JPH05112657A - Resin composition reinforced with carbon fiber for thermoplastic resin reinforcement and carbon fiber reinforced thermoplastic resin composite material - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of giving a composite material having high strength and impact resistance by impregnating an olefinic polymer modified with an unsaturated carboxylic acid (derivative) into carbon filaments while aligning the filaments under tension and cutting the obtained rod-shaped composition. CONSTITUTION:The objective composition is produced by impregnating a thermoplastic resin consisting of an olefinic polymer modified with an unsaturated carboxylic acid (derivative) into carbon filaments while aligning the filaments under tension and cutting the obtained rod-shaped composition.

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 thermoplastic resin composite material having high strength and high impact resistance. More specifically, the invention relates to a carbon fiber reinforced resin composition for reinforcing a thermoplastic resin in which carbon fibers are arrayed and bundled in the longitudinal direction, and a carbon fiber reinforced thermoplastic resin composite material containing the same, which has high strength and high impact resistance.

[0002]

2. Description of the Related Art In recent years, fiber-reinforced resin compositions prepared by mixing and dispersing short carbon fibers in various matrices have high strength, high rigidity, low specific gravity, high electrical conductivity, low coefficient of thermal expansion, and high abrasion resistance. It is attracting attention as an industrially important material due to its excellent features. Generally, when a carbon fiber is mixed and dispersed in various thermoplastic resins such as polyester, polyamide, polyolefin, and acrylic resin to obtain a fiber-reinforced thermoplastic resin composition, a large number of carbon short fibers are previously aggregated with a sizing agent or the like. The aggregate of short carbon fibers thus obtained is kneaded with a thermoplastic resin to obtain fiber-reinforced resin pellets, and the pellets are injection-molded into a desired mold to manufacture.

On the other hand, in the conventional short carbon fiber aggregate, if the fiber content is increased when the resin component and the short carbon fibers are kneaded, the force required for the kneading becomes too large, and the reinforcing material during the kneading. The desired carbon length cannot be maintained as a result of the carbon fiber being cut, and as a result, sufficient strength and rigidity cannot be obtained.Therefore, the carbon fiber reinforced thermoplastic resin composite arrayed and aligned in the longitudinal direction is cut. By using the obtained small composite as a molding raw material, high characteristics are exhibited.

[0004]

However, it is generally expected that the filling of the thermoplastic resin with the inorganic fiber such as the carbon fiber is higher than the filling of the thermosetting resin with the inorganic fiber such as the carbon fiber. The current situation is that the reinforcement effect is not so high. The reason for this is that the affinity between the inorganic fiber and the thermoplastic resin is poor. In the case of thermosetting resin, the viscosity of the resin is low and the fiber surface is easily wetted,
It is considered that the functional group on the surface-treated fiber and the reactive group of the thermosetting resin exhibit a coupling effect. on the other hand,
In the case of a thermoplastic resin, it is considered that a sufficient reinforcing effect is not obtained because the resin has high viscosity and poor reactivity. Also, especially in the case of carbon fiber, since it has fewer functional groups than other inorganic fibers, there is almost no surface treatment effect with a silane coupling agent such as glass fiber, and the high characteristics of the fiber itself can be fully utilized. The reality is that they do not.

[0005]

The inventors of the present invention have made extensive studies to solve the above problems, and as a result, have been modified with unsaturated carboxylic acids or their derivatives while aligning carbon long fibers under tension. By using a rod-shaped fiber-reinforced thermoplastic resin composition obtained by impregnating a thermoplastic resin characterized by being an olefin-based polymer, by using as a carbon fiber-reinforced resin composition for thermoplastic resin reinforcement, the above problems The present invention has been reached by finding that the above is solved.

That is, an object of the present invention is to provide a carbon fiber reinforced resin composition for reinforcing a thermoplastic resin in which carbon fibers are arrayed and bundled in the longitudinal direction, and a carbon fiber reinforced thermoplastic resin containing the same and having high strength and high impact resistance. It is to provide a resin composite material.

[0007] The object is a carbon fiber reinforced resin composition obtained by cutting a rod-shaped composition obtained by impregnating a long carbon fiber under tension with a thermoplastic resin and squeezing the rod-shaped composition. An olefin polymer modified with an unsaturated carboxylic acid or a derivative thereof,
Carbon fiber reinforced resin composition for thermoplastic resin reinforcement, and
A carbon fiber reinforced resin composition obtained by cutting a rod-shaped composition obtained by impregnating a long carbon fiber under tension with a thermoplastic resin, wherein the thermoplastic resin is an unsaturated carboxylic acid or derivative thereof. Carbon fiber reinforced resin composition for reinforcing thermoplastic resin, which is an olefin polymer modified with
0 parts by weight was blended with 100 parts by weight of the thermoplastic resin, more specifically, a carbon fiber reinforced resin composite material, more specifically, obtained by impregnating a thermoplastic resin while aligning carbon long fibers under tension. Carbon fiber reinforced resin composition obtained by cutting a rod-shaped composition to be used
This can be easily achieved by the above-mentioned carbon fiber reinforced resin composition for reinforcing thermoplastic resin, which is blended in a weight percentage.

The present invention will be described in detail below. In the present invention, various conventionally known carbon fibers can be used as the carbon fibers, and specific examples thereof include polyacrylonitrile-based, pitch-based and rayon-based carbon fibers. The olefin-based polymer used in the present invention is obtained by adding an unsaturated carboxylic acid or a derivative thereof to a polyolefin and carrying out the reaction in the presence or absence of a radical generator to give an unsaturated carboxylic acid or It is an olefin polymer obtained by chemically bonding the derivative.

The unsaturated carboxylic acid or its derivative is preferably an anhydride, and specifically, maleic anhydride, maleic acid, acrylic acid, alicyclic carboxylic acid or the like can be used. When the olefin polymer is polypropylene, the amount of the unsaturated carboxylic acid or its derivative to be bonded is 0.005 to 100 parts by weight of polypropylene.
It is also 5 parts by weight, preferably 0.01 to 1.0 parts by weight. Known methods can be applied to the method of chemically bonding the unsaturated carboxylic acid or its derivative to the olefin polymer.

The carbon fiber content in the thermoplastic resin-reinforced carbon fiber reinforced resin composition is usually 50 to 95% by weight, preferably 70 to 90% by weight. The carbon fiber reinforced thermoplastic resin composite is manufactured by a so-called pull-through method, in which the reinforcing carbon long fibers are aligned under tension and impregnated with the thermoplastic resin to be molded. In the present invention, such a rod-shaped composition is cut into a small composite having a length in the fiber direction of preferably 3 to 25 mm, more preferably 6 to 10 mm. If it deviates from this range, it is not desirable in terms of feedability during injection molding.

Next, a description will be made of a carbon fiber reinforced thermoplastic resin composite material having high strength and high impact resistance, which is obtained by blending the thermoplastic resin-reinforced carbon fiber reinforced resin composition of the present invention with a thermoplastic resin. The matrix resin is not particularly limited, and examples thereof include polycarbonate, polystyrene, polyester, polyamide, polyolefin, acrylic resin, polyoxymethylene, polyphenylene sulfide, polyphenylene ether, polyphenylene oxide, polybutylene terephthalate, polyether ether ketone, polyphenylene sulfone. , Liquid crystal polymer, acrylonitrile-butadiene-styrene resin (A
Known thermoplastic resins such as polymers such as BS resin) and fluorine resins or copolymers thereof, or polymer alloys thereof can be mentioned.

The blending ratio of the above-mentioned thermoplastic resin-reinforced carbon fiber reinforced resin composition and matrix resin is 5 to 50 parts by weight of the thermoplastic resin-reinforced carbon fiber reinforced resin composition with respect to 100 parts by weight of the thermoplastic resin. Parts, preferably 5 to
It is in the range of 20 parts by weight. When the compounding amount of the carbon fiber reinforced resin composition for thermoplastic resin reinforcement is less than 5 parts by weight, the amount of carbon fibers is small and it is difficult to exhibit high characteristics, and when it exceeds 50 parts by weight, the amount of the olefin polymer increases, Various problems occur in the processes of deterioration of physical properties, mixing with matrix resin, and dispersion. In this method, it is considered that the bond between the carbon fiber and the resin having poor adhesion is strengthened by interposing a highly reactive olefin polymer. The method of blending such a matrix resin and the olefin polymer resin composition of the present invention is not particularly limited, but usually a single-screw extruder, a twin-screw extruder, a press machine, a high-speed mixer, injection It is carried out by a method such as a molding machine. Further, to the extent that the effects of the present invention other than the above components are not impaired, other types of carbon fibers, glass fibers, aramid fibers, boron fibers, short fibers such as silicon carbide fibers and long fibers, whiskers, nickel in these,
Fiber-reinforced materials such as fibers coated with metals such as aluminum and copper or metal fibers, or reinforcing materials and stabilizers composed of fillers such as carbon black, molybdenum disulfide, mica, talc and calcium carbonate.
Lubricants and other additives can be added. Less than,
The present invention will be specifically described by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[0013]

【Example】

Example 1 A modified polyolefin resin (“Novatech AP-790P” manufactured by Mitsubishi Kasei Co., Ltd.) was used as a matrix resin, and a pitch-based carbon fiber (“Dialead K223” manufactured by Mitsubishi Kasei Co., Ltd.) was used as a reinforcing fiber. (Diameter 3m
m, fiber content 77% by weight) was adjusted by a pultrusion molding method at a molding temperature of 240 ° C. This rod-shaped composition is about 10
A carbon fiber reinforced resin composition was produced by cutting into a mm length with a cutter.

This composition and polypropylene resin ("Mitsubishi Polypro 8800J" manufactured by Mitsubishi Kasei Co., Ltd.) were blended so as to have a carbon fiber content of 20% by weight (modified polyolefin amount 6% by weight), and then molded by injection molding. Then, a test piece was obtained. Then, the physical properties were measured.

Example 2 A modified polyolefin resin ("Novatech AP-790P" manufactured by Mitsubishi Kasei Co., Ltd.) was used as a matrix resin, and a pitch-based carbon fiber ("Dilead K223" manufactured by Mitsubishi Kasei Co., Ltd.) was used as a reinforcing fiber. Composition (diameter 3m
m, fiber content 83% by weight) was adjusted by a pultrusion molding method at a molding temperature of 240 ° C. This rod-shaped composition is about 10
A carbon fiber reinforced resin composition was produced by cutting into a mm length with a cutter.

This composition was blended with polypropylene resin ("Mitsubishi Polypro 8800J" manufactured by Mitsubishi Kasei Co., Ltd.) so as to have a carbon fiber content of 20% by weight (amount of modified polyolefin of 4% by weight), followed by injection molding. Then, a test piece was obtained. Then, the physical properties were measured.

Example 3 A modified polyolefin resin (“Novatech AP-790P” manufactured by Mitsubishi Kasei) was used as a matrix resin, and a pitch-based carbon fiber (“Dialead K223” manufactured by Mitsubishi Kasei) was used as a reinforcing fiber. Composition (diameter 3m
m, fiber content 77% by weight) was adjusted by a pultrusion molding method at a molding temperature of 240 ° C. This rod-shaped composition is about 10
A carbon fiber reinforced resin composition was produced by cutting into a mm length with a cutter.

This composition and ABS resin (manufactured by Mitsubishi Kasei Polytech Co., Ltd.) were blended so as to have a carbon fiber content of 20% by weight (modified polyolefin amount: 6% by weight), and then molded by injection molding to obtain a test piece. Obtained. Then, the physical properties were measured.

Comparative Example 1 20% by weight of a short carbon fiber aggregate and the above polypropylene resin were dry blended, and then the mixture was put into a screw extruder, melt-mixed, extruded into a strand, cooled with water, and cut into a pellet. The short carbon fiber reinforced molding material thus obtained was dried at 90 ° C. for 4 hours and then molded by injection molding to obtain a test piece. Then, the physical properties were measured.

Comparative Example 2 20% by weight of a short carbon fiber aggregate, 72% by weight of the polypropylene resin, and 6% by weight of the modified polyolefin resin were dry-blended, then squeezed into a screw extruder, melt-mixed and extruded in a strand form. After cooling with water, it was cut into pellets. The short carbon fiber reinforced molding material thus obtained was dried at 90 ° C. for 4 hours and then molded by injection molding to obtain a test piece. Then, the physical properties were measured.

Comparative Example 3 20% by weight of a short carbon fiber aggregate and the above ABS resin were dry-blended, then put into a screw extruder, melt-mixed and extruded into a strand, cooled with water and cut into pellets. The short carbon fiber reinforced molding material thus obtained was dried at 90 ° C. for 4 hours and then molded by injection molding to obtain a test piece. Then, the physical properties were measured. Examples 1-3,
Table 1 shows the results of measuring the physical properties of Comparative Examples 1 to 3.

[0022]

[Table 1]

As is clear from these comparisons, the present invention has the advantages of high strength and high impact resistance. Moreover, since the treatment is easy and low cost, it is industrially very useful.

[0024]

EFFECTS OF THE INVENTION The carbon fiber reinforced thermoplastic resin composition of the present invention has a high strength by using a small composite obtained by cutting a carbon fiber reinforced modified polyolefin resin arrayed and bundled in the longitudinal direction as a forming raw material. , Has the advantage of high impact resistance. Moreover, since the treatment is easy and low cost, it is industrially very useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location D06M 15/263 // D06M 101: 40 (72) Inventor Katsuji Shimamoto Kamoshida, Midori-ku, Yokohama-shi, Kanagawa 1000-cho, Sanritsu Kasei Co., Ltd.

Claims (2)

[Claims] 1. A carbon fiber reinforced resin composition obtained by cutting a rod-shaped composition, which is obtained by impregnating a continuous carbon fiber under tension with a thermoplastic resin, wherein the thermoplastic resin is not contained. A carbon fiber reinforced resin composition for reinforcing a thermoplastic resin, which is an olefin polymer modified with a saturated carboxylic acid or a derivative thereof. 2. A carbon fiber reinforced resin composition obtained by cutting a rod-shaped composition, which is obtained by impregnating a long carbon fiber under tension with a thermoplastic resin, and wherein the thermoplastic resin is not contained. Characterized by adding 5 to 30 parts by weight of a carbon fiber reinforced resin composition for reinforcing a thermoplastic resin, which is an olefin polymer modified with a saturated carboxylic acid or a derivative thereof, to 100 parts by weight of the thermoplastic resin. Carbon fiber reinforced thermoplastic resin composite material