converging body including the carbon fibers is performed by zigzaging the converging body between the upper mold and the lower mold.