JPS6076335A - Carbon fiber for composite materials and its manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to carbon fibers for use in composite materials, and its manufacturing benefits to composite materials.

Traditionally, carbon fibers are mixed with wood for other composite materials (e.g. synthetic resins or metal matrices). When mixed with IJ Lux on composite materials, it improves its bottom inertness and improves its affinity with the matrix. In order to improve the surface area of W/1, research has been conducted on activating the surface of W/1. Previous improvement methods that applied treatment had nine drawbacks, such as the manufacturing process being complex and difficult to control, and poor work efficiency.

The present invention provides a new Noble-surface-activated mt-moisture carbon fiber for composite materials that can improve the laminar shear strength when used in composite materials, and is easy and efficient to manufacture. , formed by forming a coating of six-sided V-shaped carbon fibers, alkoxyaluminum acetylate, its hydrolyzate, or aluminum oxide.

Furthermore, the present invention provides a method for producing the above-mentioned carbon #&fiber for composite materials, in which a part of the alkoxy group of aluminum alcoholate is added to the bottom surface of the carbon fiber with ethyl acetoacetate or methyl acetoacetate. The method is characterized in that a film of a solution of a substituted alkoxyaluminum acetylate is entirely formed, and the film is left to stand or is heated.

Next, examples of the present invention will be described.

As a raw material, a part of the alkoxy group of aluminum alcoholate is replaced with ethyl acetoacetate or methyl acetoacetate to create alkoxyaluminum acetylate, and this is dissolved in a dilute alcohol bath solution for a specified period of time to obtain a solution, or as necessary. Depending on the amount of solution added as acetic acid II? The carbon fibers to be processed are then stuck to a narrow 1'iK to form a coating. Possible methods for forming the coating include immersion in the solution, spray coating with a bath solution, etc., but it is preferable to continuously pass through the solution.For example, in a U-shaped Pour the above-mentioned treatment solution into a glass container, and open the carbon fiber assembly 9 at one end.
It is efficient to use four people to guide the solution through the open end at the other end and allow the gold in the solution to pass through the solution continuously at a predetermined speed. Thus, the carbon fibers to which the solution coating was attached are air-dried in the air, and the coating is completely dried to obtain the carbon fibers for composite materials of the present invention. If necessary, the carbon fiber with the dried coating is placed in a heating oven and heated to 100°C or higher to produce a product.

In the above production method, 1 of aluminum alcoholate
By substituting the alkoxy radical sound of methyl acetoacetate or methyl acetoacetate to form alkoxyaluminum acetylate, the hydrolysis rate of aluminum alcoholate can be slowed down to facilitate the formation of the film. It has been found that the film produces a sound effect that can prevent cracking, whitening, etc. from shrinking during drying and heating. In addition, the above-mentioned air drying or relatively low temperature, e.g.
During the drying process at around 0°C, the alkoxyaluminum acetylate film comes into contact with moisture in the atmosphere and undergoes partial hydrolysis, resulting in the elimination of alkoxy groups and ethyl acetoacetate, resulting in the release of water. The resulting film contains hydrolysates such as aluminum oxide and aluminum acetylate. If necessary, heating may be carried out at a temperature of 100° C. or higher to form a partially or entirely aluminum oxide film. In this case, lOO
When heating in the range 4 to 500°C, aluminum oxide is partially formed, and a mixed film is formed with the above-mentioned film containing hydroxyl groups and acetyl groups. The film can be made of only aluminum.

In the preparation of the alkoxyaluminum acetylate solution described above, the addition of citric acid serves to further acetate a portion of the alcoholate.

To give a more detailed example of preparing the solution, an equivalent amount of alkoxyaluminum acetate is prepared by dissolving aluminum alcoholate in four equivalents of alcohol, adding an equivalent amount of ethyl acetoacetate, and stirring thoroughly. ] i!
When an equivalent amount of citric acid is added to , a portion of the alcoholate is further aceticated. Alcohol was added to this solution to prepare a diluted solution so that the alkoxyaluminum acetylate content was 0.4% by weight.

The reason why it is preferable to keep the film thickness after drying or heat treatment to 1 μm or less is because when manufacturing transparent metal oxide thin film tubes, if the thickness is greater than this, cracking and whitening will occur, the bond with the carbon fiber will break, and the coating will This is because there is a tendency not to.

The present invention also uses the carbon fiber for composite materials obtained in the above manner, and adds carbon fiber to any inorganic material such as synthetic resin, paulownia, ceramic, etc. to improve shear strength. In this case, the properties of the above-mentioned coating are used to produce a composite material.

Depending on the material of the wood to be composited with carbon fiber, from room temperature to 50°C.
Preferred composite materials can be obtained by heating at temperatures up to 0°C or above 500°C.

In this case, the coating of the carbon fiber for the material to be bonded according to the present invention is treated in advance with a coupling agent such as silane, titanium, borane, etc., and then the carbon fiber is bonded to other desired composite materials. Good too.

Next, a more detailed example will be described.

Example 1 Inpropyl Al: I-/l/A+! (i −00
3H7) 30.7mo4 was converted into isozolobyl alcohol (
1-03H70H) 22 mol was dissolved in the entire bath, and further methyl acetoacetate (0113-0001%0000i) b)
0.7 motk was added and stirred to create inbrobogisia aluminum ethyl acetoacetate, and further acetic acid (0
113000H) was added with Q and 5 mots and stirred to completely coat the prepolymer.Additionally, this was mixed with isopropyl alcohol to prepare a bath solution for carbon fiber treatment.

Next, carbon fibers are immersed in this solution to form a coating on their surfaces. Next, this is dried at room temperature, and further calcined at 200°C for 10 minutes to coat the surface of the carbon fiber with alkoxyaluminum ethyl acetylate and aluminum hydroxide, aluminum acetylate, and aluminum oxide produced by its hydrolysis. A coexisting film was formed. Next, the composite stinging charcoal $A#R fiber of the present invention and an epoxy resin mixed with a small amount of hardening agent BF3 are mixed so that the coulometric ratio is 1:1, and the composite material is molded under heat and pressure. Molded. Two 3 x 10 x 1 test pieces were prepared for each composite material of 0.0 x 10 x 1, and the total shear strength was measured using the test pieces, and the following measurement results were obtained.

Example 2 A solution having the same composition as in Example 1 above was similarly applied to the surface of the same carbon fiber to form a film, and then dried and further mixed with 1 aminoethylaminopropyl methyl dimethoxysilane Q, 2 wt% and ethyl alcohol 89.8w
t% and water 10. A silane coupling agent solution consisting of 0.0 wt. Using this, a composite molded material of the present invention with an epoxy resin as in Example 1 was obtained.

Regarding this, the layered shear strength was measured in the same way, and the following ff
The results shown in 1l were obtained.

Comparative Example Carbon fiber t to be subjected to the same surface treatment as used in Example 1
Same as in Example 1, a composite molded material with epoxy resin was made, and the cross-layer shear strength was measured in the same manner.
The results shown in ml below were obtained.

*Conventional material is a composite material that uses commercially available second-surface treated carbon fiber.

*Strained conventional product B is a composite material using carbon fiber that has been subjected to commercially available surface treatment and silane coating agent treatment.

As is clear from Kamigumi &1, the interlaminar shear strength of the product of the present invention is significantly higher than that of the untreated product.

In addition, in the treatment solution of the present invention, aluminum is added to the solution of alkoxyaluminum acetylate, titanium, titanium,
It is also possible to mix a solution of alkoxy acetylate substituted with gold ingots such as zirconium, and mix metal oxides such as titanium oxide and zirconium oxide into the coating.

According to the present invention, in light 1, a coating of a solution of an alkoxyaluminum acetylate obtained by substituting a part of the alkoxy groups of an aluminum alcoholate with methyl acetoacetate or methyl acetoacetate is formed on the surface of the carbon fiber,
By leaving this as it is or heating it, it is possible to produce 8 m fibers of carbon fiber for composite materials in a simple process, which provides a strong bond. Depending on the quality of the material, it is possible to provide a composite material with improved shear strength by heating the ifm fiber coating to a predetermined temperature, or without heating, or by using a coupling agent as necessary. It has the effect of

Patent applicant: 2 persons other than Kawai Joki Seisakusho Co., Ltd. Procedural amendments Showa Ill 5th Office II I+-7th Director of the Japan Patent Office 1, Indication of the case 1983 Patent Application No. 183691 2, Name of the invention Carbon for composite materials Relationship with the case of a person making an amendment to the legal interest in the manufacture of textiles for composite materials 3 Patent Applicant 141 Kawai Musical Instruments Manufacturing Co., Ltd. 4 Agent 5 Amendment Order No. 1 A] (Voluntary) Month, Showa 16 Column 7 of “Detailed Description of the Invention” of the specification to be amended, contents of the amendment (1) Page 7, line 8 of the specification “Isopropyl alcohol”
is corrected to "isobutetraboxyaluminum".

(2) Same book, page 7, line 10 rmoA! eJ 'k rm
To OL,” he corrected.

Claims (1)

[Scope of Claims] 1. A carbon fiber for composite material comprising a coating of alkoxyaluminum acetylate, its hydrolyzate, or aluminum oxide formed on the surface of the carbon fiber. 2. Charcoal X fiber for composite material according to claim (1), wherein the thickness of the coating is 1 μm or less. 3 Aluminum alcoholate 1 on the bottom of the carbon fiber
Carbon X for composite materials, which is characterized by forming a film of a solution of alkoxyaluminum acetylate substituted with 16 alkoxy group ethyl acetobutyrate or methyl acetoacetate, and leaving or heating the film. Fiber manufacturing method. 4. A composite material made by combining carbon fibers for composite materials with a coating of alkoxyaluminum acetylate, its hydrolyzate, or aluminum oxide formed on the bottom surface of the carbon fibers and any other wood for composite materials.