JP2005133047A - Composite resin of aromatic polyetheretherketoneketone - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite resin composition of an aromatic polyetheretherketoneketone that has improved rigidity and improved mechanical strength such as retention of strength at an elevated temperature or the like and has electrical properties such as conductivity and antistatic properties without impairing inherent properties such as heat resistance, chemical resistance and the like possessed by an aromatic polyetheretherketoneketone. <P>SOLUTION: Rigidity and mechanical strength can be improved by adding a fibrous filler such as a glass fiber, a carbon fiber, a whisker or the like to the aromatic polyetheretherketoneketone. Particularly, the addition of a carbon nanotube as a fibrous filler can contribute to improved mechanical strength and electrical properties such as conductivity, antistatic properties and the like efficiently even though added in a small amount. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

Detailed Description of the Invention

Technical field belonging to the invention

The present invention relates to a composite resin composition comprising an aromatic polyetheretherketone ketone and a fibrous filler.
For more details,

1

(Wherein X is a direct bond,

2

,

Chemical 3

,

Or, it is a divalent aliphatic hydrocarbon group, Ar is a phenylene group, and n is an integer of 0 to 3. It is related with the composite resin composition which consists of the aromatic polyetheretherketone ketone and the fibrous filler which have a repeating unit represented by this.

  Said formula

1

Aromatic polyether ether ketone ketone resin having a repeating unit represented by the formula is promising as an engineering plastic having excellent heat resistance, flame retardancy, chemical resistance and the like for electric parts and automobile parts.

  Composite materials obtained by adding glass fiber, carbon fiber and reinforcing fiber fillers such as polyetherketone and polyetheretherketone are commercially available (for example, Victrex PEEK, 150GL130 brand is 30 A polyetheretherketone composite filled with glass fiber by weight%). A method for imparting conductivity by adding carbon fibrils to polycarbonate, polyphenylene ether, polyamide, polyester, etc. is described in JP-A-8-508534. However, the above formula

1

A composite resin comprising an aromatic polyetheretherketone ketone having a repeating unit represented by formula (I) and a fibrous filler such as glass fiber, carbon fiber, whisker, or carbon nanotube has not been developed yet.

Problems to be solved by the invention

  The present invention has improved mechanical strength such as rigidity and strength retention at high temperature without impairing the original properties such as heat resistance and chemical resistance of aromatic polyether ether ketone ketone, and also has conductivity and antistatic properties. It is an object of the present invention to provide a composite resin composition of an aromatic polyether ether ketone ketone having electrical properties such as properties.

Means for solving the problem

  As a result of intensive studies to solve the above problems, the present inventors can improve the rigidity and mechanical strength by adding a fibrous filler to the aromatic polyetheretherketone ketone, In addition, by adding carbon nanotubes that are fibrous fillers, it has been found that electrical properties such as electrical conductivity and antistatic properties can be efficiently imparted even with a small amount of improvement in mechanical strength. The present invention has been reached.

  That is, the following formula

1

(Wherein X is a direct bond,

2

,

Chemical 3

,

Or, it is a divalent aliphatic hydrocarbon group, Ar is a phenylene group, and n is an integer of 0 to 3. A composite resin composition comprising an aromatic polyetheretherketone ketone having a repeating unit represented by formula (II) and a fibrous filler is provided.

Hereinafter, the present invention will be described in detail.
The resin used in the present invention has the following formula:

1

(Wherein X is a direct bond,

2

,

Chemical 3

,

Or, it is a divalent aliphatic hydrocarbon group, Ar is a phenylene group, and n is an integer of 0 to 3. Aromatic polyether ether ketone ketone having a repeating unit represented by
The aromatic polyether ether ketone ketone used here can be produced by applying the methods described in Japanese Patent No. 1607984, Japanese Patent No. 2664180 and the like.

  Addition of a fibrous filler is effective in improving the rigidity and mechanical strength of aromatic polyether ether ketone ketone and imparting electrical conductivity.

  Examples of the fibrous filler used include glass fibers, carbon fibers, aramid fibers, potassium titanate whiskers, magnesium sulfate whiskers, aluminum borate whiskers, and carbon nanotubes. These fillers can be used alone or in combination.

The addition amount of the fibrous filler is preferably 1 to 70% by mass of the composite resin, and if it is less than 1% by mass, the reinforcement of the resin and the appearance of conductivity are unsatisfactory, and if it exceeds 70% by mass, the composite resin is melted. The fluidity of the resin becomes poor, making it difficult to mold, and the molded product becomes brittle.

  The amount of filler such as glass fiber, carbon fiber, aramid fiber, whisker or the like used mainly for the reinforcement of the resin is more preferably 5 to 70% by mass in view of the reinforcing effect. When these resin-reinforced composite resins with filler are used for melt molding such as injection molding and sheet molding, the amount of filler is suitably 5 to 40% by mass, and the filler content is 40% by mass. If it is more, the melt viscosity of the composite resin is high and it is difficult to obtain a satisfactory molded product. When the composite resin is subjected to compression molding or melt molding and used in a masterbatch that is diluted with the same resin and / or other thermoplastic resin, the composite resin containing 40 to 70% by mass filler is applied. I can do it.

On the other hand, the amount of carbon nanotubes added mainly to impart conductivity to the resin is wide, ranging from those requiring high conductivity to those having relatively low conductivity used for antistatic applications. There is a demand for composite resins, and 1 to 70% by mass is required. When a composite resin containing carbon nanotubes is used for melt molding such as injection molding and sheet molding, the amount of filler is suitably 1 to 40% by mass, and the filler content is more than 40% by mass. In addition, the composite resin has a high melt viscosity and it is difficult to obtain a satisfactory molded product.
When the composite resin is subjected to compression molding or melt molding and used in a masterbatch that is diluted with the same resin and / or other thermoplastic resin, the composite resin containing 40 to 70% by mass filler is applied. I can do it.

  Usually, when a fibrous filler is added to a resin to obtain a composite resin composition, the fibers are cut by shearing at the time of blending, and the length of the fibers becomes shorter than before the addition. For example, when glass fiber or carbon fiber having a fiber length of 1.5 to 6 mm is blended with a thermoplastic resin (polyamide, polyester, polycarbonate, etc.), the fiber length is about 500 μm or less. If the fiber length of the filler is too short, the effect of reinforcing the rigidity and mechanical strength of the resin is insufficient.

  In the composite resin containing a fibrous filler in the aromatic polyetheretherketone ketone of the present invention, the aspect ratio (fiber length / fiber diameter) of the filler in the composite resin must be 10 or more. It is.

The fiber length can be measured from a transmission microscope or electron microscope photograph. Specifically, a thin section is cut out from a composite resin molded article using a microtome, placed on a microscope or electron microscope data base, transmitted light is applied in the thickness direction of the section, and the section surface perpendicular to the thickness direction Take a photo of Multiple photos are taken at different locations on the section surface. Next, the length of all the fibers on the photograph taken is measured, and the number is counted. Of course, the length measured from the photograph is the projection length of the thin section of the fiber onto a predetermined plane, and does not indicate the absolute length of the fiber itself. Therefore, the “average fiber length” calculated by the following formula was used as an index.
Fiber length (“average fiber length”) = sum of all fiber lengths / number of all fibers

  The composite resin composition of the present invention is a molding method generally used for other thermoplastic resins, for example, injection molding, extrusion molding, hollow molding, sheet molding, rotational molding, thermoforming, compression molding, laminate molding, and the like. Applicable to the method.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example-1
Repeat unit

4

An aromatic polyether ether ketone ketone having a glass transition temperature of 158 ° C. and a melting temperature of 363 ° C., a potassium titanate whisker having a cross-sectional diameter of about 0.45 μm and an average fiber length of 20 μm (manufactured by Otsuka Chemical Co., Ltd. -D) is mixed with 40 parts by mass of the potassium titanate whisker to 60 parts by mass of the aromatic polyetheretherketone ketone, and the mixture is mixed at 400 ° C. with an extruder (Ikegai biaxial kneading extruder PCM-45). The mixture was melt-kneaded and extruded, and the strand was cooled and cut to obtain pellets.
The obtained pellets were injection molded (Sumitomo Nestal 47/28 injection molding machine, cylinder temperature 440 ° C., mold temperature 140 ° C.) to prepare test pieces for measuring various mechanical properties.
The test piece for measuring the mold shrinkage rate is a 64 × 64 × 3 mm flat plate, and the gate is prepared using a mold provided with a film gate having a thickness of 1 mm on one side of 64 mm.
Flexural strength and flexural modulus were measured according to ASTM D-790, HDT, and HDT after annealing (thermal deformation temperature) according to ASTM D-618.
In addition, these mechanical properties are neat polymer (natural) and repeating units of aromatic polyetheretherketone ketone as raw materials.

5

The physical properties of the neat polymer of the aromatic polyether ketone (Victrex PEEK-HT) represented by the present invention and the composite resin of the present invention were compared,

Table 1

Summarized in

Table 1

As can be seen from the above, the mechanical properties of the composite resin of the present invention are less than 1/3 of the molding shrinkage compared to the neat polymers of aromatic polyether ether ketone ketone and aromatic polyether ketone, It was found that strength, flexural modulus, and HDT before and after annealing were significantly improved. The annealing condition in this example is 230 ° C. × 2 hours.

Example-2
Repeat unit

4

An aromatic polyether ether ketone ketone (manufactured by Yoshida High Materials Co., Ltd.) having a glass transition temperature of 158 ° C. and a melting temperature of 363 ° C. and a glass fiber (manufactured by Asahi Fiber Glass Co., Ltd.) and a cross section Potassium titanate whisker having a diameter of about 0.2 μm and an average fiber length of 20 μm (Tismo-D, manufactured by Otsuka Chemical Co., Ltd.), the aromatic polyether ether ketone ketone, glass fiber, and potassium titanate whisker in a mass% of 40:50: The mixture was mixed at a ratio of 10, and the mixture was melt-kneaded at 400 ° C. with an extruder (Ikegai twin-screw kneading extruder PCM-45) and extruded, and the strand was cooled with water and cut to obtain pellets.
A test piece for measuring the mechanical properties of the obtained pellets was prepared in the same manner as in Example 1, and the mechanical properties were measured while comparing with the neat polymer of the aromatic polyether ether ketone ketone which is the raw material of the present invention. ,

Table 2

Summarized in

Table 2

As can be seen, the composite resin of the present invention has a small absolute value of molding shrinkage, exhibits good moldability, and has high bending strength and bending elastic modulus.
Further, since the composite resin of the present invention has an extremely high heat deformation temperature, it can be used in a wide temperature range, and it can be seen that it is an excellent molding material as a precision machine part.

Example-3
Repeat unit

4

A structure in which a multilayer of graphite is rolled up with a cylindrical substance composed of 100% carbon atoms on an aromatic polyether ether ketone ketone having a glass transition temperature of 158 ° C. and a melting temperature of 363 ° C. 7% by mass of fine fibrous material, so-called carbon nanotube (diameter 0.01 μm (10 nm), length 1 to 10 μm, 5 nm hollow core with 8 layers of graphite layers) (93/7% by mass) was mixed, and the mixture was melt-kneaded at 400 ° C. with a twin-screw kneading extruder (Ikegai PCM-45), and then the strand was cooled with water and cut to obtain pellets.
A test piece was prepared from the obtained pellets in the same manner as in Example 1, and mechanical properties and electrical characteristics were measured.

Table 3

Summarized in

Table 3

According to the present invention, the composite resin kneaded with the carbon nanotubes does not deteriorate the physical properties of the aromatic polyether ether ketone ketone, and can impart conductivity to the insulating resin by adding a small amount of carbon nanotubes. The heat-resistant composite resin of the present invention can be used in a wide range of applications.

The invention's effect

  The composite resin comprising the aromatic ether ether ketone ketone and the fibrous filler of the present invention is excellent in mechanical strength, heat resistance and impact strength, and the composite resin added with carbon nanotubes is the aromatic polyether ether ketone ketone. Since electrical conductivity and antistatic performance can be realized without impairing physical properties, the industrial utility is great, and it can be used in a wide range of fields.

Claims (8)

The following formula

(In the formula, X is a direct bond, embedded image

Or, it is a divalent aliphatic hydrocarbon group, Ar is a phenylene group, and n is an integer of 0 to 3. A composite resin composition comprising an aromatic polyether ether ketone ketone having a repeating unit represented by formula (1) and 1 to 70 mass% of a fibrous filler.   The composite resin composition according to claim 1, wherein the fibrous filler has an aspect ratio of 10 or more.   The fibrous filler is one or more fillers selected from glass fiber, carbon fiber, aramid fiber, whisker and carbon nanotube, and the total content thereof is in the range of 1 to 70% by mass. 3. A composite resin composition according to item 2.   The composite resin composition according to claim 2, wherein the fibrous filler is glass fiber and the content thereof is in the range of 5 to 70 mass%.   The composite resin composition according to claim 2, wherein the fibrous filler is carbon fiber and the content thereof is in the range of 5 to 70 mass%.   The composite resin composition according to claim 1, wherein the fibrous filler is an aramid fiber and the content thereof is in the range of 5 to 70 mass%.   The composite resin composition according to claim 2, wherein the fibrous filler is a whisker and the content thereof is in the range of 5 to 70 mass%.   The composite resin composition according to claim 2, wherein the fibrous filler is a carbon nanotube and the content thereof is in the range of 1 to 70 mass%.