JPS6256366A - Carbon fiber reinforced carbon composite material - 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] (Industrial application field) The present invention is a polystyrylbilinone resin (hereinafter referred to as a polystyrylbilinone resin).

PSP resin) and carbon fiber base material? The present invention relates to a carbon composite material, that is, a C/C composite material.

(Prior art and its problems) In general, C/C composites have high specific strength and specific modulus, and have excellent mechanical performance at high temperatures, so they are used as brake materials for rocket nozzles, aircraft, racing cars, etc. has been done. C/C composites can be roughly divided into two types: (1) Resin impregnation method in which a thermosetting resin such as phenol resin or furan resin is impregnated into an all-carbon fiber intermediate base material, molded and cured, and then carbonized (2) Carbonization using methane, etc. It is produced by two methods: hydrogen is introduced into the product at a relatively low concentration and kept at high temperature, and carbon is directly deposited in the gas phase using the CVD method. In the case of the resin impregnation method of (1), the phenol resin, furan resin, etc. have a low carbonization residual rate (carbonization rate) after carbonization firing, and the resulting C/C
The composite is of low strength. In order to improve the strength of such composites, both the resin impregnation and carbonization processes are repeated, but the composites obtained in this way have poor working efficiency and are expensive to manufacture. be.

(Means for solving all the problems) As a result of intensive studies on C/C composite molding materials with a high carbonization rate, the inventors of the present invention found that C/C composite molding materials with a high carbonization rate can be obtained by using PSP resin as an IJ hook. /C It was discovered that a composite molding material could be obtained and this led to the present invention.

That is, the present invention provides a carbon fiber-reinforced carbon composite material made by completely carbonizing a molding material containing a PSP resin and a carbon fiber base material.

The PsP resin used in the present invention is disclosed in French Patent No. 22
61296 and 2378.052, an aromatic dialdehyde such as terephthalaldehyde and at least two reactive methyl groups such as 2,6-lutidine, 2,4,6-collidine. It is obtained by polycondensation with a pyridine derivative substituted by Such resins usually have the general formula %() (where R and R4 are the same or different hydrocarbon groups and represent segments which can contain heteroatoms, A1 is the same or different ether groups, represents a stereotransfer bonding group such as a sulfone group, represents an atom or group forming a bridge between JRl and the aromatic ring of the styrylpyridine chain, R2 represents hydrogen or a methyl group, an ethyl group, k e l +011 indicates an integer that may be equal to zero.)].

PSP resin has excellent heat resistance, flame resistance, low smoke generation, and a high carbonization rate compared to phenolic resins, polyimide resins, etc. Table 1 shows the results of a comparison of carbonization rates for each resin.

Table 1 Note that the carbonization rate of PSP resin at 1000°C in an inert atmosphere is as high as 65%, and in order to obtain such a high carbonization rate when pitch or phenolic resin is used, carbonization must be performed under pressure. Considering these factors, this resin is a preferable matrix for the C/C conyff knot molding material.

The PSP resin used in the present invention may be an epoxy resin or a phenol 4i1 resin as long as it does not impair the purpose of the present invention.

Melamine resin, urea resin, furan resin, xylene resin,
Thermosetting resin such as thermosetting polyimide resin; yje ref 1J-ren resin, polyarylene sulfide resin,
I Realylene Keto/Resin, Polyarylene Ether Resin, Polycarbonate Resin, Polyvinyl Chloride Resin, Polysulfone Resin, Polyimide Resin, Polyamide Imide Resin, 7f! Riami P resin, f! Thermoplastic resins such as urethane resin, I-reester resin, and fluorocarbon resin can be used in combination.

The epoxy resin that can be used in the present invention desirably has at least two or more epoxy groups 1c in one molecule, and may be a commercially available epoxy resin, such as Epiklon manufactured by Dainippon Ink and Chemicals (Sam). Examples include those sold under trademarks. Preferred epoxy resins include, for example, brominated epoxy resins and novolak phenol epoxy resins, which have excellent heat resistance and flame retardancy.

Incidentally, it is preferable that a curing agent and a curing accelerator such as an amine compound and an acid anhydride are added to the epoxy resin.

Phenol resins, melamine resins, xylene resins, urea resins, and furan resins (hereinafter abbreviated as phenolic resins) that can be used in the present invention include phenol, cresol, alkylphenol, alkylcresol, melamine, urea, and furfural.

It is a product obtained by condensing furfuryl alcohol or the like with an aldehyde such as formalin or glyoxol in the presence of an acid or alkali catalyst, such as Glyofen and Percam manufactured by Dainippon Ink and Chemicals Co., Ltd.

Resins commercially available under trademarks such as Foundlets can be used.

Polyimide resins that can be used in the present invention include bismaleimide and its derivatives, such as polyamino bismaleimide manufactured by Rhone Poulenc of France, which is generally known as kelimide or quinel, and BT resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
Thermosetting polyimide resins such as bismaleimide-triazine resins are preferred, but other polyimide resins can also be used.

Among the other resins mentioned above, the processing temperature of PSP resin, e.g. 2
It is preferable to use a resin that can be cured at a temperature of about 00°C, and specifically, phenolic resins and thermosetting polyimide resins are preferable.

The amount of the resin that can be used together with the PSP resin is usually 1 to 40 Mm% based on the PSP resin.

The carbon fiber base material used in the present invention can be used without any limitation in shape, such as long fibers, short fibers, woven or knitted fabrics, sheets, mats, and -''2-par.

The molding material to be formed into a C/C composite in the present invention usually contains 10 to 70% by weight of the total carbon fiber base material. Such a molding material is usually produced by the resin impregnation method described above.

When short fibers are used as a carbon fiber base material, the molding material is made by mixing the fibers and resin to a semi-cured state, and then making it into a K-let shape and using it as an injection molding material. Material for injection molding and hot press molding in the form of short fibers, made into a semi-hardened state, mixed with fiber and resin, made into a sheet and made into a semi-hardened state, so-called 7-domolding compound, mixed with fiber and resin. Then, it was made into a block and semi-hardened. Examples include a so-called bulk molding compound, a molding material in which short fibers are previously formed into a sheet, mat, or peno, and this is impregnated with a resin to bring it into a semi-cured state.

In addition, as for products using long fibers, there are fabrics woven with long fibers in advance,
Knitted fabric or sheet, pine) and heat? −-' −, etc., are impregnated with resin to a semi-cured state, and the nine-silipreg and the long fibers (tow) themselves or the long fibers are aligned in a certain direction, and completely impregnated with resin to a semi-cured state. Includes tow prepreg and unidirectional prepreg.

These molding materials are used depending on the shape, required performance, required number, etc. of the final molded product, and are molded by various methods such as injection molding, hot press molding, autoclave molding, and transfer molding.

Of course, the molding material of the present invention can also be molded by the so-called hand lay-up method by adding a strong acid such as phosphoric acid, sulfuric acid, or hydrochloric acid as a catalyst, but if necessary, it is possible to mold the molding material by selecting one of these molding methods. Good.

The carbon fiber base material used in the present invention includes inorganic fillers such as glass fibers, metal fibers, ceramic fibers, potassium titanate, asbestos, silicon carbide, ceramics, silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite,
Zeolite.

Mica, mica, nephelinsinite, Merck, atalpulgite, wollastonite, PMF, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium dioxide.

Zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite digypsum, glass beads, glass powder, glass balloon, quartz.

Examples include quartz glass, and fibrous fillers are preferred. Note that it is appropriate to add the filler to the molding material in 1 to 10 layers.

In the present invention, when impregnating the fiber base material with PSP resin,
In order to reduce the viscosity of the resin and facilitate impregnation, various m-agents can be added to the PSP resin as needed. Examples of such bath agents include ketones such as acetone, methyl ethyl keto/etc., methanol, ethanol, propatool, Alcohols such as butanol; methyl acetate, ethyl acetate,
Esters such as propyl acetate, butyl acetate, cellosolves, and ethyl ether; aromatic agents such as benzene, toluene, and xylene; chloroform, carbon tetrachloride, methylene, and chloride.

Halogenated hydrocarbons such as tricrene; high-boiling magents such as trimethylformamide, dimethylacetamide, zomethylsulfoxide, and N-methylpyrrolidone can be used.

When these m-agents are added to impregnate the viscosity of the resin into a metal-finished fiber base material, the bath agent is completely removed by heating, and at the same time the resin i
Although B-stage can be achieved, the amount of residual charge at that time is desirably 10 or less, and more preferably 2 or less.

The temperature of the molding material used in the present invention is usually 100 to 250°C.

It is preferably used after being cured at 150 to 250°C. Further, after such curing treatment, it is preferable to further perform a post-curing treatment at 200 to 300°C for 1 hour or more.

In the C/C composite material of the present invention, the temperature of all the above molding materials is usually 1500°C or higher, preferably 2000 to 3000°C.
It is manufactured by carbonizing at ℃ for about 10 minutes to 4 hours. At this time, it is preferable to apply pressure.

In addition, the composite material usually has a carbon fiber base material containing 50 to 8
5iQ%, preferably 60 to 80 times.

(Effects of the Invention) The composition of the present invention has excellent heat resistance, flame retardance, mechanical strength when heated, etc., and is useful for brake materials for aircraft, racing cars, etc., rocket nozzles, etc.

(Example) Next, the present invention will be further explained with reference to Examples and 3 Examples. Note that parts and parts in the examples are based on weight.

[Example 1] PSP 6022M (PSP resin, resin content 75%, 5
NPE), 23.3 parts of Ebicuron N-740-80M (resin content 80%, Dainippon Ink & Chemicals Co., Ltd.) as an epoxy resin, and 6.4 parts of diaminodiphenylsulfone (1st class reagent). In addition, it was diluted with acetone to make a liquid with a solid content of 40 g. The content of PSP resin in the solid content of this bath liquid was 80 inches.

Carbon fiber trading card cloth 6343 (fabric weight 200.9 parts m2, manufactured by Toshiku Co., Ltd.) was impregnated with this m night, and 130C1
B-stage was obtained by drying for 6 minutes to obtain a woven prepreg. This glycileg was sufficiently flexible and had little surface tackiness and was in good condition. Moreover, the prepreg has 3
The residual volatile content line of 90 with a weight of 009 parts m2 and a dulling time of 10 minutes at 200°C was 1.5 yen.

Obtained Gripreg15. y'light t200℃, 50k
Hot press molded under pressure of li'/cm2, 30
You can mold out the laminate in minutes and meet your friends. Then cure at 250℃ for 3 hours! :fc,. The resulting laminate No. 7 had a fiber content of 68%.

Then, the product Jul was placed in an electric furnace and heated for 20 minutes in a nitrogen atmosphere.
Carbonization was performed at 00°C for 30 minutes to prepare a C/C combo knot composite material. The content of carbon fiber in the obtained composite material is 7
It was double spotting. All physical properties of this composite material are shown in Table 2.

Table 2 [Example 2] No addition of z, 1 xy resin or diaminodiphenylsulfone, B-staging at 80°C for 20 minutes, hot pressing pressure t 10 kg/cm2 and post-curing time eS
A composite material was obtained in the same manner as in Example 1 except for changing the distance between U and F (laminate board before composite: 741st fiber board, unit weight 2700.!i'/m2, thickness 1.76 m). Its carbon fiber content was 74.5 ply.

Table 3 shows the physical properties of the materials to be bonded.

Table 3 [Example 3] PSP 6022M 133 parts, Ebicuron N 740
-80M 11.7 parts, cyamino zophenyl sulfone 3
．． Part 2.

Add 0.5 part of chlorophenylated urea and 20.8 parts of Zolaiofen 5900 (resin content: 60 t, manufactured by Dainippon Ink & Chemicals @) as a phenolic resin, and further adjust the solid content to 40 t with acetone. All used, below Example 1
A C/C composite material was obtained under the same conditions. The carbon fiber content of this composite material was 72 times denser, and its physical properties are shown in Section 4.

Table 4 [Example 4] PSP resin (PSP 6022-PC, manufactured by SNP, 1
Viscosity at 80°C: approx. 1500 mPa-8)
After adding and mixing uniformly, the mixture was sieved through a 32-mesh sieve to obtain a resin mixture with a uniform particle size. Thus obtained resin mixture 2
In addition to 55.9% of carbon fiber with a fiber length of 3m per 00g, it is well dispersed. The resulting resin mixture was wrapped flat in aluminum foil to prevent it from scattering, placed in an oven, and heated at about 200°C, while 1 part of the volatile matter was distilled off under reduced pressure at mHg. When the resin is beaten after cooling, the resin is uniformly adhered to the carbon fibers, and a molding material containing 23 layers of carbon fibers is obtained.

The bulk specific gravity of the resulting molded material is approximately 0.25! j/cm
”.This product was heated at 250℃ for 1 hour, 60 lessons/
- The molded product was molded under pressure and post-cured at 250°C for 16 hours to obtain a molded product. Then, in the same manner as in Example 1, C/
C combo knot composite material gold obtained. Its carbon fiber content! ′
i22 weight N%. All physical properties of the composite material are shown in Table 5.

Claims (1)

[Claims] A carbon fiber-reinforced carbon composite material made by carbonizing a molding material containing a polystyrylpyridine resin and a carbon fiber base material.