JP3136883B2 - Carbon fiber reinforced resin composite and prepreg - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon fiber reinforced resin composite material and a prepreg as an intermediate substrate thereof, and more particularly to a carbon fiber reinforced resin composite material having high impact resistance and a prepreg as an intermediate substrate thereof.

[0002]

2. Description of the Related Art Carbon fiber reinforced resin composite materials are used for sports,
Although widely used in aerospace and the like, in actual applications, not only static characteristics but also dynamic characteristics such as impact are important. Conventionally, the relationship between the impact resistance characteristics of carbon fiber composite materials and the characteristics of carbon fibers constituting the carbon fiber reinforced resin composite materials is not clear, and there has been no carbon fiber reinforced resin composite material having sufficiently high impact resistance.

[0003]

An object of the present invention is to solve the above-mentioned problems, that is, to provide a carbon fiber reinforced resin composite material having excellent impact resistance and a carbon fiber reinforced resin prepreg as an intermediate base material. To provide.

[0004]

In order to solve the above-mentioned problems, the carbon fiber reinforced resin composite material of the present invention has the following constitution. That is, the specific gravity is 1.75 or less, the tensile modulus is 29 tf / mm ² or more, the tensile strength is 500 kgf / mm ² or more,
Surface nitrogen concentration N measured by photoelectron spectroscopy ESCA
/ C and the surface oxygen concentration O / C are 0.02-
0.2, an aliphatic compound having a plurality of epoxy groups
Epoxy sizing agent consisting of
And a sheet edge peel strength of 22 %.
A carbon fiber reinforced resin composite material characterized by being reinforced with carbon fibers of kgf / mm ² or more.

[Means for Solving the Problems]

[0005] The carbon fiber reinforced resin prepreg of the present invention has the following constitution. That is, the specific gravity is 1.75 or less, the tensile modulus is 29 tf / mm ² or more, and the tensile strength is 500 kg.
f / mm ² or more, table measured by photoelectron spectroscopy ESCA
The surface nitrogen concentration N / C and the surface oxygen concentration O / C are respectively
0.02 to 0.2, having a plurality of epoxy groups
Epoxy sizing agent composed of aliphatic compound
A carbon fiber reinforced resin prepreg characterized by being provided with 0.01 to 5% per fiber unit weight and reinforced with carbon fibers having a board edge peel strength of 22 kgf / mm ² or more.

The carbon fiber reinforced resin composite material and the prepreg of the present invention will be described in detail. The carbon fiber constituting the carbon fiber reinforced resin composite material or the prepreg of the present invention has a specific gravity of 1.75 or less and a tensile modulus and a strength of 29 tf / mm ² measured by a strand tensile test, respectively.
Above and carbon fiber of 500 kgf / mm ² or more
Surface nitrogen concentration N / C measured by optical method ESCA and
And the surface oxygen concentration O / C is 0.02-0.2, respectively.
Yes, consisting of aliphatic compounds with multiple epoxy groups
An epoxy-based sizing agent is used in an amount of 0.
In addition, the steel sheet is provided with an edge delamination strength (EDS) of 22 kgf / mm ² or more as measured by a composite test.

A carbon fiber having a specific gravity of more than 1.75 has a small weight reduction effect, preferably at most 1.74, more preferably at most 1.73. Tensile modulus is 29 tf / mm ²
If it is less than 500 kgf / mm ² , the impact resistance is low, and it is necessary to produce a thick composite material in order to exhibit the desired properties, which is not preferable because the merit of weight reduction is small. More preferably, the elastic modulus is 29.5 tf / mm ^2.
Above, more preferably 30 tf / mm ² or more, and the tensile strength is more preferably 520 kgf / mm ² or more, and still more preferably 550 kgf / mm ² or more.

[0008] Also, E measured by a composite test
If the DS is less than 22 kgf / mm ² , the maximum load becomes low due to delamination at the time of impact, which is not preferable. More preferably, it is 23 kgf / mm ² or more, and further preferably, it is 24 kgf / mm ² or more.

That is, the carbon fiber used in the present invention is EDS which is an index of tensile strength, elastic modulus, and adhesion to resin.
And the specific gravity is low, and as a total effect thereof, the impact characteristics of the carbon fiber reinforced resin composite material are excellent.

The carbon fiber used in the present invention can be obtained as follows, but is not limited thereto.

As the carbon fibers of the present invention, known polyacrylonitrile (PAN) -based, pitch-based, and vapor-grown carbon fibers can be used.
Based carbon fibers are preferred. The case of PAN-based carbon fiber will be described in detail below as an example.

As the spinning method, a wet method, a dry method, a dry-wet method and the like can be adopted, but a wet method or a dry-wet method in which a high-strength yarn is easily obtained is preferable, and a dry-wet spinning is particularly preferable. P for spinning dope
A solution or suspension of a homopolymer or copolymer of AN can be used. The precursor yarn is solidified, washed, stretched, and applied with an oil agent to obtain a precursor fiber, which is further subjected to flame resistance, carbonization, and, if necessary, graphitization.

As the conditions for carbonization or graphitization, the maximum temperature in an inert atmosphere is 140 to obtain the carbon fiber of the present invention.
0 ° C. or higher, preferably 1600 ° C. or higher. The higher the firing temperature, the higher the modulus of elasticity is, but the tensile strength and the adhesive strength to the resin are reduced, and the specific gravity is increased. Therefore, it is preferable to optimize the temperature, and the temperature is preferably 1400 ° C to 2200 ° C, more preferably 1600 ° C to 2000 C or lower is good. It is also preferable to combine stretching at the same firing temperature in order to improve tensile strength and elastic modulus. In order to improve the strength and the elastic modulus, fine carbon fibers are preferable, and the single fiber diameter of the carbon fibers is 7.5 μm or less, preferably 6.5 μm or less, more preferably 5.5 μm or less.

The obtained carbon fiber is further subjected to a surface treatment and a sizing treatment to become a carbon fiber. As an electrolyte used for the electrolytic treatment, a solution, preferably an aqueous solution, of an acid such as sulfuric acid or nitric acid, an alkali such as sodium hydroxide, ammonium carbonate, or tetraethylammonium hydroxide, or a salt thereof is used. In the case of carbon fibers obtained by dry-wet spinning, an aqueous solution of an alkali or salt is preferable. As the electrolyte, the presence of a basic amine compound or an ammonium salt is effective. For example, ammonium carbonate, ammonium hydrogen carbonate,
Ammonium carbonate, ammonia, triethylamine, cyclohexylamine, ammonium nitrate, ammonium sulfate, or a mixture thereof can be used. The pH of the electrolyte is more preferably 8 or more. If the pH is less than 8, the dissolution of graphite oxide generated by electrolytic oxidation is small, and there is a possibility that adhesion to the resin may be reduced.

The amount of electricity in the electrolytic treatment varies depending on the elastic modulus of the carbon fiber used. In the case of a carbon fiber having a high modulus of elasticity, energy for destroying the developed graphite structure on the surface is required, so that a high amount of electricity is required. Become. However, applying a large amount of electricity at once increases the voltage, which is a safety issue,
There is a problem that defects are likely to occur in carbon fibers. Therefore, it is necessary to reduce the processing amount per tank and increase the number of processing tanks. Specifically, the amount of electricity per 1 g of carbon fiber and one tank is 2 coulombs / g.
g · tank or less, more preferably 2 coulomb / g · tank or more and 80 coulomb / g / tank or less. 2 coulombs / g
If the length is less than the tank, the crystallinity of the surface layer does not sufficiently decrease, and the number of treatment tanks needs to be increased, resulting in poor productivity. on the other hand,
If it exceeds 100 coulombs / g · tank, the strength of the carbon fiber substrate is greatly reduced. In addition, from the viewpoint of maintaining the reduction in crystallinity in an appropriate range, the total amount of electricity in the energization treatment is from 2 coulombs / g to 1,000 coulombs / g, and
It is preferable to be 0 to 500 coulombs / g or less. The processing time is preferably from several seconds to ten and several minutes, more preferably from about 10 seconds to two minutes.

Also, in the step of washing and drying after the electrolytic treatment, if the drying temperature is too high, the functional groups present on the outermost surface of the carbon fiber are easily lost by thermal decomposition. Therefore, it is desirable to dry at the lowest possible temperature,
Specifically, it is desirable to dry at a drying temperature of 250 ° C. or lower, more preferably 210 ° C. or lower.

The carbon fiber after the surface treatment has a surface nitrogen concentration N / C and a surface oxygen concentration O / C measured by photoelectron spectroscopy (hereinafter, ESCA) of 0.02 or more, respectively.
It is required to be 0.2 or less, preferably 0.0
It is preferably from 3 to 0.15. That is, when N / C and O / C are out of the above ranges, there is a possibility that the adhesion to the resin may be reduced.

The compound used as a sizing agent is
Epoxy sizing agents are preferred, and aliphatic compounds having a plurality of epoxy groups are particularly preferred. The number of epoxy groups is preferably 2 to 4 in order to effectively bridge the carbon fiber and the matrix resin and to suppress the reaction between the sizing agents. In addition, the sizing agent has a rigid and sterically large compound at the interface between the carbon fiber and the matrix resin at the interface between the carbon fiber and the matrix resin.
It is desirable that the molecular weight be small. Specifically, the epoxy equivalent is from 80 to 1,000, more preferably from 90 to 50.
0 or less, the molecular weight is 100 or more and 2000 or less,
Further, it is preferably 200 or more and 1000 or less. As the compound, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene oxide diglycidyl ether, polypropylene diglycidyl ether and the like are effective.

The amount of the sizing agent to be adhered must be 0.01% or more and 5% or less per unit weight of carbon fiber.
It is important, and more preferably 0.1% or more and 2% or less.
If it is less than 0.01%, the bridging between the carbon fiber and the matrix resin is insufficient, and the effect of improving the adhesive properties is small.
If the ratio exceeds the above range, the reaction between the sizing agents increases, and the polymer of the sizing agent occupies between the carbon fibers and the matrix resin.

The solvent used for the sizing agent includes water, methanol, ethanol, dimethylformamide, dimethylacetamide, acetone and the like. Water is preferred from the viewpoint of easy handling and disaster prevention. Therefore, it is preferable to use an epoxy compound which is insoluble or hardly soluble in water by adding an emulsifier, a surfactant and the like to make it dispersible in water.

After the sizing agent application treatment, the drying temperature in the drying step is preferably from 150 ° C. to 350 ° C., more preferably from 180 ° C. to 250 ° C.
When the temperature is lower than 150 ° C., the solvent of the sizing agent cannot be completely removed, which may adversely affect the adhesive properties of the composite, and the drying time is long, which is not industrially practical.
If the temperature is 350 ° C. or higher, the curing of the sizing agent proceeds,
Since the carbon fiber bundle is hardened and the spreadability of the bundle is deteriorated, there is a possibility that good composite molding cannot be performed.

The carbon fiber thus obtained is combined with a resin by a known method such as a prepreg method, a filament winding method, etc., and is cured into a composite material through a post-molding or heat treatment step.

In the case of the prepreg method, a carbon fiber reinforced resin prepreg is obtained by impregnating the carbon fiber in a unidirectional, woven, yarn or mat form with a resin to obtain a carbon fiber reinforced resin prepreg. After the shaping step, the carbon fiber reinforced resin composite material is formed by heat molding by a method such as press, autoclave or lapping.

The matrix resin is not particularly limited.
Since the sizing agent compound has an epoxy group, an epoxy resin having high affinity is preferable.If the curing temperature is too high, the sizing agent imparted to the carbon fiber is liable to be degraded or decomposed, and adheres to the resin. The curing temperature is 250 ° C. or less, and
Epoxy resins at 0 ° C. or lower are preferred. Specifically, an epoxy resin cured at 180 ° C disclosed in Japanese Patent Publication No. 63-60056 and an epoxy resin cured at 130 ° C disclosed in Japanese Patent Publication No. 4-80054 are preferably used in the present invention. Can be It is more preferable to use a resin whose toughness is increased by mixing rubber particles and thermoplastic particles, or to reinforce the prepreg layer with thermoplastic resin particles or fibers for improving the impact characteristics of the composite material.

The impact characteristics of the obtained composite material are measured by a Charpy impact tester, and not only the total absorbed energy but also the instrumented Charpy which is used to determine the maximum load and the absorbed energy from the impact force curve to the maximum load is used. This is very important. In the case of brittle materials such as carbon fiber composite materials, the absorbed energy after the maximum load at which fracture starts is an indicator of the ease of fragmentation, but the maximum load or the absorbed energy up to the maximum load is more important in terms of function retention It can be said. The carbon fiber reinforced resin composite material of the present invention has a high maximum load and a high absorption energy up to the maximum load. The so-called ductility index, which is a value obtained by dividing the absorbed energy after the maximum load when the unidirectional flat plate is subjected to impact fracture by flat wise by the absorbed energy up to the maximum load , is 0.2 to 0.6, preferably 0.3 to 0. 5 is good. When the ductility index is larger than 0.6 , the maximum load is low because the fracture starts due to shear, and the energy is absorbed by the further progress of the shear fracture, and even if the total absorbed energy until the final fracture is high, There is a possibility that practical function retention ability is low. On the other hand, the ductility index
If it is less than 0.2, it will be extremely brittle, and other properties, particularly, tensile strength and the like may be reduced.

Although the carbon fiber of the present invention can be used alone, it can also be combined with other carbon fibers or other reinforcing fibers to form a composite material, and it is preferable to optimize it according to the application. It can be applied to sports applications such as golf shafts, tennis rackets, fishing rods, and aerospace applications, but is particularly effective for golf shafts in which impact characteristics are important. The golf shaft can be formed by a conventionally known technique such as a lapping method,
Further, in order to maximize the shaft characteristics, it is preferable to optimize the lamination structure or the combination with carbon fibers or other reinforcing fibers having other characteristics.

[0027]

The present invention will be described more specifically with reference to the following examples. The strand tensile modulus and strength and EDS in the present invention were determined by the following methods.

(Strand Tensile Modulus and Strength) JI
The measurement was performed according to the SR-7601 resin impregnated strand test method. As a resin formulation, "BAKELITE"
ERL422 / 3/3 boron monoethylamine / acetone = 100/3/4 parts was mixed well and used.

The (EDS) resin was prepared as follows according to Example 1 disclosed in Japanese Patent Publication No. 4-80054. That is, 3.5 kg of Epicoat 1001 manufactured by Yuka Shell Epoxy
(35 parts by weight), Yuka Shell Epoxy Co. 828
2.5 kg (25 parts by weight), 3.0 kg (30 parts by weight) of Epicron N740 manufactured by Dainippon Ink and Chemicals, 1.5 kg (15 parts by weight) of Epicoat 152 manufactured by Yuka Shell Epoxy and Denka Co., Ltd. 0.8 kg (3 parts by weight) of formal # 20 and 0.5 kg (5 parts by weight) of dichlorophenyldimethylurea were added and stirred for 30 minutes to obtain a resin composition. This was coated on release paper to form a resin film.

First, a resin film in which a resin to be combined with carbon fibers is coated on a silicon-coated paper is wound around a steel drum having a circumference of about 2.7 m, and then the carbon fibers drawn from a creel are traversed on the resin film via a traverse. After winding and arranging the resin, the resin film is re-covered from above the fiber, and then the resin is impregnated into the fiber by rotating and pressing with a pressure roll to obtain a resin having a width of 300 mm and a length of 2.
A 7 m unidirectional prepreg is prepared.

At this time, the drum is heated to 60 to 70 ° C. in order to improve the resin impregnation between the fibers, and the basis weight of the prepreg is adjusted by adjusting the rotation speed of the drum and the feed speed of the traverse. A prepreg having 200 g / m ² and a resin amount of about 35% by weight was prepared.

The prepreg thus produced was cut,
(+ 25 / -25 / + 25 / -25 / 90) Laminated with the configuration of _s , using an autoclave at 135 ° C., 3 kgf / cm ²
Heat and cure for 2 hours underneath.
A cured plate of mm was prepared.

The test piece had a width of 25.4 mm and a length of 230 mm. The measurement was carried out using a normal tensile test jig and a test length of 127.
mm, and measured at a strain rate of 1 mm / min. The peel strength was determined from the load at the time when peeling started on the side surface of the test piece.

Further, the specific gravity of the carbon fiber described in this example, O / C and N / C measured by ESCA, and the instrumented Charpy impact energy were determined as follows.

(Specific gravity) The specific gravity was measured by the floatation / sedimentation method of JIS R-7601.

(O / C and N / C) Surface oxygen concentration O / C or surface nitrogen concentration N / C measured by ESCA
Means a value obtained according to the following procedure. First, after cutting a carbon fiber bundle from which a sizing agent or the like was removed with a solvent and spreading and arranging it on a stainless steel sample support, the photoelectron escape angle was 90 °, and MgKα _1,2 was used as an X-ray source, The inside of the sample chamber is kept at a vacuum of 1 × 10 ⁻⁸ Torr. As a correction of the peak due to charging during measurement, first, C _1S
Is adjusted to 284.6 eV. The C _1S peak area is determined by drawing a linear baseline in the range of 282 to 296 eV. The O _1S peak area is obtained by drawing a linear baseline in the range of 528 to 540 eV, and the N _1S peak area is obtained by drawing a linear baseline in the range of 398 to 410 eV. Here, the surface oxygen concentration O / C is determined by the above O _1S peak area and C _1S
The ratio of the number of atoms calculated by dividing the ratio of the peak areas by the sensitivity correction value specific to the device. For example, when ESCA-750 manufactured by Shimadzu Corporation is used, the sensitivity correction value unique to the above-described apparatus is 2.85. Here, the surface oxygen concentration N / C refers to the atomic ratio calculated by dividing the ratio of the N _1S peak area to the C _1S peak area by a sensitivity correction value unique to the apparatus. For example, when ESCA-750 manufactured by Shimadzu Corporation is used, the sensitivity correction value unique to the above-described apparatus is 1.7.

(Instrumented Charpy Impact Energy) Using the one-way prepreg described above, JIS-K-7077
, And the maximum load, the absorbed energy up to the maximum load, and the absorbed energy after the maximum load are measured using a Charpy impact tester that is instrumented. The dimensions of the test piece were 6 mm in thickness, 10 mm in width, and 60 mm in length, and the distance between spans was 40 mm.

Example 1 Acrylonitrile (AN) 9
Using a copolymer consisting of 9.7 mol% and methacrylic acid 0.3 mol%, an acrylic fiber having a single fiber denier of 0.6 d and a filament number of 18,000 was obtained by a dry-wet spinning method. The obtained fiber bundle is heated in the air at 240 to 280 ° C. at a draw ratio of 1.03 to convert it into oxidized fiber, and then the temperature is raised to 180 ° C. in a temperature range of 300 to 500 ° C. in a nitrogen atmosphere. / Min and 10% stretching, then 1
It was baked to 700 ° C. Using an aqueous solution of ammonium bicarbonate having a concentration of 0.2 mol / l as an electrolytic solution, the amount of electricity supplied per tank is set to 10 coulombs / g. Processed. At that time, the electrolytic solution turned black. The carbon fiber subjected to the electrolytic treatment was subsequently washed with water and dried in 150 ° C. heated air. Subsequently, a sizing agent obtained by adding 5% of a nonionic emulsifier to glycerol triglycidyl ether is diluted with water so that the component becomes 1% by weight, and a sizing agent mother liquor is prepared. And dried at 180 ° C. The adhesion amount was 0.4%.

The specific gravity of the carbon fiber thus obtained was 1.73, and the strand tensile strength and elastic modulus were 570 kgf / mm ² and 31 tf / mm ² , respectively. O / C and N
/ C was 0.09 and 0.03, respectively. Also E
DS was 25 kgf / mm ² .

FIG. 1 shows a load-time diagram when the Charpy impact characteristics of the unidirectional material were measured. The maximum load is as high as 5.5 kN and the absorbed energy up to the maximum load is 6
It was as large as 6 kJ / m ² . The ductility index was 0.34. Using this material, 20 golf shafts were made,
When a robot actual hit test was performed under the conditions of a head speed of 50 m / sec and a high heel hit, none of the robots was damaged even after 100 actual hits.

(Comparative Example 1) A carbon fiber obtained by spinning and firing in the same manner as in Example 1 was used, and the concentration was 0.1 mol / l.
The sulfuric acid aqueous solution was used as an electrolytic solution, and the amount of electricity supplied was 10 coulombs / g, and the treatment was performed in one tank. The carbon fiber subjected to the electrolytic treatment was subsequently washed with water and dried in 150 ° C. heated air.

Subsequently, a sizing agent obtained by adding 5% of a nonionic emulsifier to Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd. was diluted with water so that the content of the component became 1% by weight, and a sizing agent mother liquor was prepared. A sizing agent was applied to the carbon fiber by the method, and drying was performed at 180 ° C. The adhesion amount was 0.5%.

The specific gravity of the carbon fiber thus obtained was 1.73, and the strand tensile strength and the elastic modulus were 560 kgf / mm ² and 31 tf / mm ² , respectively. O / C and N
/ C was 0.12 and 0.01, respectively. Also E
DS was 16 kgf / mm ² .

FIG. 2 shows a load-time diagram when the Charpy impact characteristics of the unidirectional material were measured. The maximum load is as low as 4.3 kN, and the absorbed energy up to the maximum load is 4
It was as small as 6 kJ / m ² . The ductility index was 0.96. Using this material, 20 golf shafts were made,
When a robot actual hit test was performed in the same manner as in Example 1, only four of them did not break until after 100 actual hits.

Comparative Example 2 Acrylonitrile (AN) 9
Using a copolymer consisting of 9.7 mol% and 0.3 mol% of methacrylic acid, a single fiber denier of 0.1 was obtained by a wet spinning method.
6d, an acrylic fiber having 18,000 filaments was obtained. The obtained fiber bundle is fired in the same manner as in Example 1,
Carbon fiber was used. The obtained carbon fiber was concentrated at a concentration of 0.1 mol /
One sulfuric acid aqueous solution was used as an electrolytic solution, and the amount of electricity supplied was set to 40 coulombs / g, and the treatment was performed in one tank. The carbon fiber subjected to the electrolytic treatment was subsequently washed with water and dried in 150 ° C. heated air. Subsequently, a sizing agent obtained by adding 5% of a nonionic emulsifier to glycerol triglycidyl ether,
A sizing agent mother liquor was prepared by diluting with water so that the components became 1% by weight, a sizing agent was applied to carbon fibers by a dipping method, and drying was performed at 180 ° C. 0.4% adhesion amount
Met.

The specific gravity of the carbon fiber thus obtained was 1.73, and the strand tensile strength and the elastic modulus were 450 kgf / mm ² and 31 tf / mm ² , respectively. O / C and N
/ C was 0.16 and 0.01, respectively. Also E
DS was 22 kgf / mm ² . FIG. 3 shows a load-time diagram when the Charpy impact characteristics of the unidirectional material were measured. The maximum load was as low as 4.1 kN, and the absorbed energy up to the maximum load was as small as 45 kJ / m ² . The ductility index was 0.17. Using this material, 20 golf shafts were produced, and a robot actual hit test was performed in the same manner as in Example 1. As a result, only two of them did not break until 100 actual hits.

[0047]

Industrial Applicability According to the present invention, carbon fiber excellent in impact resistance suitable for sports applications such as golf shafts, tennis rackets, fishing rods and aerospace applications, and particularly suitable for golf shafts in which impact characteristics are important. A reinforced resin composite can be provided.

[Brief description of the drawings]

FIG. 1 shows a load-time diagram of the composite material obtained in Example 1 in an instrumented Charpy impact test.

FIG. 2 shows a load-time diagram of the composite material obtained in Comparative Example 1 in an instrumented Charpy impact test.

FIG. 3 shows a load-time diagram in an instrumented Charpy impact test of the composite material obtained in Comparative Example 2.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FIB29L 31:52 (56) References JP-A-5-49717 (JP, A) JP-A-4-361616 (JP, A) JP-A-63-221169 (JP, A) JP-A-61-124677 (JP, A) JP-A-62-149968 (JP, A) JP-A-2-269867 (JP, A) JP-A 1-272867 (JP JP, A) JP-A-63-135232 (JP, A) JP-A-5-42536 (JP, A) JP-A-5-170952 (JP, A) JP-A-7-70925 (JP, A) (58) ) Surveyed field (Int.Cl. ⁷ , DB name) C08J 5/04-5/10 C08J 5/24 B29B 11/16 B29B 15/08 A63B 53/10

Claims (3)

(57) [Claims] 1. A specific gravity of 1.75 or less and a tensile modulus of 29 tf.
/ mm ² or more, tensile strength 500 kgf / mm ² or more, photoelectron spectroscopy
Surface nitrogen concentration N / C measured by the method ESCA and
The surface oxygen concentration O / C is 0.02 to 0.2, respectively.
And an aliphatic compound having a plurality of epoxy groups.
Add a oxy sizing agent in an amount of 0.0
A carbon fiber reinforced resin composite material provided with 1 to 5% and reinforced with carbon fiber having a board edge peel strength of 22 kgf / mm ² or more. 2. The carbon fiber reinforced resin composite material according to claim 1, wherein the carbon fiber reinforced resin composite material is a golf shaft. 3. The specific gravity is 1.75 or less, and the tensile modulus is 29 tf.
/ mm ² or more, tensile strength 500 kgf / mm ² or more, photoelectron spectroscopy
Surface nitrogen concentration N / C measured by the method ESCA and
The surface oxygen concentration O / C is 0.02 to 0.2, respectively.
And an aliphatic compound having a plurality of epoxy groups.
Add a oxy sizing agent in an amount of 0.0
A carbon fiber reinforced resin prepreg, which is provided with 1 to 5% and reinforced with carbon fiber having a board end peel strength of 22 kgf / mm ² or more.